Journal of Hazardous Materials 252–253 (2013) 428–461

Contents lists available at SciVerse ScienceDirect

Journal of Hazardous Materials

journal homepage: www.elsevier.com/locate/jhazmat

Review

A review on zinc and nickel adsorption on natural and modified

zeolite, bentonite and vermiculite: Examination of process
parameters, kinetics and isotherms
S. Malamis a,b,∗ , E. Katsou a,b
a
School of Chemical Engineering, National Technical University of Athens, 9 Iroon Polytechniou St., Zographou Campus, 15773, Athens, Greece
b
Department of Biotechnology, University of Verona, Strada Le Grazie 15, 37134, Verona, Italy

h i g h l i g h t s

• Important parameters: sorbate and sorbent type and concentration, pH, ionic strength.
• Presence of competing ions adversely impacts on process.
• Variability in nickel and zinc removal due to parameters variation.
• Langmuir is the isotherm that best suits data in most cases.

a r t i c l e i n f o a b s t r a c t

Article history: Adsorption and ion exchange can be effectively employed for the treatment of metal-contaminated
Received 7 January 2012 wastewater streams. The use of low-cost materials as sorbents increases the competitive advantage of
Received in revised form 22 February 2013 the process. Natural and modified minerals have been extensively employed for the removal of nickel
Accepted 11 March 2013
and zinc from water and wastewater. This work critically reviews existing knowledge and research on
Available online xxx
the uptake of nickel and zinc by natural and modified zeolite, bentonite and vermiculite. It focuses on the
examination of different parameters affecting the process, system kinetics and equilibrium conditions.
Keywords:
The process parameters under investigation are the initial metal concentration, ionic strength, solution
Zinc
Nickel pH, adsorbent type, grain size and concentration, temperature, agitation speed, presence of competing
Adsorption ions in the solution and type of adsorbate. The system’s performance is evaluated with respect to the
Ion exchange overall metal removal and the adsorption capacity. Furthermore, research works comparing the process
Minerals kinetics with existing reaction kinetic and diffusion models are reviewed as well as works examining the
Kinetics performance of isotherm models against the experimental equilibrium data.
Equilibrium studies © 2013 Published by Elsevier B.V.
Process parameters

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 429
2. Metal removal mechanisms . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 429
3. Mineral characteristics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 430
4. Parameters impacting on adsorption . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 430
4.1. Initial metal concentration . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 430
4.2. Liquid medium . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 431
4.3. Solution pH . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 432
4.4. Temperature and thermodynamics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 434
4.5. Adsorbent grain size . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 436
4.6. Adsorbent concentration . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 437
4.7. Adsorbent type . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 437

∗ Corresponding author at: School of Chemical Engineering, National Technical University of Athens, 9 Iroon Polytechniou St., Zographou Campus, 15773, Athens, Greece.
Tel.: +30 210 7723108; fax: +30 210 7723285.
E-mail addresses: malamis.simos@gmail.com (S. Malamis), ekatsou@yahoo.gr (E. Katsou).

0304-3894/$ – see front matter © 2013 Published by Elsevier B.V.

http://dx.doi.org/10.1016/j.jhazmat.2013.03.024
 S. Malamis, E. Katsou / Journal of Hazardous Materials 252–253 (2013) 428–461 429

4.8. Competitive adsorption . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 438

4.9. Ionic strength . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 442
4.10. Agitation speed . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 443
4.11. Evaluation of parameters . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 443
5. Removal efficiencies . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 444
6. Kinetics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 444
7. Isotherms . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 452
8. Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 456
Nomenclature . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 456
Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 457
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 457

1. Introduction applications, adsorption and ion exchange can be grouped together

as sorption for a unified consideration.
Intense industrial activity results in the contamination of waste-
water with several heavy metals, including zinc and nickel. The 2. Metal removal mechanisms
extensive use of nickel and zinc in industry means that consider-
able amounts of these metals can find their way into the aquatic To investigate the suitability of an adsorbent, it is necessary
environment. Nickel is employed in several industrial activities, to characterize its porous structure and its surface composition
including mineral processing, electroplating, production of paints which consists of several functional groups. Adsorption of metals
and batteries, manufacturing of sulphate and porcelain enamelling on the active sites results in the formation of outer and inner-
[1–3]. Zinc is released into the aquatic environment through several sphere complexes. Outer-sphere complexes occur if at least one
industrial activities, such as mining, metal coating, battery produc- water molecule is interposed between the surface functional group
tion and its use in paints, ceramics, wood, fabrics, drugs, sun blocks and the bound ion. On the contrary, inner-sphere complexes occur
and deodorants [4–6]. Human exposure to these heavy metals at when water molecules are not interposed between the bound ion
significant levels is associated with serious health effects. Nickel and the functional group of the adsorbent and the sorbate forms a
is associated with dermatitis, nausea, coughing, chronic bronchi- direct coordinate-covalent bond with surface functional groups on
tis, gastrointestinal distress, reduced lung function and lung cancer the variable charge surface [19]. Specific adsorption involves the
[3,7–9]. Zinc is associated with short-term “metal-fume fever”, nau- formation of inner-sphere complexes, while non-specific adsorp-
sea, diarrhoea, depression, lethargy, and neurological signs, such as tion involves the formation of weaker outer-sphere complexes.
seizures and ataxia [7–9]. Consequently, there is a need to effec- Outer-sphere complexes are formed through electrostatic interac-
tively remove these metals from wastewater in order to ensure tions between metal cations and the negatively charged centres.
adequately treated effluent quality for various uses. Several pro- Therefore, metal binding takes place through ion exchange at the
cesses are available for the removal of heavy metals from water planar sites of the adsorbent [26,27]. At the earlier adsorption
and wastewater including chemical precipitation, adsorption, ion stages, outer-sphere complexes are formed at the external sur-
exchange, flotation, membrane filtration, electrochemical treat- face sites. As metal concentration increases, metal ions are forced
ment and coagulation–flocculation. The advantages and disadvan- into internal surface sites forming also inner-sphere complexes.
tages of each process have been summarized by O’Connell et al. [10]. These complexes are more stable compared to the outer-sphere
Adsorption and ion exchange processes can be used for the complexes due to the formation of covalent bonds or combinations
removal of heavy metals from wastewater. The competitive advan- of covalent and ionic bonding. During their formation, protons are
tage of such processes can increase when low-cost sorbents/ion released and the process causes a total decrease in solution pH.
exchangers are used. A wide variety of heavy metals can be removed The type of surface complexes affects the rate and the reversibil-
from the liquid phase at significant quantities and kinetics are ity of the adsorption. Outer-sphere complexation is usually rapid
usually fast. The drawbacks are that the performance depends and reversible, while inner-sphere complexation is slower and may
on sorbent’s selectivity towards the metal, while in many cases be irreversible [28]. Inner-sphere complexation is influenced by the
pre-treatment is required to improve its adsorption capacity [10]. ionic strength of the solution. Outer-sphere complexation is partic-
Various natural minerals have been applied for the removal of ularly influenced by pH, since at pH < 4 most silanol and aluminol
nickel and zinc. In many cases these minerals have been chem- groups on the edges are protonated and thus metal adsorption
ically and/or thermally modified to increase the metal uptake. decreases [26,29]. Also, the metals can be transferred from the bulk
Also, in some cases a mixture of minerals with other sorbents is solution to the solid phase due to precipitation on the mineral’s
employed to treat wastewater [11]. Some reviews summarize the surface. Mineral addition in electrolyte solution can reduce metal
work conducted on the removal of heavy metals by different sor- solubility and enhance metal precipitation on the mineral surface
bents [12–19]. Certain reviews have focused on the examination even in a non-saturated environment. At low surface coverage com-
of kinetics and others on equilibrium [20–25]. Nevertheless, the plexation tends to dominate. As the surface coverage increases
uptake of zinc and nickel by natural and modified minerals has nucleation occurs and results in the formation of distinct entities or
not been adequately summarized. The present work aims to crit- aggregates on the surface; as loading increases further, surface pre-
ically review information concerning the factors that impact the cipitation becomes the dominant mechanism [6,28]. Precipitation
adsorption and ion exchange, the system kinetics and equilibrium mostly depends on solution pH and initial metal concentration [14].
with respect to various models that have been applied in the liter- Moreover, co-precipitation of metals may play an important role in
ature. Much of the information summarized in this work has been the surface precipitation mechanism, where the metal is drifted
tabulated; this way it is easy to compare the experimental condi- from another metal that is contained in high concentration in the
tions and results of various works. Since both ion exchange and solution [30]. Surface precipitation is favoured by the pH increase.
adsorption are usually involved in the uptake of heavy metals by Hence, the addition of minerals that significantly increases the pH
minerals, in the context of this work hereafter the term adsorp- enhances metal removal from the bulk solution [14,19]. Precipita-
tion also includes the ion exchange that takes places. In practical tion is a much slower process than complex formation [31].
430 S. Malamis, E. Katsou / Journal of Hazardous Materials 252–253 (2013) 428–461
3. Mineral characteristics
Zeolites are natural, hydrated aluminosilicate minerals with
crystalline microporous structure and belong to the mineral type of
‘tectosilicates’. The zeolite structure consists of three-dimensional
frameworks of SiO4 and AlO4 that are linked to each other by
sharing oxygen atoms. The replacement of tetravalent silicon by
trivalent aluminium in the mineral’s structure creates a net neg-
ative charge that is counterbalanced by the presence of cations
(usually Ca2+ , Na+ and K+ ) which are situated in cavities [32,33].
These cations are exchangeable with other cations including heavy
metals. The zeolite’s framework structure encloses cavities occu-
pied by large ions and water molecules which are able to move,
allowing ion exchange. Zeolites can be classified by considering the
topology of the framework. Zeolites having the same topology con-
stitute a zeolite framework type. Currently there are 206 known
framework types recognized by the Structure Commission of the
International Zeolite Association [33]. An important feature is the
effective width of the channels which determines the accessibility
of the channels to incoming cations. Zeolite channels are formed by
different combinations of linked rings of tetrahedra. The channels
that are wider at their narrowest parts can receive larger cations
into their structure [32].
Bentonite is an aluminium phyllosilicate (clay) consisting
mostly of montmorillonite. The main characteristic of montmoril-
lonite is its ability to absorb water molecules between its sheets,
resulting in a significant expansion [34]. The crystal structure of
montmorillonite is composed of two layers of silica tetrahedra with
a central layer of alumina octahedron between them [30]. The tetra-
hedral and octahedral sheets are combined in such a way that the
tips of the tetrahedra of each silica sheet and one of the hydroxyl
layers of the octahedral sheet form a common layer [35]. The dis-
tance between the layers is not fixed since the layers can expand.
Due to its layered structure the mineral is characterized by internal
(i.e. interlayer) and external surfaces (i.e. edge). Different exchange-
able cations can replace the ions in the montmorillonite structure.
In particular, in the tetrahedral sheets the tetravalent silicon can
be replaced by trivalent aluminium, while in the octahedral sheets
the aluminium can be substituted by other ions such as divalent
magnesium. As a result, the layer charge becomes negative and
is mostly neutralized by hydrated cations in the interlayer space.
These cations are bonded by electrostatic forces to the internal
surfaces and can be exchanged with other cations [30].
Vermiculite is a type of clay that is usually found in nature in its
magnesium form. It is composed of two layers of silicon tetrahedra,
in which silicon is partially replaced by aluminium, and a layer of
OH− groups and magnesium ions, forming a strongly bound mica
stack. A hydrated layer is located between the stacks consisting
of divalent metals. Thus, the two layers are bonded together by
one octahedral layer and the structure is commonly referred to as
2:1 phyllosilicate [36,37]. The mineral’s structural analysis shows
that the water molecule sites form a distorted hexagonal arrange-
ment with each site being linked to single oxygen on the silicate
layer surface. The magnesium ions lie between the water sheets
and are octahedrally coordinated with the water molecules [38].
When tetravalent silicon is replaced by trivalent aluminium in the
tetrahedral layer of the vermiculite sheet, a negative charge is gen-
erated on the layer which is counterbalanced by interlayer cations;
in the case of vermiculite these are mainly magnesium cations that
are easily exchanged with other cationic species [32,39].
4. Parameters impacting on adsorption
The mineral’s adsorption capacity and the system’s kinet-
ics for metal uptake from the liquid phase depends on several
physicochemical factors related to the sorbate, the sorbent, and
the liquid phase characteristics including the solution pH, initial
metal concentration in the solution, presence of other cations, ionic
strength, temperature, type of the liquid phase, mineral type, grain
size and concentration, type of sorbent pre-treatment and agitation
speed.
4.1. Initial metal concentration
The initial metal concentration in the liquid phase significantly
affects the adsorption process. The impact depends on several
parameters, such as the type of metal and the liquid medium, the
presence of competing cations, the availability of the functional
groups on the adsorbent’s surface and the ability of these groups to
bind metal ions. In most cases, the increase of the initial metal con-
centration results in an increase in the amount of metal adsorbed
per unit mass of adsorbent until a plateau is reached and in a
decrease in the overall removal efficiency [40–43].
At low initial metal concentrations the ratio of metal cations
to adsorbent mass is low and thus adsorption does not depend on
initial concentration [44,45]. Increasing the initial concentration
means that more metals are available and thus, more metal ions
are adsorbed for constant adsorbent mass. At higher initial metal
concentrations the driving force to overcome the mass transfer
resistance for the migration of the metals from the bulk solution
to the mineral surface increases [9]. However, each unit mass of
adsorbent is subjected to a larger number of metal cations, which
gradually fill up the sites until saturation is reached. In such a
case, further increase of metal concentrations is not accompanied
with an increase in the amount of metal adsorbed per unit mass
of adsorbent. The determination of the maximum metal concen-
tration where total saturation of the adsorbent occurs is important
for practical applications. Furthermore, the level of surface precip-
itation strongly depends on the initial metal concentration. At low
metal concentrations, the adsorbent surface coverage is low and
the formation of surface complexes is the main mechanism. The
increase of metal concentration favours the concentration of com-
pounds and aggregates on mineral surface. A further increase in
metal concentration results in saturation of adsorption sites and
surface precipitation is the main uptake mechanism [46]. The sat-
uration of active sites is usually faster in the cases where minerals
exhibit low selectivity for a metal. However, this is not always the
fact, since the metal complexes formed or entrapped in the min-
eral’s surface may accelerate the surface saturation even at low
concentrations of metals that present high affinity for the specific
mineral.
Several studies have documented the effect of initial metal
concentration on metal uptake by minerals as shown in Table 1
[40,42,44,47–65]. In most cases the increase of initial concentration
resulted in an increase of the adsorption capacity and a decrease
of the overall removal efficiency. Ijagbemi et al. [42] examined
the adsorption of nickel on montmorillonite and found that the
adsorption capacity increased with increasing metal concentration,
while after a certain concentration a plateau was reached. Çoruh
and Ergun [40] found that by increasing the initial nickel concen-
tration the equilibrium solid phase concentration (qe ) increased
for both natural and chemically modified clinoptilolite, while the
removal efficiency decreased. The latter has also been reported for
the adsorption of nickel on montmorillonite [44,47], on natural
zeolite [48] and on calcined Bofe bentonite [49].
A similar picture was obtained for zinc adsorption on natural
and modified minerals. Erdem et al. [62] examined the adsorption
of Zn2+ on natural zeolite for varying initial metal concentration
and found that the adsorption efficiency decreased with increasing
metal concentration. Kaya and Ören [58] found that the increase of
zinc initial concentration in the solution resulted in an increase of
 S. Malamis, E. Katsou / Journal of Hazardous Materials 252–253 (2013) 428–461 431

Table 1
Studies on the effect of initial zinc and nickel concentration (C0 ) on the adsorption process.

Metal Mineral C0 range C0 for which highest C0 for which highest Reference
(mg L−1 ) adsorption is obtained (mg L−1 ) (%) removal occurs
(mg L−1 )

Ni Clinoptilolite 12.5–200 200 12.5 [40]

NaCl clinoptilolite
HCl and NaCl clinoptilolite
Ni Montmorillonite 50–300 200–300 [42]
Ni Montmorillonite 10–60 60 10 [44,47]
ZrO-montmorillonite
TBA-montmorillinite
Ni Natural zeolite 1–100 100 [48]
Ni Calcined Bofe bentonite 100–400 100 [49]
Nia Clinoptilolite 1–30 10 [50,51]
Chabazite
Ni Clinoptilolite 10–800 10 [52]
Nia Jordanian zeolite 50–400 400 [53]
(phillipsite) tuff
Nia Clinoptilolite 50–3000 10 [54]
Ni Zeolite 5.87, 31.69, 5.87 [55]
61.63
Ni Na-montmorillonite 50–100 100 50 [56]
Acid modified montmorillonite 75
a
Zn Clinoptilolite 1–30 10 [50,51]
Chabazite
Zna Clinoptilolite 50–3000 10 [54]
Zn Zeolite 6.54, 30.73, 6.54 [55]
63.42
Zn Vermiculite 25–500 500 25 [57]
Zn Natural bentonite 1–200 ∼60–200 [58]
Na-bentonite ∼80–200
Zn Natural zeolite 37.27–659.03 32.27 [59]
Zn Gordes zeolite 1–20 14 (14–20) [60]
Bigadic zeolite 14 (14–20)
Zn Cankiri bentonite 20–160 ∼80–160 [61]
Zn Zeolite 50–400 50 [62]
Zn Bentonite 30–50 50 [63]
Zn Zeolite 5–20 20 [64]
Zn Turkish zeolite 78.59–1012.78 5.63–78.59 [65]
a
Mixed metal solution.

qe on natural bentonite and Na-bentonite up to a certain point and
thereafter remained almost constant. A similar trend was observed
by Ören and Kaya [60] for zinc uptake by Gordes and Bigadic zeo-
lite. Veli and Alyüz [61] studied the adsorption of zinc on Cankiri
bentonite and reported that adsorption increased up to a certain
level, and thereafter remained stable with further concentration
increase. Perić et al. [59] reported that the increase of initial zinc
concentration resulted in a decrease of metal adsorption on natural
zeolite. Wu et al. [57] reported that the increase of initial zinc con-
centration led to an increase of qe of vermiculite and a reduction
of the removal efficiency. Increased removal efficiencies at low ini-
tial metal concentrations have also been reported by Erdem et al.
[62] and Cabrera et al. [55]. Ouki and Kavannagh [50,51] studied
the adsorption of nickel and zinc on chabazite and found that the
maximum removal efficiency occurred at the medium range of the
initial metal concentrations.
4.2. Liquid medium
The prediction of metals adsorption on minerals in aqueous
solutions may not reflect the true mineral behaviour when complex
liquids are treated. Thus, adsorption must be evaluated in the liquid
where the adsorption process actually takes place [66]. The pres-
ence of ligands in wastewater may enhance or suppress adsorption,
depending on the ligand, the adsorbent and the metal [67]. The
mineral’s performance is usually lower in wastewater compared to
aqueous solutions, due to the:
• presence of competing ions in wastewater for which minerals
may exhibit higher selectivity [68,69],
• adsorption of metals on suspended solids contained in wastewa-
ter and/or metals precipitation [70,71]; this reduces the soluble
metal concentration available for mineral adsorption
• formation of soluble, stable complexes that are not adsorbed on
the mineral’s surface [27]. In this case the formation of solu-
ble complexes becomes competitive to surface complexation and
metal adsorption decreases [28,72] due to the hindrance of metals
to reach the active sites and/or to the capturing of adsorption sites
by ligands [73].
In some other cases, the presence of ligands may enhance
adsorption through the [26,27]:
• formation of negatively charged complexes between the ligands
and the metals, which interact with positively charged, mineral
surface sites,
• complexation of metals with ligands that bond to the mineral
surface,
• outer-sphere complexation between metal ions and negatively
charged ligand–surface complexes,
• formation of positively charged metal–ligand complexes, which
are ion exchanged with the mineral’s cations,
• accumulation of negatively charged ligands in the double layer
of positively charged particles, which reduces the electrostatic
repulsion between metals and the surface.

• competition among ligands and metals for the available mineral Malandrino et al. [27] studied the impact of ligands on heavy
surface sites, metal adsorption for vermiculite and concluded that ligands having
432 S. Malamis, E. Katsou / Journal of Hazardous Materials 252–253 (2013) 428–461
high complexation constants resulted in significant reduction of
the mineral’s adsorption capacity. Abollino et al. [74] found that
the presence of ligands in solutions influenced the adsorption
of heavy metals on Na-montmorillonite due to the formation of
metal–ligand complexes that hinder adsorption. Abollino et al. [26]
concluded that ligands and their concentration were more criti-
cal to the adsorption process than the type of clay. The presence
of anions may affect the metal adsorption due to: the formation
of metal complexes that exhibit higher affinity for the adsorbent
than the free metals forms; binding of metals with anions form-
ing soluble substances that remain in the liquid phase and cannot
be adsorbed by the minerals; interaction of anions with the min-
eral, changing the state of the active sites [75,76]. Yang et al. [68]
examined the effect of Cl− , NO3 − and ClO4 − on nickel adsorption on
bentonite from aqueous solutions and concluded that their impact
was negligible. The low removal of Ni, Hg, Cu, Fe3+ and Cr3+ was
attributed to the presence of SO4 2− , HPO4 2− and NO3 − that form
stable complexes with metal ions and decrease adsorption [77–79].
The decrease in metal adsorption on bentonite due to the increase in
the concentration of NaCl and CaCl2 has also been documented. The
formation of stable metal complexes decreases adsorption. Also,
the competition of Na+ and Ca2+ with heavy metals for active sites
may decrease heavy metal uptake [80].
Álvarez-Ayuso et al. [81] used natural and synthetic zeo-
lite (NaP1) to treat electroplating wastewater. Synthetic zeolite
effectively treated acid zinc and nickel electroplating process
wastewater. However, synthetic zeolite performed poorly when it
treated zinc cyanide electroplating wastewater; this is attributed
to the formation of complexes between Zn2+ and CN− . Álvarez-
Ayuso and García-Sánchez [82] found that the performance of
Na-bentonite for Zn removal from acid electroplating effluents
decreased by 10% compared to that obtained for the treatment
of synthetic solutions, while the capacity of Na-bentonite for Zn
uptake from cyanide-containing wastewater was very low, due
to the formation of stable Zn(CN)4 2− complexes and the low
selectivity of the mineral for these complexes. On the contrary,
Na-bentonite exhibited similar efficiency for Ni uptake from syn-
thetic solutions and Ni-electroplating effluents. In another study,
Álvarez-Ayuso and García-Sánchez [83] employed natural vermic-
ulite in columns to treat wastewater originating from a nickel
electroplating process and achieved similar purification levels to
those obtained for the treatment of synthetic solutions. Pitcher
et al. [84] found that the performance of synthetic zeolite for the
removal of Zn from synthetic solutions and motorway stormwa-
ter containing Zn, Cd, Pb and Cu was similar, while zinc uptake
by natural zeolite (modernite) from motorway stormwater was
lower compared to that obtained for synthetic solutions. The lat-
ter was attributed to the presence of dissolved contaminants in
Fig. 1. (a) Zn and (b) Ni speciation as a function of pH in dilute aqueous solutions, T = 25 ◦ C [88,89].
motorway stormwater. Katsou et al. [85] investigated the removal
of nickel, zinc, lead and copper from multi-metal wastewater using
aluminosilicate minerals combined with ultrafiltration membranes
and found that although the overall metal removal obtained was
higher in wastewater compared to aqueous solutions, the adsorp-
tion capacity of minerals was lower. This was mainly attributed
to the formation of particulate metal forms that limited the liquid
phase metal concentration available for the adsorption process, but
were successfully retained by the membranes. Researchers have
also studied nickel and zinc removal from wastewater using natu-
ral and Na-modified bentonite [82], vermiculite [83], acid-alkaline,
physically and chemically modified clay containing montmoril-
lonite and hydromica [86], natural and modified zeolite [87].
4.3. Solution pH
It is well recognized that the pH is an important parameter
impacting on the adsorption process. Fig. 1, shows the different
species of zinc and nickel in aqueous solutions. At pH < 6 the Ni2+
and Zn2+ forms of nickel and zinc dominate [88,89]. The solution pH
significantly affects the ionisation degree, the metal chemistry and
the mineral’s surface properties [6,90–92]; it impacts on the extent
of metal precipitation and the type of complexes formed between
the ligands and metals. It is one of the most important parameters
influencing not only site dissociation, but also the solution chem-
istry of the heavy metals since hydrolysis, complexation by organic
and/or inorganic ligands, redox reactions, precipitation and avail-
ability of heavy metals are all influenced by it [93,94]. The different
metal species dominating in the solution at various pH differ in
their charge and ability to adsorb on the mineral.
The activity of the adsorbent’s functional groups is strongly
affected by solution pH. The point of zero charge pH (pHpzc ) is the
pH of the solution at which the overall observed charge on the sur-
face of the mineral is zero. At pH < pHpzc , the functional groups are
protonated and the positively charged surfaces dominate. In this
case, the attraction of negatively charged ions is possible to occur. In
highly acidic environment, several functional groups become pro-
tonated and act as positively charged species, resulting in reduced
attraction between the metals and the minerals. Deprotonation of
functional groups occurs at increasing pH and these behave as neg-
atively charged moieties, attracting heavy metals [3,95]. However,
at alkaline environment, the solubility of metals decreases allowing
precipitation, which may complicate the sorption process [45]. Pre-
cipitation occurring at alkaline environment masks the true extent
of metal sorption on minerals; this is why it is important when
the mineral behaviour is examined at high pH values to deter-
mine the soluble metal concentration prior to the addition of the
mineral.
 S. Malamis, E. Katsou / Journal of Hazardous Materials 252–253 (2013) 428–461 433

Table 2 [11,26,40,42,44,47–57,60,61,63,68,81–83,92,96–108] maximum removal due to adsorption is in some cases reported

summarizes the effect of pH on adsorption of nickel and zinc on zeo- to be higher than 8, this also includes precipitation that occurs
lite, bentonite and vermiculite. In all studies, the lowest adsorption at such basic pH values. Argun [98] found that the optimal solu-
occurred at acidic environment (pH ≤ 3), while the highest adsorp- tion pH for adsorption of Ni2+ on natural zeolite was 6, while at
tion was usually observed in the pH range of 5.0–8.0. Although the an acidic environment the performance of clinoptilolite reduced

Table 2
Studies showing the effect of pH on the adsorption of nickel and zinc on zeolite, bentonite and vermiculite.

Metal Mineral Examined pH range pH of highest pH of lowest Reference

adsorption adsorption

Ni Vermiculite 2.5–8.0 8.0 2.5 [26]

Montmorillonite 3.5–8.0 3.0
Ni Clinoptilolite 3–9 7–8 3 [40]
NaCl clinoptilolite
HCl and NaCl clinoptilolite
Ni Montmorillonite 2.5–9.0 6.0–8.0 2.5 [42]
Ni Montmorillonite 1–10 10 1 [44]
Ni Montmorillonite 1 [47]
ZrO-montmorillonite 1–10 10
TBA-montmorillinite
Ni Zeolite 1–10 6 1–2 [48]
Ni Zeolitea 3–6 4 3 [50,51]
Ni Chabazitea 3–6 5 3, 6 [50,51]
Ni Clinoptilolite 3.4–7.5 7.5 3.4 [52]
Ni Jordanian zeolite tuff 2.5–4.5 4.0 2.5 [53]
(phillipsite)
Ni Clinoptilolitea 1–5 4 1 [54]
Ni Zeolite ∼2.3–7.8 ∼2.3 ∼7.8 [55]
∼2.5–7.9 ∼2.5 ∼7.9
Ni Na-montmorillonite 3–9.3 9.3 3 [56]
Acid modified montmorillonite
Ni GMZ Na-bentonite 2–12 ≈8.5 2 [68]
Ni Synthetic zeolite 3–6 4–6 3 [81]
Ni Na-bentonite 3–6 6 3 [82]
Ni Natural vermiculite 3–6 6 3 [83]
Ni Zeolite 4A 3, 4 4 3 [92]
Ni Zeolite 3–9 4–7 3 [96]
Bentonite
Vermiculite
Ni Clinoptilolite 2–9 6–8 2 [98]
Ni Chitosan-clinoptilolite 2.0–6.0 5.0 2.0 [99]
composite
Ni Natural bentonite 1–5 3 1 [100]
Ni Na-bentonite 2–9 6–8 2 [101]
Ni Na-montmorillonite 3–9 9 3 [102]
Ni Vermiculite 1.2–9.0 5.2–9.0 1.2 [103]
Zn Zeolite–Portland cement 3–8 6.0 3.0 [11]
mixture
Zn Vermiculite 2.5–8.0 7.0–8.0 2.5 [26]
Montmorillonite 3.5–8.0 3.0
Zn Bentonite 2–10 6 2 [49]
Zn Clinoptilolitea 3–6 4–5 3 [50,51]
Zn Chabazitea 3–6 4–5 6 [50,51]
Zn Clinoptilolitea 1–5 1 5 [54]
Zn Zeolite ∼2.3–7.2 ∼7.2 ∼2.3 [55]
Zn Vermiculite 1.3–6.3 4.4–6.3 1.3 [57]
Zn Gordes zeolite 3–8 4–6 3 [60]
Bigadic zeolite 6
Zn Cankiri bentonite 2–10 8 2 [61]
Zn Bentonite 3.81–7.69 6.76 3.81 [63]
Zn Synthetic zeolite 3–6 6 3 [81]
Zn Na-bentonite 3–6 6 3 [82]
Zn Zeolite 4A 3, 4 4 3 [92]
Zn Zeolite 4–9 6–7 4 [97]
Bentonite
Vermiculite
Zn Zeolite 2–7 7 2 [104]
Zn Zeolite 4A 1–8 6.0 1.0 [105]
Zeolite 13X
Bentonite
Zn Natural bentonite 2–9 3 [106]
Composite E20 bentonite 5–6 2
Composite A85 bentonite 2
Zn Na-dodecylsulphate 1.5–3.5 ≈3.3 1.5 [107]
montmorillonite
Zn Bentonite <3–10 6 <3 [108]
a
Multi-metal solution.
434 S. Malamis, E. Katsou / Journal of Hazardous Materials 252–253 (2013) 428–461
due to the presence of protons that competed with nickel ions for
the available adsorption sites. Precipitation was observed at pH
higher than 8. Ijagbemi et al. [42] reported similar findings for nickel
adsorption on montmorillonite. In another study, Ijagbemi et al.
[56] stated that the increasing adsorption on Na-montmorillonite
and acid modified montmorillonite that was observed when the
solution pH increased, was attributed to the lower concentration of
H3 O+ since more sites became available to nickel ions. The authors
also mention that surface complexation significantly contributed
to the adsorption process; the latter could explain the dependence
of adsorption on solution pH. Çoruh and Ergun [40] found that
the highest adoption capacity of natural and modified clinoptilo-
lite occurred at the pH range of 7–8, while the adsorption was
also high and stable at the pH range of 4–6. Sprynskyy et al. [52]
reported that the optimal pH for adsorption of nickel on clinoptilo-
lite was 7.5, while the lowest performance was obtained at pH 3.4
due to competition with hydrogen ions. Song et al. [102] reported
a gradual increase of sorption of Ni2+ on Na-montmorillonite as
the pH increased from 3 to 9. However, at pH 9, precipitation sig-
nificantly contributed to nickel removal, masking the true metal
adsorption. Yang et al. [68] concluded that at pH < 8, the sorption
of nickel on GMZ Na-bentonite was dominated by ion exchange
while at pH > 8 inner-sphere surface complexation was the dom-
inant uptake mechanism. Katsou et al. [96] found that at the pH
range of 4–7 the removal of nickel due to adsorption on ben-
tonite, zeolite and vermiculite was stable, while the highest nickel
removal obtained at pH ≥ 8 was mainly attributed to precipita-
tion. Kocaoba et al. [48] obtained the maximum adsorption for
nickel on zeolite at pH ≥ 6, but the authors mention that at the
alkaline region the true adsorption capacity was lower since pre-
cipitation also occurred. Cabrera et al. [55] also reported that the
highest adsorption of nickel on zeolite was obtained at pH close to 8,
with highly acidic environment resulting in the lowest adsorption.
Ouki and Kavannagh [50,51] found that the lowest nickel adsorp-
tion on chabazite occurred at the lowest and highest pH (i.e. 3
and 6), while for clinoptilolite the lowest adsorption occurred at
acidic environment. Da Fonseca et al. [103] found that the max-
imum amount of Ni2+ adsorbed on vermiculite was observed at
pH 5.2–9.0. However, at pH 9 significant amount of nickel was
removed through the formation of precipitates. Gupta and Bhat-
tacharyya [44,47] observed a gradual increase of Ni2+ on natural
montmorillonite, poly(hydroxyl-zirconium) modified montmoril-
lonite and TBA-montmorillonite up to pH 8.0, while at higher pH
there was a much rapid rise indicating precipitation [109]. The
authors explained the variations in nickel ions adsorbed with pH
on the basis of competition between the metal and H3 O+ ions for
capturing the available adsorption sites on the clay surface.
Mockovčiaková et al. [106] concluded that at pH 5–6 adsorp-
tion was stable for zinc uptake on natural and modified bentonite.
Mishra and Patel [108] reported that at pH < 3 there was practically
no removal of zinc by bentonite due to the high proton concen-
tration, while the highest adsorption capacity was obtained at pH
6. Kaya and Ören [58] studied the impact of pH on the adsorption
of zinc on natural and Na-modified bentonite and found that at pH
4–7 a plateau was reached with negligible difference in the adsorp-
tion of zinc, while at higher pH precipitation enhanced the metal
Table 3
Thermodynamic parameters used to describe adsorption systems.
Equation Comment
G = H − TS Gibbs free energy (G) as a function of enthalpy (H) and entropy (S) change at constant temperature
G = − RTlnKeq
o
Correlation of standard Gibbs free energy G◦ with the equilibrium adsorption constant Keq
lnKeq = − Ho /(RT) + So /R Calculation of H◦ and S◦ from the slope and intercept of the Van’t Hoff plot
lnka = lnAa − Ea /(RT) Apparent activation energy (Arrhenius)
removal. Purna Chandra Rao et al. [105] studied the adsorption of
zinc on zeolite 4A, zeolite 13X and bentonite and concluded that
the highest adsorption occurred at pH 6.0. Álvarez-Ayuso et al. [81]
reported that NaP1 zeolite exhibited stable adsorption capacity for
Ni2+ uptake at pH ranging from 4 to 6, while the highest adsorp-
tion capacity for Zn2+ was obtained at pH 6. Sen and Gomez [63]
reported that the increase of pH up to 6.67 increased the adsorp-
tion capacity of bentonite towards zinc, while the further increase
resulted in a subsequent reduction. Ok et al. [11] reported that the
highest adsorption of zinc on a zeolite–Portland cement mixture
occurred at pH 6. Ouki and Kavannagh [50,51] found that the low-
est zinc adsorption on chabazite occurred at the highest pH that
was examined (i.e. pH 6), while for clinoptilolite the lowest adsorp-
tion occurred at highly acidic environment. The selectivity order
of minerals for specific metals is also influenced by solution pH
[26,74].
4.4. Temperature and thermodynamics
Temperature is directly related to the kinetic energy of the
metal ions in the solution. An elevation in temperature subse-
quently results in an increase in the diffusion rate of the sorbate.
In addition, temperature alternations will affect the equilibrium
adsorption capacity of the sorbent for a particular sorbate [110].
Usually, at elevated temperatures the metal uptake is higher due
to higher affinity of the mineral for the metal and/or an increase
in the active sites of the solid. At higher temperature the energy
of the system facilitates the attachment of metals on the mineral’s
surface [111,112].
Temperature increase results in changes related to both kinet-
ics and equilibrium attributed to: (i) increase in the kinetic energy
which facilitates the access of the metal ions to the active adsorp-
tion sites, (ii) increase in the surface activity of the mineral resulting
in higher affinity or increase in the active adsorption sites, (iii)
decrease in the mass transfer resistance. The increase in tem-
perature is accompanied with a decrease in the thickness of the
boundary layer surrounding the mineral, so that the mass trans-
fer resistance of the adsorbate in the boundary layer decreases,
facilitating the diffusion of metals in the adsorbent. Thus, the effec-
tive diffusion coefficient of ions in solid phase usually increases
and an increase in external mass transport is observed [113,114].
As temperature is increased, the retarding specific or electro-
static interactions become weaker and the ions become smaller
because solvation is reduced [115]. However, at very high tem-
peratures physical damage to the mineral can occur, reducing its
adsorption capacity [45,116]. In most cases it is desirable to eval-
uate the adsorption capacity of minerals at room temperature,
since at higher temperature the operational cost of the process
increases.
Variations in temperature cause changes in the thermodynamic
parameters (i.e. G◦ , H◦ and S◦ ). These parameters can be
calculated using the equations of Table 3 [9,98,116–118]. Small
fluctuations in temperature are usually not considered critical. A
positive value of the standard enthalpy change (H◦ > 0) shows
that adsorption is an endothermic process, while negative value
shows that the process is exothermic (H◦ < 0). A negative value of
 S. Malamis, E. Katsou / Journal of Hazardous Materials 252–253 (2013) 428–461 435

the standard Gibbs free energy of adsorption (i.e. G◦ < 0) means
that the process is spontaneous. A temperature rise results in a
higher negative value of the Gibbs free energy; this indicates that
temperature elevation also increases the spontaneity [110]. H◦
is a measure of the interaction level between the metal and the
adsorbent implying the strength of bonding. Physical adsorption is
always an exothermic process; as temperature increases the bonds
between the metals and the adsorbent become weaker. However,
in some cases in literature it has been observed that although the
process is characterized as endothermic the heat evolved during
adsorption is of the same order of magnitude observed in physical
processes [119].
The effect of temperature on Ni2+ and Zn2+ uptake by
minerals and the thermodynamic parameters of the adsorp-
tion system are summarized in Table 4 [40,42,44,47,49,53,57,63,
68,96,98,100–102,104,107,120–127]. Most studies of nickel and
zinc adsorption show that an increase in temperature enhances
the adsorption process. Rajic et al. [120] studied the removal of
nickel using natural zeolitic tuff and found that the increase in
temperature from 25 to 65 ◦ C resulted in a threefold increase

Table 4
Studies on the effect of temperature on nickel and zinc uptake by zeolite, bentonite and vermiculite, thermodynamic parameters.

Metal Mineral Examined temperature Temperature of highest Thermodynamic parameters Reference

range (◦ C) adsorption (◦ C)

Ni Clinoptilolite 10–90 90 G◦ : −8.68 to 17.27 kJ mol−1 [40]

NaCl clinoptilolite
HCl and NaCl clinoptilolite
Ni Montmorillonite 15–40 40 G◦ : 4.30 kJ mol−1 (at 25 ◦ C) [42]
H◦ : 28.9 kJ mol−1
S◦ : 82.5 J mol−1 K−1
Ni Montmorillonite 30–40 30 G◦ : −57.1 kJ mol−1 (at 30 ◦ C) [44,47]
H◦ : −45.1 kJ mol−1
S◦ : −146.4 J mol−1 K−1
Ni ZrO-montmorillonite 30–40 30 G◦ : −33.3 kJ mol−1 (at 30 ◦ C)
H◦ : −37.7 kJ mol−1
S◦ : −133.8 J mol−1 K−1
Ni TBA-montmorillinite 30–40 30 G◦ : −37.7 kJ mol−1 (at 30 ◦ C)
H◦ : −43.1 kJ mol−1
S◦ : −160.5 J mol−1 K−1
Ni Calcined Bofe bentonite 20–75 20 G◦ : −1.39 kJ mol−1 (at 20 ◦ C) [49]
H◦ : −7.33 kJ mol−1
S◦ : −20.33 J mol−1 K−1
Ni Zeolite 20–35 35 – [53]
Ni GMZ Na-bentonite 30–60 60 G◦ : −17.24 kJ mol−1 (at 30 ◦ C) [68]
H◦ : 10.92 kJ mol−1
S◦ : 92.8 J mol−1 K−1
Ni Zeolite 15–35 35 – [96]
Bentonite
Vermiculite
Ni Clinoptilolite 20–60 20 G◦ : −2.89 kJ mol−1 (at 20 ◦ C) [98]
H◦ : −4.32 kJ mol−1
S◦ : 49 J mol−1 K−1
Ni Bentonite 20–60 60 G◦ : −23.85 kJ mol−1 (at 20 ◦ C) [100]
H◦ : 14.21 kJ mol−1
S◦ : 81.46 J mol−1 K−1
Ni Na-bentonite 25–55 55 – [101]
Ni Na-montmorillonite 20–67 67 G◦ : −17.3 kJ mol−1 (at 20 ◦ C) [102]
H◦ : 28.1 kJ mol−1
S◦ : 148.1 J mol−1 K−1
Ni Zeolite tuff 25–65 65 G◦ : −9.7 kJ mol−1 (at 25 ◦ C) [120]
H◦ : 37.9 kJ mol−1
S◦ : 160 J mol−1 K−1
Ni Zeolite 25–100 100 – [121]
Ni Bentonite 25–50 50 G◦ : −7.34 kJ mol−1 (at 25 ◦ C) [122]
H◦ : 2.58 kJ mol−1
S◦ : 32.7 J mol−1 K−1
Ni Bentonite 20–60 60 G◦ : −17.3 kJ mol−1 (at 20 ◦ C) [123]
H◦ : 13.9 kJ mol−1
S◦ : 110 J mol−1 K−1
Zn Vermiculite 15–45 45 – [57]
Zn Bentonite 30–65 30 G◦ : −2.36 kJ mol−1 (at 30 ◦ C) [63]
H◦ : 12.31 kJ mol−1 (at 30 ◦ C)
S◦ : 32.85 J mol−1 K−1 (at 30 ◦ C)
Zn Zeolite 25–45 45 – [104]
Zn Na-dodecylsulphate 25–55 55 G◦ : −9.17 kJ mol−1 (at 25 ◦ C) [107]
montmorillonite H◦ : 7.39 kJ mol−1
S◦ : 6.39 J mol−1 K−1
Zn Zeolite A 25–60 60 – [124]
Zn Na-clinoptilolite 25–65 65 G◦ : −14.1 kJ mol−1 (at 25 ◦ C) [125]
H◦ : 22.4 kJ mol−1
S◦ : 123 J mol−1 K−1
Zn Bentonite 20–50 20 – [126]
Zn Bentonite 20–80 20 – [127]
436 S. Malamis, E. Katsou / Journal of Hazardous Materials 252–253 (2013) 428–461

of adsorption, showing that the process was endothermic and
spontaneous. Enhanced removal of nickel at elevated tempera-
tures has also been documented in several studies involving nickel
uptake by natural minerals [42,53,68,96,100–102,122]. On the con-
trary, Gupta and Bhattacharyya [44] found that the temperature
increase from 30 to 40 ◦ C resulted in a decrease of nickel adsorp-
tion on montmorillonite indicating an exothermic reaction. The
authors attributed this behaviour to the increased solubility of
the metal ions in the solution which favoured the migration of
metal ions from the solid to the liquid phase. Similar results
have been obtained by Argun [98] for the removal of nickel from
clinoptilolite.
The effect of temperature has also been examined for the uptake
of zinc from natural minerals. El-Kamash et al. [124] reported that
the increase of temperature resulted in an increase of the adsorp-
tion capacity on synthetic zeolite A towards zinc. The authors
suggested that this occurred due to the increase of active sites
and due to the change in pore size and the enhanced rate of intra-
particle diffusion. Similar findings were reported by Minceva et al.
[104] for adsorption on zeolite, by Lin and Juang [107] for sorption
on Na-dodecylsulphate montmorillonite and by Wu et al. [57] for
vermiculite. On the contrary, Bereket et al. [126], Sen and Gomez
[63] and Mellah and Chegrouche [127] found that the temperature
decrease enhanced the adsorption of zinc on minerals.
4.5. Adsorbent grain size
The effect of mineral particle size on nickel and zinc removal
has been investigated by several researchers. The most promi-
nent results are summarized in Table 5 [27,52,53,60,64,65,
83,97,100,128,129]. The specific area of the mineral depends on
particle size, pore size distribution and surface roughness. Particles

Table 5
Studies on the effect of grain size on nickel and zinc uptake by zeolite, bentonite and vermiculite.

Metal Mineral Examined grain size range Grain size of highest adsorption (␮m) Reference
(␮m)

Ni Vermiculite <90 <90 (small effect) [27]

90–300
<300
Ni Clinoptilolite 1400–2000 120–350 [52]
500–710
120–350
Ni Zeolite 355–710 45–90 [53]
180–355
90–180
45–90
Ni Jordanian zeolite tuff (phillipsite) 355–710 45–90 [53]
180–355
90–180
45–90
Ni Natural vermiculite 1000–2000 <100 [83]
600–1000
200–600
<100
Ni Natural bentonite 53–300 53 [100]
Ni Scolecite >250 No effect [128]
177–250
149–177
62–149
<62
Zn Vermiculite <90 <90 [27]
30–90
<300
Zn Bigadic zeolite Gordes zeolite 212–300 53–106 [60]
106–212
53–106
Zn Zeolite 250–300 90–125 [64]
150–250
125–200
90–125
Zn Turkish zeolite 1000–2000 300–420 [65]
840–1000
590–840
500–590
420–500
300–420
Zn Vermiculite 1400–2000 <180 [97]
500–1400
180–500
<180
Zn Scolecite >250 <149 (small impact) [128]
177–250
149–177
62–149
<62
Zn Zeolite 2500–5000 <300 (small impact) [129]
1000–2500
300–1000
<300
 S. Malamis, E. Katsou / Journal of Hazardous Materials 252–253 (2013) 428–461
with smaller diameter are characterized by larger specific surface
area, and thus adsorption is enhanced and shorter time is required
to reach equilibrium. Each adsorption site is characterized by its
‘availability’ and ‘accessibility’ with respect to the incoming ion.
Availability is related to equilibrium characteristics and accessi-
bility to kinetics. The availability of active sites remains almost
constant between larger and smaller particles, since the concentra-
tion of the available sites is constant. However, the accessibility of
metal ions to available sites is facilitated when the adsorbent con-
sists of smaller particles, since the diffusion paths of ions become
shorter [130]. Thus, the reduction in particle size is expected to
favour kinetics.
Although the grain size can affect the adsorption capacity, usu-
ally the differences are not critical. Most studies showed that the
smaller grain size favoured the adsorption capacity due to the
mineral’s larger specific surface area [52,53,60,97,100,129]. Some
studies reported that the grain size did not impact, or had a small
impact on the adsorption capacity [27,53,128]. In porous materials,
the internal surface area is much more critical than the external one.
Therefore, changes in the external surface imposed by the grain size
will have a limited effect on the mineral’s adsorption capacity [60].
In terms of kinetics, it has been reported that the impact of grain size
is more important during the early stages of adsorption [129,131];
this can be related to the fact that external diffusion is usually criti-
cal at the initial stages of adsorption. In the adsorption processes in
which film diffusion is dominant, the grain size seems to influence
more the adsorption process, while in the cases where intraparticle
diffusion is dominant the impact of the mineral grain size attenu-
ates. Inglezakis and Poulopoulos [130] reported that the conduction
of experiments with adsorbents of different diameter reveals the
control stage of adsorption. The rate is proportional to the particle
radius when film diffusion is the control stage and inversely propor-
tional to the square root of the particle radius, when intraparticle
diffusion controls the process.
4.6. Adsorbent concentration
The mineral mass in the solution also affects the adsorption pro-
cess, since it determines the availability of active sites. The increase
of the adsorbent concentration results in more sites being avail-
able in the same solution volume. At low mineral concentrations
high amount of sorbate is readily available to be captured by few
available sites. An increase in the solid concentration increases
the surface area of the adsorbent, which in turn increases the
number of binding sites for the same liquid volume and thus the
total amount of metal that is removed increases [132]. However,
the amount of metal adsorbed per unit mineral mass decreases.
At high mineral concentrations the available metal concentration
is insufficient to cover completely the exchangeable sites on the
adsorbent, usually resulting in low metal uptake [133]. Moreover,
the interference between binding sites due to increased adsorbent
concentration can result in a low specific uptake [134]. The inter-
actions between mineral particles become more important when
the mass of the adsorbent in the liquid phase is higher and may
cause physical blockage of some adsorption sites, decreasing the
adsorption efficiency. These interactions can create electrostatic
interferences such that the electrical surface charges on the closely
packed particles diminish attractions between the adsorbed solutes
and surfaces of individual grains [63,135]. In parallel, the interac-
tions between particles may cause desorption of metal ions, when
their adsorption on mineral is reversible. At low mineral concen-
trations, metal ions in the solution would not only be adsorbed
on the surface of the sorbent, but would also enter into its inner
parts, thus facilitating the concentration gradient of metal ions
[136]. Hence, although the number of adsorption sites per unit
mass of an adsorbent should remain constant, independent of the
437
adsorbent mass, the increase in the adsorbent amount in a given
liquid volume reduces the number of available sites per unit mass
of adsorbent, as the effective surface area is likely to decrease [47].
Moreover, the addition of mineral affects the solution pH, which
usually increases with increasing mineral concentration [137]. This
may be attributed to the increase of the amount of negatively
charged sites which can adsorb more H+ resulting in an increase
in the pH of the final solution.
Table 6 [40,42,44,47–49,53–55,58,60,61,63,65,68,96,98,100–
102,105,108,123,127,138] shows several studies reporting the
impact of mineral concentration on nickel and zinc removal.
Most studies report that higher mineral concentrations resulted in
increased metal removal [40,44,47,49,55,61,68,105,108,138] and
reduced amount of metal adsorbed per unit mass of adsorbent
[44,47,49,53,58,60,63,138]. Two reasons can explain this decrease
in the adsorption capacity: the first is associated with the unsatu-
rated adsorption sites and the second one with particle aggregation
resulting in a decrease of the total surface area and an increase of
the diffusion path length [139]. These interactions between min-
eral particles become important when the adsorbent mass in the
solution is high and may physically block some adsorption sites
from the incoming metal ions [63]. Kaya and Ören [58] found that
the increase in mineral concentration resulted in a decrease of
zinc uptake. The authors mentioned that lower mineral concen-
trations resulted in enhanced adsorption due to the increase in
the solid/liquid interface area, resulting from the dilution of the
suspension [140]. Wu et al. [57] stated that for given initial metal
concentration the equilibrium adsorption capacity decreases as the
mineral concentration in the solution increases until it approaches
a critical value at which all ions have been adsorbed on the mineral.
4.7. Adsorbent type
The adsorbent type has a profound effect on adsorption.
Table 7 [26,40,47,56,58,60,81–83,92,96,97,105,106,123,141–155]
summarises the studies comparing the performance of different
types of natural and modified minerals for nickel and zinc uptake.
In most cases the chemical and/or thermal treatment of the mineral
resulted in an increase of its adsorption capacity, while in certain
cases the opposite was observed. Çoruh and Ergun [40] reported
that chemical conditioning of zeolite with HCl and NaCl increased
its adsorption capacity. Na-rich forms of clinoptilolite are known to
have an enhanced exchange capacity, since part of the more tightly
bound K+ and Ca2+ cations are exchanged with strong Na+ solutions.
Conditioning with HCl and NaCl solutions can remove fine dust par-
ticles from the surface of clinoptilolite crystals making the channel
apertures more easily accessible to metal ions [40,128,156,157].
Álvarez-Ayuso et al. [81] found that the adsorption of synthetic
zeolite NaP1 was 10 times higher than that of natural zeolite for
nickel and zinc. Moreover, Álvarez-Ayuso and García-Sánchez [82]
concluded that Ca-bentonite exhibited lower adsorption for Ni and
Zn uptake than Na-bentonite. Esposito et al. [93] concluded that
coal fly ash zeolite 4A and commercial zeolite 4A exhibited sim-
ilar performance for zinc and nickel removal. Vieira dos Santos
and Masini [66] showed that in multi-metal solutions (contain-
ing zinc and nickel) the performance of chabazite was superior
to that of clinoptilolite, while the exposure of zeolite to concen-
trated NaCl solutions converted them to a homoionic state in the
Na-form which improved their exchange capacity. Blais et al. [146]
found that the alkaline treatment of vermiculite with 0.75 M NaOH
increased its performance, while acid treatment with 0.75 M H2 SO4
resulted in inferior performance. The mineral’s adsorption capac-
ity was significantly affected by the pH variation resulting from
alkaline and acid treatment. Bhattacharyya and Gupta [142,143]
reported that acid activation of montmorillonite resulted in a slight
increase of its adsorption capacity towards nickel that could be
438 S. Malamis, E. Katsou / Journal of Hazardous Materials 252–253 (2013) 428–461

Table 6
Studies on the effect of adsorbent concentration on nickel and zinc uptake by zeolite, bentonite and vermiculite.

Metal Mineral Mineral concentration (g L−1 ) Concentration of highest Concentration of highest Reference
adsorption (g L−1 ) removal efficiency (g L−1 )

Ni Clinoptilolite 2.4–40 30–40 [40]

NaCl clinoptilolite
HCl and NaCl clinoptilolite
Ni Montmorillonite 2–30 30 [42]
Ni Montmorillonite 2–6 2 6 [44,47]
ZrO-montmorillonite
TBA-montmorillinite
Ni Natural zeolite 2–22 22 [48]
Ni Calcined Bofe bentonite 5–40 5 40 [49]
Ni Jordanian zeolite tuff 1–8 1 [53]
(phillipsite)
Ni Clinoptilolite 25–100 2 [54]
Ni Zeolite 5–100 100 [55]
Ni GMZ Na-bentonite −1.2 1–1.2 [68]
Ni Zeolite 5–15 15 [96]
Bentonite
Vermiculite
Ni Clinoptilolite 0.5–30 15–30 [98]
Ni Natural bentonite 10–100 100 [100]
Ni Na-bentonite 1–6 6 [101]
Ni Na-montmorillonite −0.9 0.8–0.9 [102]
Ni Bentonite 0.1–5 0.1 5 [123]
Ni Bentonite 1–8 8 [127]
Zn Clinoptilolite 25–100 2 [54]
Zn Zeolite 5–100 100 [55]
Zn Natural bentonite 1–10 1 1 [58]
Na-bentonite 1–2 1
Zn Gordes zeolite 1–10 1 1 [60]
Bigadic zeolite
Zn Cankiri bentonite 1–9 4–9 [61]
Zn Bentonite 0.25–0.75 0.25 [63]
Zn Turkish zeolite 5–50 25–50 [65]
Zn Zeolite 4A 5–30 25–30 [105]
Zeolite 13X
Bentonite
Zn Bentonite 5, 10, 20 20 [108]
Zn Vermiculite 50–150 50 150 [138]

attributed to the increase in the mineral surface area and pore
volume. Cayllahua [89] found that zeolite modification with NaCl
and CH3 COONa increased nickel adsorption by 25–30% compared
to natural zeolite. Stefanović et al. [149] found that chemical condi-
tioning of clinoptilolite tuff with NaCl and CaCl2 resulted in higher
zinc uptake. Olu-Owolabi and Unuabonah [154] reported that ben-
tonite modification with sulphate and phosphate ions increased
the adsorption capacity for zinc uptake. Athanasiadis and Helm-
reich [148] reported that the NaCl clinoptilolite exhibited up to
100% higher sorption capacity for zinc compared to that of natural
clinoptilolite. Cincotti et al. [147,152] and Cerjan-Stefanović et al.
[158] found that Na-modified clinoptilolite performed better than
natural clinoptilolite with respect to zinc removal. Kaya and Ören
[58] also concluded that Na-modified bentonite performed better
than natural bentonite for zinc removal. Purna Chandra Rao et al.
[105] found that synthetic zeolite 4A and 13X had a higher affinity
towards zinc uptake compared to bentonite.
Some studies report that mineral modification adversely
impacted on its performance. Gupta and Bhattacharyya [47]
found that natural montmorillonite performed better than ZrO-
montmorillonite and TBA-montmorillonite as the introduction of
ZrO and TBA groups in clay blocked some of the available adsorption
sites. Similarly, Mockovčiaková et al. [106] found that natural ben-
tonite performed better than synthetic bentonite with respect to
zinc removal. Abollino et al. [26] compared the adsorption capacity
of Na-montmorillonite and vermiculite for nickel and zinc removal.
The authors concluded that montmorillonite performed better than
vermiculite at low pH in the presence of effluents having high ionic
strength, while vermiculite was more suitable for the removal of
heavy metals from the examined effluents at high pH. Katsou et al.
[96,97] found that the mineral order for nickel removal was ver-
miculite > bentonite > zeolite, while for zinc removal the order was
bentonite > zeolite > vermiculite, showing the high affinity of ver-
miculite towards nickel and of bentonite towards zinc. Zamzow
and Murphy [159] found that the adsorption capacity of different
types of zeolite for zinc uptake in wastewater exhibited signifi-
cant variability as it ranged from 5.6 to 44.1 mg g−1 . Pitcher et al.
[84] concluded that synthetic zeolite was more effective (>96%)
for the removal of Zn2+ from both multi-metal synthetic solutions
and stormwater compared to natural zeolite (10–42%). The higher
performance of synthetic zeolite was attributed to its higher alu-
minium content, its purity, its exchangeable and homoionic form,
its lower grain size and its larger internal area [84,131].
4.8. Competitive adsorption
The presence of other cations apart from the one that must be
removed from wastewater has a negative influence on the adsorp-
tion process [136]. The adsorbent’s performance depends on the
type and concentration of other cations that co-exist in the liquid
phase and more importantly with the selectivity of the adsorbent
for cations compared to its selectivity towards the heavy metal
under investigation. The presence of other cations in the solution
can reduce the adsorption capacity compared to that obtained for
the uptake of each metal individually in single metal systems, par-
ticularly when the mineral is more selective for the competing
cations rather than the heavy metal. Malamis et al. [160] stud-
ied the competitive adsorption of Ni and Zn on zeolite, bentonite
and vermiculite in multi-metal solutions containing Ni, Zn, Cu and
Pb. Katsou et al. [96,97] studied the adsorption of Ni and Zn on
 S. Malamis, E. Katsou / Journal of Hazardous Materials 252–253 (2013) 428–461 439

Table 7
Impact of adsorbent type on nickel and zinc adsorption.

Metal Sorbent Adsorption Reference

capacitya
(mg g−1 )

Ni Vermiculite 25.33 [26]

Na-montmorillonite 3.64
Ni Natural zeolite 8.69 [40]
Modified zeolite (HCl + NaCl) 10.75
Modified zeolite (NaCl) 10.46
Ni Montmorillonite 21.14 [47]
ZrO-montmorillonite 10.45
TBA-montmorillonite 8.50
Ni Na-montmorillonite 10.04 [56]
Acid modified montmorillonite 7.31
Ni Zeolite 1.98 [81]
Ni Synthetic (NaP1) zeolite 20.1
Ni Na-bentonite 24.2 [82]
Ni Ca-bentonite 6.3
Ni Natural vermiculite 19.3 [83]
Exfoliated vermiculite 5.91
Ni Commercial zeolite 4A 7.90 [92]
Ni Coal fly ash prepared zeolite 4A 8.96
Ni Vermiculite 25.51 [96]
Bentonite 19.92
Zeolite 16.86
Ni Natural bentonite 50 [123]
Washed bentonite 20
Calcined bentonite 22
Ni Na-zeolite 1.30 [141]
Gördes (natural) zeolite 1.44
Bigadic (natural) zeolite 2.74
Bigadic (natural) zeolite 1.26
Ni Acid-activated montmorillonite 29.5 [142]
Montmorillonite 28.4
Ni Acid-activated montmorillonite 21.3 [143]
Montmorillonite 21.1
Ni TBA-montmorillonite 19.7 [144,145]
Montmorillonite 28.4
Ni Vermiculite 0.229 [146]
Ni Acid (H2 SO4 ) treated vermiculite 0.139
Ni Alkaline (NaOH) treated vermiculite 0.643
Zn Vermiculite 23.40 [26]
Na-montmorillonite 3.61
Zn Na-modified bentonite 54 [58]
Natural bentonite 24
Zn Gordes zeolite 6 [60]
Bigadic zeolite 3
Zn Zeolite 3.45 [81]
Zn Synthetic (NaP1) zeolite 32.6
Zn Na-bentonite 23.1 [82]
Zn Ca-bentonite 5.8
Zn Commercial zeolite 4A 31.58 [92]
Zn Coal fly ash prepared zeolite 4A 30.80
Zn Vermiculite 31.65 [97]
Bentonite 39.5
Zeolite 18.66
Zn Zeolite 4A 42.82 [105]
Zeolite 13X 38.31
Bentonite 35.17
Zn Natural bentonite 36.63 [106]
Composite E20 bentonite 29.67
Composite A85 bentonite 14.10
Zn Vermiculite 0.266 [146]
Acid (H2 SO4 ) treated vermiculite 0.137
Alkaline (NaOH) treated vermiculite 0.737
Zn Sardinian clinoptilolite 3.27 [147]
Na-modified zeolite 14.06
Zn Clinoptilolite 4.40 [148]
NaCl-modified clinoptilolite 8.00
Zn Zeolite 17.00 [149]
Na-modified zeolite 49.69
Zn Natural clinoptilolite 17.50 [150]
Na-clinoptilolite 14.20
NH4 -clinoptilolite 19.70
Zeolon P4A clinoptilolite 154.97
Na-zeolon 4A clinoptilolite 134.20
NH4 -zeolon P4A clinoptilolite 111.90
440 S. Malamis, E. Katsou / Journal of Hazardous Materials 252–253 (2013) 428–461
Table 7 (Continued)
Metal Sorbent
Zn Clinoptilolite
Philipsite
Chabazite
Analcime
Bentonite
Zn Clinoptilolite
Na-clinoptilolite
Zn Heated (110 ◦ C) bentonite
Heated (200 ◦ C) bentonite
Heated (200 ◦ C) bentonite
0.5 mol L−1 H2 SO4 bentonite
2.5 mol L−1 H2 SO4 bentonite
Zn Bentonite
Sulphate-modified bentonite
Phosphate-modified bentonite
Zn Montmorillonite
HyA-montmorillonite
HAS-montmorillonite
a
Adsorption capacity in most cases refers to qm and in some cases to qe .
the same natural minerals in single metal solutions. In the latter
case the adsorption was significantly higher due to the absence of
other ions in the solutions. However, in several cases the mineral
adsorption capacity for the uptake of all metals remains relatively
constant. The reduction in the adsorbent’s performance depends on
its selectivity and affinity for the respective ion in comparison with
the competing ions, as well as the ionic properties and the concen-
tration of each ion. The parameters that impact on the performance
of an adsorbent are related to the adsorbent characteristics, the
properties of the metal ions and the liquid medium characteristics
[93,161].
The metal ions having smaller hydrated ionic radius have easier
access to the mineral’s surface and can diffuse more easily inside
its pores. On the other hand, the presence of ions having a larger
hydrated ionic radius results in a more rapid saturation of the
adsorption sites. Furthermore, electronegativity and ionic poten-
tial provides an indication of the power of adherence of the metal
ions to the solid. The metals exhibiting the highest electronega-
tivety exhibit the greatest uptake by the adsorbent. Furthermore,
the metals having the highest ionic potential are strongly retained
by the adsorption sites exhibiting high negatively charged density.
Nevertheless, their interaction with certain functional groups of the
adsorbent can be weaker than that of other metals having lower
ionic potential [162]. The adsorption of metals exhibiting higher
affinity to the minerals is not impeded much in a competitive envi-
ronment of metal ions. The presence of competing metals impacts
to a much greater level in the cases where the metals are retained
by the minerals at the active adsorption sites with weak bonds. For
example, the selectivity of zeolite 4A for the uptake of metals from
a multi-metal solution followed the order: Cu > Cr3+ > Zn > Co > Ni.
The increase in the concentration of the metal ions in the solu-
tion resulted in a significant reduction of the adsorption of Zn, Co
and Ni. The lower zeolite selectivity for these metals compared to
Cu and Cr3+ resulted in reduced adsorption capacity. The afore-
mentioned selectivity order cannot be attributed to the hydration
energy of ions, neither to the free hydration energy. The metals
having the highest free energy of hydration should prefer the liq-
uid rather than the solid phase. Researchers attribute the higher
removal of Cu and Cr3+ to the higher precipitation of metal hydrox-
ides on the mineral surface and pores [93]. A similar case has been
recorded by Panayotova and Velikov [163]. The higher selectivity
of clinoptilolite for lead contributes to a significant reduction of
adsorption of Ni, Cu and Zn when these metals co-exist, with the
lower decrease being observed for the adsorption of Zn [54]. The
Adsorption Reference
capacitya
(mg g−1 )
3.16 [151]
1.70
7.98
3.67
3.08
4.58 [152]
8.17
3.32 [153]
4.54
2.88
2.29
16.36–24.48 [154]
17.17–26.19
17.50–26.63
215.63 ± 11.12 [155]
395.88 ± 25.52
396.02 ± 10.81
mineral’s selectivity for the uptake of different heavy metals in a
multi-metal environment follows the order Pb > Zn > Cu > Ni, which
is the same as the one observed in single metal solutions. Sprynskyy
et al. [52] found a significant decrease of Ni adsorption on clinop-
tilolite in multi-component solutions (Pb, Cu, Cd and Ni) compared
to single solutions which was probably caused by the propinquity
of the sorbents to the other metals in the solution. The other metals
in the solution were only slightly affected by the presence of com-
peting ions. Specifically, the selectivity order of clinoptilolite in the
presence of other metals has the following order Pb > Cu > Cd > Ni.
The preference of Na-bentonite for Cu can explain the significant
decrease of Ni adsorption which is observed when both metals (i.e.
Cu and Ni) co-exist in the solution [101]. Futalan et al. [164] drew
similar conclusions since they mention that the adsorption of Ni on
bentonite was impeded due to the presence of Pb and Cu in the solu-
tion. Mishra and Patel [108] stated that the capacity of bentonite
for Zn uptake was lower when Pb was present in the solution com-
pared to single metal solutions, while the adsorption capacity of
bentonite for Pb was the same in single and binary (Pb–Zn) metal
solutions.
The temperature significantly influences the performance of
competitive adsorption. Donat et al. [100] found that in the pres-
ence of other metals (i.e. Pb, Cd and Cu) nickel adsorption on
bentonite was lower. The temperature increase contributed to a
reduction of adsorption inhibition caused by the presence of both
Ni and Cu in the solution. Lead adsorption was found to be more
sensitive in the presence of Ni and Cu compared to Cd, while the
adsorption order of metals on bentonite from multi-metal solutions
was Pb > Cu > Ni > Cd.
The initial concentration of competing cations in the solution
influences the adsorption of heavy metals on minerals. The pres-
ence of a metal having higher initial concentration in the solution
is usually accompanied by higher adsorption due to its competitive
advantage compared to the other metals that co-exist in the solu-
tion. Ibrahim et al. [165] attribute the selectivity order of zeolite
(Ni > Cr3+ > Cu > Fe > Zn) for the uptake of different metals to a large
extent to the initial metal concentration contained in galvaniz-
ing wastewater (Ni > Cu > Cr3+ > Fe > Zn). However, the initial metal
concentration is only one of the several parameters that can have an
influence on competitive adsorption. Other properties such as the
ionic size, valence, hydrated energy, ionic potential are parameters
that can determine the selectivity order of minerals for metals. Zeo-
lites having high Si/Al ratio have a preference towards monovalent
metal cations having low charge density. Among divalent metal
 S. Malamis, E. Katsou / Journal of Hazardous Materials 252–253 (2013) 428–461
cations, the mineral’s selectivity depends on hydration energy,
with the mineral being more selective towards the cations hav-
ing lower hydration energy. The mineral has higher selectivity for
the metals that have larger valence (electrostatic interaction), fact
that explains the greater adsorption of Cr3+ compared to Cu2+ .
Among two metals having the same valence, selectivity usually
increases with a reduction in the hydrated ionic radius. Wu et al.
[138] concluded that the addition of Cd and H+ in the solution con-
tributes to the reduction of Zn adsorption on vermiculite, since
the increase of the concentration of competing cations affects
more the adsorption process. Similar results were observed for
the study of Zn adsorption on vermiculite in Zn–Cd–K solution
[43]. Covelo et al. [166] investigated the competitive adsorption of
heavy metals on vermiculite and found that the selectivity order
was: Cu > Zn > Pb > Cd > Cr > Ni. The adsorption of Cu is stronger
compared to the other metals and as a result it is preferred by
vermiculite in the presence of competing cations. Abollino et al.
[74] mention that the higher charge density results in greater
electrostatic attraction of the metals ions on Na-vermiculite. The
mineral selectivity order was Cr3+ > Ni > Mn > Zn > Cu > Cd = Pb. In
this case the metals having the larger ionic radius and the smaller
charge density have unfavourable adsorption characteristics. At
the same time these metals are influenced more by the proto-
nation of the surface groups of the adsorbent at low pH and
thus their uptake by minerals becomes more difficult. Ouki and
Kavannagh [50,51] investigated the performance of zeolite and
chabazite for the uptake of Ni and Zn from multi-metal aqueous
solutions and found that the clinoptilolite selectivity sequence was
Pb > Cu > Cd > Zn > Cr > Co > Ni, while the corresponding selectivity
for chabazite was Pb > Cd > Zn > Co > Cu > Ni > Cr.
The presence of alkali metals and alkaline earth metals in the
solution can influence the adsorption process; the increase of the
alkali metal concentration usually limits the adsorption process.
Yang et al. [68] found that the simultaneous presence of Na+ ,
Ca2+ and K+ in the solution reduces the adsorption of Ni on GMZ-
bentonite. Calcium was found to have greater influence in the
adsorption of Ni on bentonite compared to the other cations. El-
Bayaa et al. [167] found that the presence of Na+ in the solution
has a smaller impact on the adsorption of Cr3+ and Cu2+ than
that of NH4 + and K+ . The latter is attributed to the lower mineral
selectivity towards Na+ . Sodium is characterized by a large hydra-
tion radius and forms outer-sphere complexes with the mineral.
The adsorption of Ni and Cd on zeolite and bentonite decreases
significantly due to the presence of Mg2+ , Ca2+ and Fe3+ [105].
The influence of competing cations is greater for zeolite (4A and
13X) compared to bentonite, while the presence of Mg results in
greater reduction of Zn and Cd uptake by minerals compared to Ca
and Fe.
According to the Eisenmann–Sherry model, zeolite selectivity
for the various cations is a function of their free hydration energy
and of the electrostatic interactions among the free ions and those
located in the zeolite structure [168]. The preference of a mineral
for a metal ion as opposed to another one depends upon whether
the electrostatic (Coulombic) energy of the ionic interaction with
the anionic grid prevails over its difference in the free energy of
hydration. In zeolites having low Si/Al ratio which are character-
ized by a high charge grid and thus high capacity, the selectivity
reduces with the increase of the ionic radius and cations having a
higher charge density are preferred when monovalent cations are
exchanged. When monovalent cations are exchanged with diva-
lent ones, the zeolite having low Si/Al ratio usually prefers divalent
cations. In zeolites having high Si/Al ratio which are characterized
by low charge grid and thus lower capacity, their selectivity reduces
with the increase (in absolute value) of the free energy of hydra-
tion. In the clinoptilolite grid a low anionic field is created which
enhances its selectivity for (i) ions with low charge density such as
441
NH4 + and Cs+ when monovalent cations are exchanged and (ii) ions
with low hydration energy such as Pb2+ when divalent cations are
exchanged with monovalent ones.
The selectivity order of metal cations in clinoptilolite with
Si/Al ratio of 4.2 is given by Caputo and Pepe [169] as:
Cs+ > NH4 + > Pb2+ > Na+ > Sr2+ > Cd2+ > Zn2+ ≈ Cu2+ . This order con-
firms the high selectivity of clinoptilolite for monovalent cations
with low charge density. Furthermore, the high mineral selec-
tivity for Pb2+ is attributed to the low hydration energy of the
cation. Langella et al. [69] have found similar results as the clinop-
tilolite selectivity order is: NH4 + > Pb2+ > Na+ > Cd2+ > Cu2+ ≈ Zn2+ .
Consequently, clinoptilolite selectivity is mainly determined by
the free energy of hydration of the cations. Tsitsishvili et al.
[170] found the following selectivity order for natural zeo-
lites: Ba2+ > Pb2+ > Cd2+ > Zn2+ > Cu2+ . According to Blanchard et al.
[171], the selectivity of Na-clinoptilolite follows the order
Pb2+ > NH4 + > Cu2+ , Cd2+ > Zn2+ , Co2+ > Ni2+ > Hg2+ . Similar results
were obtained by Ouki and Kavannagh [50,51], since the perfor-
mance of clinoptilolite for the removal of heavy metals from multi-
metal solutions reduces in the order: Pb > Cu > Cd > Zn > Cr > Co > Ni.
Wang and Peng [18] summarize the selectivity order of clinoptilo-
lites having different origin for the competitive adsorption of heavy
metals and confirm the high mineral selectivity for lead. From the
above discussion, it can be concluded that the hydration energy, the
charge density (ratio of charge/ionic radius) and the dimensions of
the hydrated ions provide an indication of the mineral’s preference
for the different metals during competitive adsorption. However,
the mineral’s selectivity also depends on other parameters such as
the geometry and/or the orientation of the ion. For example, clinop-
tilolite is very selective for the ammonium ion, despite its high
hydration energy (−1329 kcal mol−1 ). This happens because NH4 +
can easily penetrate through the clinoptilolite’s channels by suit-
ably transforming its orientation [172]. Wingenfelder et al. [129]
attribute the higher hindrance of Zn and Cd adsorption on zeo-
lite and the low hindrance of Pb adsorption that occurs with the
increase of Ca2+ concentration in the solution to the low Si/Al ratio
and the low charge density of zeolite. Lead is characterized by the
lowest hydration energy and as a result its adsorption on zeolite
is favoured. At the same time its presence in the solution reduces
the adsorption of Cd and Zn, while the presence of other cations
(i.e. Ca2+ ) has a small impact on lead adsorption. Panayotova and
Velikov [173] compared the removal of Ni and Zn obtained by a
natural Bulgarian zeolitic rock in single and in multi (Ni, Zn, Pb,
Cu, Cd) metal solutions and concluded that there was a significant
decrease in metal uptake in multi-metal solutions. Moreover, the
authors reported that the presence of Ca2+ in single and multi-
metal solutions decreased metal uptake by zeolite in the order
Zn ≈ Cd > Ni > Cu; the presence of Mg2+ in multi-metal solutions did
not significantly impact on metal removal, while the availability
of Mg2+ in single heavy metal solutions resulted in a significant
decrease in Ni and Zn uptake by zeolite. In the study of Panay-
otova and Velikov [163] the presence of Mg2+ in wastewater slightly
decreased the uptake of Ni and Zn by NaCl-zeolite from multi-metal
solutions (Pb, Cd, Cu, Zn, Ni), while a significant decrease in the
adsorption of both metals by the modified zeolite was observed
due to the presence of Ca2+ that is characterized by lower hydration
energy compared to the two heavy metals.
Most documented studies show that nickel and zinc adsorption
on minerals decreases in the presence of other cations. On the
other hand, certain researchers mention that the presence of alkali
metals and alkaline earths does not significantly impact on the
adsorption of heavy metals [165]. In some works, researchers
have found that although the individual adsorption capacity of
the mineral for each metal decreases in multi-metal solutions
compared to single metal solutions, the total metal uptake by the
mineral is actually higher. For example, Jha et al. [174] found that
442 S. Malamis, E. Katsou / Journal of Hazardous Materials 252–253 (2013) 428–461

the adsorption of Ni and Cu on composite activated carbon-zeolite
decreases when the two metals co-exist in the same solution,
while this decrease becomes more significant when Cd is added
in the solution. Nevertheless, the total adsorption capacity for
all metals is larger in multi-component solutions, showing that
the adsorption of a metal from single metal solutions leaves
certain adsorption sites empty. This happens because certain
adsorption sites have the ability to attract specific metals. Table 8
[27,50,51,54,57,92,96,97,101,108,128,138,146,161,166,174–176]
presents the adsorption capacities of minerals for nickel and zinc
ions in multi-component solutions; in most cases a comparison is
made with the respective ones obtained in single metal solutions.
4.9. Ionic strength
Wastewater contains various cations (e.g. Na+ , K+ , Ca2+ , Mg2+ ,
NH4 + ) and anions (e.g. Cl− , SO4 2− , PO4 3− , HCO3 − ) that may limit the
mineral uptake of heavy metals. The impact of ionic strength can be
attributed to the competition among cations, the metal’s activity,
the interface potential, the solution pH and to the properties of the
electric double layer. When the adsorbent’s surface is in contact
with metals, the cations that are adsorbed are surrounded by an
electric double layer due to electrostatic interactions. These inter-
actions decrease when the ionic strength increases. This decrease
is attributed to the weaker repulsive forces of the electric double
layer since the latter is compressed at high ionic strength, while
attractive van der Waal forces remain independent of the solution’s
ionic strength. The surface potential decreases with the compres-
sion of the double layer, while the surface charge density remains
constant. The compression of the double layer may favour the
uptake of metal ions by the adsorbent. Thus, in some cases high
adsorption capacity is observed with high ionic strength [177,178].
However, the competition between the electrolyte cations (e.g. Na+ ,
K+ ) and the heavy metals for the available adsorption sites can

Table 8
Competitive adsorption of nickel and zinc on zeolite, bentonite and vermiculite.

Solution Adsorbent Ni2+ adsorption Zn2+ adsorption Reference

(mg g−1 ) (mg g−1 )

Multi (Ni, Zn, Cd, Cu, Mn, Pb) Vermiculite 25.33 23.40 [27]
Multi (Pb, Cd, Cu, Zn, Cr, Ni, Co) Clinoptilolite 0.9 2.7 [50,51]
Multi (Pb, Cd, Cu, Zn, Cr, Ni, Co) Chabazite 4.5 5.5 [50,51]
Single Zn Clinoptilolite – 8.21 [54]
Single Ni 5.08 –
Multi (Pb, Zn, Cu, Ni) Clinoptilolite 0.5 3.53 [54]
Single Zn Vermiculite 1.06 [57]
Ternary (Zn, Cd, K) 0.70
Multi (Co, Cr, Cu, Zn, Ni) Zeolite 4A 7.9 [92]
Multi (Co, Cr, Cu, Zn, Ni) 31.6
Multi (Co, Cr, Cu, Zn, Ni)
Multi (Co, Cr, Cu, Zn, Ni) Coal fly ash prepared 8.96 30.80 [92]
Multi (Co, Cr, Cu, Zn, Ni) zeolite 4A
Multi (Co, Cr, Cu, Zn, Ni)
Single Ni and Zn Vermiculite 15.76 22.76 [96,97]
Zeolite 5.52 12.9
Bentonite 8.93 24.20
Single Ni Na-bentonite 13.97 [101]
Binary (Ni, Cu) 10.91
Single Zn Bentonite – 9.12 [108]
Binary (Pb–Zn) 7.56
Binary (Pb–Zn) 5.80
Multi (Cu, Zn, Ni, Co, Pb, Cd) Scolecite 0.9 2.1 [128]
Single Zn Vermiculite 0.85 [138]
Binary (Zn, Cd) 0.10
Binary (Zn, H) 0.10
Multi (Al, Ca, Cd, Cr, Cu, Fe, Mg, Mn, Ni, Vermiculite 0.23 [146]
Pb, Zn) 0.27
Multi (Al, Ca, Cd, Cr, Cu, Fe, Mg, Mn, Ni, Acid (H2 SO4 ) treated 0.139 [146]
Pb, Zn) vermiculite 0.137
Multi (Al, Ca, Cd, Cr, Cu, Fe, Mg, Mn, Ni, Alkaline (NaOH) 0.643 0.737 [146]
Pb, Zn) treated vermiculite
Multi (Ni, Cu, Pb, Zn) Vermiculite 9.54 7.14 [161]
Zeolite 3.71 4.11
Bentonite 7.44 8.30
Multi (Cd, Cr, Cu, Ni, Pb, Zn) Vermiculite 0.32 2. 64 [166]
Single Ni Activated 70.43 [174]
Binary (Ni, Cu) carbon–zeolite 20.54
Ternary (Ni, Cu, Cd) composite (type 1) 21.72
Single Ni Activated 62.22 [174]
Binary (Ni, Cu) carbon–zeolite 22.30
Ternary (Ni, Cu, Cd) composite (type 2) 22.30
Single Zn Zeolite 3.926 [175]
Binary (Zn, Cd) 2.02
Binary (Zn, Cd) 0.881
Binary (Ni, Pb) Vermiculite 13.04 – [176]
Binary (Ni, Ag) 14.27
Binary (Ni, Cd) 9.01
Tertiary (Ni, Ag, Pb) 12.77
Tertiary (Pb, Ni, Cd) 8.73
Tertiary (Ag, Ni, Cd) 9.16
Multi (Ag, Ni, Cd, Pb) 8.09
 S. Malamis, E. Katsou / Journal of Hazardous Materials 252–253 (2013) 428–461
decrease the amount of metals that is adsorbed on the minerals
[45,179,180].
The increase in ionic strength can influence adsorption in two
ways: (i) it decreases the solution-phase activity of the metal and
(ii) it increases the concentration of competing ions [19,64]. The
decrease in the metal’s activity resulting from the elevated ionic
strength is due to the increase in the concentration of the accompa-
nying anions of the electrolyte solution. These anions create stable,
soluble complexes with the heavy metals which are not easily
adsorbed by the mineral. Several studies have shown that at low
ionic strength, metal adsorption on minerals occurs both at the pla-
nar sites of the adsorbent (i.e. outer-sphere complexes) as well as
at the mineral edges (i.e. inner-sphere complexes). The increase
in the ionic strength results in an increase of the concentration of
the cations (e.g. Na+ , K+ , Ca2+ , Mg2+ ) that compete with the heavy
metals particularly for the planar mineral sites, which in several
cases exhibit lower affinity for heavy metals [26,167,181]. There-
fore, at high ionic strength metal adsorption takes place mainly
through the formation of inner-sphere complexes with the func-
tional groups at the mineral edges which have high affinity for the
heavy metals. Several salts have been employed to examine the
effect of ionic strength on adsorption including NaCl, NaNO3 , KCl,
MgCl2 , CaCl2 , NaClO4 [9]. Most studies show that an increase in
ionic strength decreases the mineral’s adsorption capacity [64,81],
while there are also some studies showing that the ionic strength
has a small impact on adsorption [64,182] or even that it has a
positive contribution [138].
Álvarez-Ayuso et al. [81] studied the effect of ionic strength
by employing 0–0.1 M Ca(NO3 )2 ·4H2 O as electrolyte at pH 6 for
nickel and zinc adsorption on synthetic zeolite. The authors found
that the presence of calcium reduced the adsorption performance
by 55–60% for both metals. Song et al. [102] investigated the
adsorption of nickel on Na-montmorillonite in the presence of
0.01–0.1 M NaClO4 . The authors found that at low pH (<7) the
ionic strength affected the adsorption process, while at higher pH
it did not influence it. Yang et al. [68] investigated the adsorp-
tion of nickel on GMZ Na-bentonite for NaClO4 concentrations of
0.001, 0.01 and 0.1 M and found that ionic strength influenced the
adsorption process for pH < 8, while at pH > 8 the ionic strength
was not an important factor. Respectively, the adsorption of Ni on
Na-montmorillonite was found to be influenced by the increase
in the concentration of NaClO4 at pH < 7, while at higher pH the
ionic strength did not impact on the metal removal process. This
behaviour can be associated to outer and inner-sphere complexa-
tion. At low pH the main mechanism of adsorption is that of ion
exchange (formation of outer-sphere complexes), while at higher
pH the formation of inner-sphere complexes prevails. The metals
that are connected with strong bonds to the available adsorption
sites are not significantly affected by the ionic strength. On the other
hand, the outer-sphere complexes are affected by the solution’s
ionic strength [26,28]. It is postulated that when ionic strength
influences the adsorption process outer-sphere complexation is
important, while in the opposite case inner-sphere complexation
is important [183,184]. Consequently, the impact of ionic strength
on adsorption can be employed to distinguish between the forma-
tion of inner and outer-sphere complexes. The electrolyte’s cations
compete with heavy metals for the formation of bonds with the
functional groups of the adsorbent that are mainly electrostatic in
nature, while they do not influence significantly the adsorption of
metals that are linked with strong bonds (e.g. covalent bonds) with
the adsorption sites [185].
Trgo and Perić [182] concluded that the dissolution of zeolitic
tuff is affected more by ionic strength than by the pH. Baker et al.
[64] investigated the effect of ionic strength in batch and column
experiments for zinc adsorption on zeolite. The authors found that
that the change in ionic strength (i.e. 0.01–0.05 M NaClO4 ) in the
443
column studies had little influence on adsorption, while in batch
experiments a significant reduction in adsorption performance
was observed when NaClO4 concentration increased from 0.03 to
0.04 M. Wu et al. [138] were able to obtain a linear positive cor-
relation between the ionic strength and the amount of zinc that
is adsorbed on zeolite. Álvarez-Ayuso et al. [81] mention that the
increase of Ca(NO3 )2 ·4H2 O concentration in the solution reduces
the adsorption of Ni, Zn and Cd, indicating that ion exchange is the
dominant process. The presence of Ca(NO3 )2 ·4H2 O impacts on the
adsorption of Ni and Zn, contributing to the decrease of their uptake
by 55–60%, since the hydration energy of Ca2+ is significantly lower
than that of Ni and Zn.
4.10. Agitation speed
The rate of the adsorption process may be controlled by external
mass transfer or/and intraparticle diffusion. External mass trans-
fer is usually important at the initial stages of the process. The
application of appropriate agitation increases ion mobility in the
solution and thus, the mass transfer resistance reduces [45,116].
At high agitation rates, the boundary layer becomes thinner, which
usually enhances the rate of solute diffusion through the boundary
layer [186]. Under high agitation speed, the external diffusion coef-
ficient increases [187]. In most cases the increase in stirring speed
is associated with an increase in the rate of adsorption, particu-
larly during the early stages of the process. Shawabkeh et al. [188]
used zeolite produced by Jordanian oil shell ash to remove zinc
from wastewater and found that the rate of adsorption increased
with increasing agitation speed. Kocaoba et al. [48] investigated the
effect of agitation speed (5–250 rpm) on adsorption of nickel on
natural zeolite and found that the uptake increased up to 150 rpm
and thereafter remained constant. Other researchers found that
high agitation rates do not influence or have a negative impact on
metal adsorption. In these cases it seems that diffusion of metal
ions from the bulk solution to the mineral surface through the
boundary layer is not the rate limiting step, or a breaking up of
mineral particles may have occurred. Mellah and Chegrouche [127]
examined the impact of various agitation speeds (i.e. 200, 350
and 500 rpm) on zinc removal by bentonite and found that dur-
ing the first 15 min the adsorption was higher for 200 rpm. The
authors mention that the lack of homogeneity and/or the break-
ing up of particles at higher agitation speeds were the most likely
reasons for this behaviour. On the contrary, Trgo and Perić [182]
stated that the potential breaking up of mineral particles enhanced
the adsorption performance since freshly broken adsorption sites
were revealed; thus greater stirring speeds increased the number
of available adsorption sites. Taparcevska et al. [189] investigated
the impact of agitation speed (150–190 rpm) on Zn2+ removal from
aqueous solutions by employing zeolite and concluded that the rate
of zinc adsorption on zeolite was not significantly influenced by the
degree of stirring. Thus, mass transfer across the boundary layer did
not impact the adsorption rate of the process. According to McKay
[190] and Meshko et al. [191] the variation in the external mass
transfer coefficient with agitation speed was more significant only
when low (<50 rpm) stirring speeds were employed.
4.11. Evaluation of parameters
The prominent parameters affecting the adsorption process are
the solution pH, the adsorbate type and concentration and ionic
strength. Furthermore, the presence of competing ions in the liq-
uid medium and/or certain wastewater compounds can adversely
impact on the adsorption process. The chemical and/or thermal
pre-treatment of natural mineral also modifies its cation exchange
capacity. However, mineral modification is not always associated
with increased metal uptake. The adsorbent properness for the
444 S. Malamis, E. Katsou / Journal of Hazardous Materials 252–253 (2013) 428–461

Table 9
Evaluation of the effect of several parameters on mineral adsorption capacity and on heavy metal removal.

Parameter Evaluation result

Adsorption capacity Metal removal (%)

Presence of competing ions ↓ It depends on metal type ↓

Composition of liquid medium where adsorption takes place ↓ In wastewater compared to aqueous solutions ↑ In wastewater compared to aqueous solutions
Presence of ligands ↓ It depends on metal and ligand type ↑ Insoluble metals ↓ Soluble metal complexes
Increase in initial metal concentration ↑ Until a specific value ↓
Decrease in mineral grain size ↑ Or relatively constant ↑
Increase in solution pH ↑ Until a specific value and then↓ ↑
Increase in mineral concentration ↓ Or remains almost stable ↑
Increase in total suspended solids of wastewater ↑
Increase in temperature ↑ ↑

removal of one or more metals must be examined in the real envi-
ronment (i.e. true effluents) that it will be applied. The evaluation of
the adsorbent efficiency must be based on the comparative assess-
ment of the impact of several parameters (e.g. pH, composition of
liquid medium, presence of other ions and compounds). Table 9
summarizes the common tendencies concerning the impact of sev-
eral parameters on the adsorption of metals on bentonite, zeolite
and vermiculite in wastewater and aqueous solutions.
5. Removal efficiencies
It is evident that the adsorption performance depends on
several parameters which have been reviewed in this work.
Depending on the operating conditions, the removal efficiencies
of zinc and nickel by zeolite, bentonite and vermiculite are vari-
able and are summarized in Table 10 [6,11,26,40,47–52,54–57,
59–62,64,65,68,74,80–82,84,96–98,100–102,105,108,123,125,126,
128,129,141–146,153,155,163,173].
6. Kinetics
The prediction of the rate at which adsorption takes place is an
essential factor for the successful design of an adsorption system.
The adsorbate residence time and the reactor dimensions depend
on the adsorption system kinetics [21]. The examination of system
kinetics can reveal the adsorption mechanism. In adsorption
studies it is important to determine the underlining mecha-
nisms which may include external diffusion, internal diffusion
and/or chemical reactions. To identify these mechanisms several
reaction kinetics and diffusion models are available. Table 11
[63,98,187,192–209] shows the reaction kinetic and diffusion
models employed to study the adsorption process. The kinetic
models that are usually examined consist of the pseudo-first-order,
the pseudo-second-order and Elovich’s model. These models are
widely employed for examining the kinetics of adsorption. Table 12
[40,42,44,47,49,56,61,63,68,92,96–99,101,105,120,123–125,142,
154,174,176,210] summarizes the results obtained by employ-
ing reaction kinetic models to predict the kinetics of Ni and
Zn uptake by minerals. Several researchers have reported that
the adsorption of these metals on minerals follows the pseudo-
second-order model [44,56,63,68,105,108,120,123–125], while
some researchers have indicated the applicability of the pseudo-
first-order model [107,173]. The fit of the linear forms of these
equations to experimental data is conducted using linear regres-
sion analysis. The non-linear equations are solved by minimizing
a specific error function among the experimental and the model
values. The second-order equation describes the chemical sorption
and thus some type of chemical reaction is considered to take
place that includes valence forces with the exchange of ions or
the formation of covalent bonds [211–213]. However, the good fit
of the second-order model with the experimental data does not
necessarily reveal the true nature of the mechanism that takes
place [214]. The reaction kinetic equation limits the uptake rate
in only one mechanism [215]. Nevertheless, metal adsorption on
minerals is considered a diffusion process in which more than one
stage may be observed to take place.
Table 13 [40,44,47,49,56,63,86,87,98,99,120,124,125,142,189,
204] lists the diffusion model constants including the effective
diffusion coefficients (Deff ) concerning Ni and Zn adsorption on
minerals. The adsorption of metal ions on a solid surface occurs
due to the concentration difference between the liquid and the
solid phase. The transfer of metal ions from the liquid to the solid
phase is a complex process, which involves the diffusion into the
boundary layer that surrounds the solid particles, as well as, on
the surface and the interior of the solid particles. The adsorption
of metal ions on the solid surface includes the following stages
[63,216]: (i) the transfer of the metal ions from the bulk solution
to the liquid–solid interface which takes place through convection,
(ii) the diffusion of the metal ions through the boundary layer that
surrounds the solid particles, reaching the solid surface (i.e. film
diffusion), (iii) the diffusion of metal ions on the surface (surface
diffusion) and the interior (pore diffusion) of the solid particle (iv)
the adsorption of the metal ions to active adsorption sites on the
mineral’s surface. This stage is considered to be an equilibrium
reaction.
The stages that define the process may take place either in par-
allel or in series. If they take place in parallel and are independent
of each other, then the total rate is given by the sum of the rate
of each stage. On the contrary, if they take place in series then at
steady state conditions these have the same rate which is equal
to the total rate. In solid–liquid systems and in non-catalytic reac-
tions the stages are considered to take place in series [172]. The
slowest stage is the rate controlling step. According to Helfferich
[217] stage (iv) takes place very quickly and does not influence the
rate of diffusion. In addition, stage (i) occurs very quickly since the
metal ions are readily available at the surface of the boundary layer.
Therefore, the total rate of adsorption is defined either by the rate
of the boundary layer diffusion (rate ii) or by the rate of the intra-
particle diffusion (rate iii) or by the rates of both stages. If the third
stage is the only one that controls the process, then a concentra-
tion gradient exists only within the solid, while when the process
is controlled only by the second stage, then there is a concentra-
tion gradient only in the boundary layer [217–220]. In Fig. 2 [220],
stages (ii) and (iii) are represented diagrammatically. The top part
of Fig. 2 shows the external mass transfer resistance that occurs at
the liquid–solid interface. At the lower part of Fig. 2 intraparticle
diffusion is shown to take place.
Sprynskyy et al. [52] noted that the adsorption of nickel on
clinoptilolite was a three-stage process associated with fast adsorp-
tion at the initial stage, an inversion stage with the prevalence
of desorption at the second stage and moderate adsorption of
nickel inside the mineral’s micro-crystal interior at the third stage.
Al-Degs et al. [219] investigated the uptake of zinc by a natural
aluminosilicate and carbonate sorbent and found that the sorption
 S. Malamis, E. Katsou / Journal of Hazardous Materials 252–253 (2013) 428–461 445

Table 10
Summary of removal efficiencies achieved by adsorption of nickel and zinc on zeolite, bentonite and vermiculite.

Metal Solution/ Adsorbent C0 (mg L−1 ) pH/T (◦ C) Adsorbent Removal Reference

Wastewater concentration (g L−1 ) efficiency (%)

Ni Aqueous Montmorillonite 5.87 5.5/Room temp. 1 g/column >99 [26]

Ni Aqueous Vermiculite 5.87 5.5/Room temp. 1 g/column 33 [26]
Ni Aqueous Vermiculite 5.87 8.0/Room temp. 1 g/column 78 [26]
Ni Aqueous Clinoptilolite 50 8/23 10 68.2 [40]
NaCl clinoptilolite 77.1
HCl and NaCl clinoptilolite 92.5
Ni Aqueous ZrO-montmorillonite 50 1.0–8.0/30 2.0 17.7–38.6 [47]
TBA-montmorillinite 17.1–33.1
Ni Aqueous Zeolite 100 10/25 8 91.9 [48]
6/25 8 86.5
Ni Aqueous Calcined Bofe bentonite 50 2.18–9.94/20 10 15.0–87.5 [49]
Ni Aqueous Calcined Bofe bentonite 50 5.3/20 5–40 28.31–81.93 [49]
Ni Aqueous Calcined Bofe bentonite 2.66–177 5.3/20 10 93.23–13.56 [49]
Nia Aqueous Clinoptilolite 10 5/– 5 30 [50,51]
Zna 88
Nia Aqueous Chabazite 10 5/– 5 99 [50,51]
Zna 99
Ni Aqueous Clinoptilolite 50 5/25 50 57 [54]
Zn 98
Ni Aqueous Clinoptilolite 10–40 6.2/25 2.5 [52]
Ni Nickel Synthetic zeolite 50 4.0/Room temp. 2.5 86 [52]
electroplating
wastewater
Ni Aqueous Zeolite 31.69 7.8/20 20 80 [55]
Ni Aqueous Zeolite 6.22 7.5/20 100 75 [55]
Ni Aqueous Na-montmorillonite 50 6.5/25 6 90 [56]
Acid modified 75 58
montmorillonite
Ni GMZ-Bentonite 6.0 8.5/30 0.5 >90 [68]
Aqueous 6.4/30 1.0–1.2 52
Ni EDTA Na-montmorillonite 5.87 5.5/25 Fixed bed column 8.5 [74]
NTA 5.9
Tartaric acid 65.3
Oxalic acid 93.9
Manolic acid 100
Succinic acid 96.3
Glutaric acid 98.6
Citric acid 95.3
Ni Aqueous Na-bentonite 100 6/22 10 100 [82]
Ca-bentonite 100
Na-bentonite 100
Ca-bentonite 100
Ni Aqueous Vermiculite 320 6/25 10 51.3 [96]
Bentonite 29.8
Zeolite 19.0
Ni Aqueous Clinoptilolite 25 7/20 15 93.6 [98]
Ni Aqueous Bentonite 100 3.0/60 2.5 72.72 [100]
Ni Na-bentonite 50 9.0/25 1 80 [101]
Aqueous –/25 6 >95
Ni Aqueous Na-montmorillonite 5.87 9/20 0.6 ≈95 [102]
5.8/20 0.8 42
Ni Aqueous Bentonite 500 –/25 100 98.4 [123]
8/25 10 77.8
Ni Aqueous Scolecite 30 6/ 5 10 [128]
Room temp.
Ni Synthetic and Na-zeolite 50 7/25 10 36 [141]
wastewater Gördes zeolite 10 40
Bigadic zeolite 5 38
Bigadic zeolite 10 35
Ni Aqueous Montmorillonite 10 5.7/30 2.0 84.3 [142]
50 62.7
Ni Aqueous Acid-activated 10 5.7/30 2.0 91.5 [142]
montmorillonite 50 69.2
Ni Aqueous Montmorillonite 50 1.0–10.0/30 2.0 50.1–96.4 [143]
Acid-activated 56.3–99.2
montmorillonite
Ni Aqueous Montmorillonite 50 5.7/30 2.0 62.7 [144,145]
TBA-montmorillonite 26.5
Ni Multi metal Vermiculite 14.67 2.0/25 20 33.3 [146]
aqueous Acid treated vermiculite 21.1
solution
Ni Aqueous Zeolite 50 6/Room temp. 10 45 [163]
NaCl-zeolite 58
Ni Multi (Pb, Cd, Zeolite 50 6/Room temp. 10 15 [163]
Cu, Zn, Ni) NaCl-zeolite 22
446 S. Malamis, E. Katsou / Journal of Hazardous Materials 252–253 (2013) 428–461

Table 10 (Continued)

Metal Solution/ Adsorbent C0 (mg L−1 ) pH/T (◦ C) Adsorbent Removal Reference

Wastewater concentration (g L−1 ) efficiency (%)

Ni Aqueous Zeolite-clinoptilolite 50 –/Room temp. 10 44 [173]

Zn 57
Zn Aqueous Clinoptilolite 5 6.74–6.70/25 10.5 98 [6]
10–100 94–66
Zn Aqueous Fe-oxide clinoptilolite 10–100 6.90–6.75/25 10.5 >99 [6]
Zn Aqueous Zeolite–Portland cement 600 8.0/23 40 90 [11]
mixture
Aqueous Montmorillonite 6.54 5.5/ 1 g/column >99 [26]
Zn Room temp.
Zn Aqueous Vermiculite 6.54 5.5/ 1 g/column 32 [26]
Room temp.
Zn Aqueous Vermiculite 6.54 8.0/ 1 g/column >99 [26]
Room temp.
Zn Aqueous Zeolite 30.73 7.4/20 20 71 [55]
Zn Aqueous Zeolite 6.93 7.0/20 100 90 [55]
Zn Aqueous Vermiculite 25–500 Unadjusted/25 10 74.04–9.92 [57]
150 99.42–62.39
Zn Aqueous Zeolite 37.27–659 5.53–5.26/23 10 92 [59]
Zn Aqueous Gordes zeolite 20 4/ 1 68 [60]
Bigadic zeolite Room temp. 68
Zn Cankiri bentonite 100 8.0/23 5 >98 [61]
Aqueous
Zn Aqueous Zeolite 50 6–7/25 20 45.96 [62]
Zn Aqueous Jordanian zeolite (column) 5 6/27 5 97.6 [64]
20 99.0
Zn Aqueous Jordanian zeolite 5 6/27 5 77 [64]
(batch system) 20 85
Zn Aqueous Turkish zeolite 21 5.6/25 20 100 [65]
Zn EDTA Na-montmorillonite 6.54 5.5/25 Fixed bed column 0.3 [74]
NTA 0.1
Tartaric acid 49.4
Oxalic acid 63.9
Manolic acid 81.2
Succinic acid 97.4
Glutaric acid 99.3
Citric acid 94.4
Zn Aqueous Humic acid-immobilized- 25 10/30 2 99 [80]
amine-modified
polyacrylamide/bentonite
composite
Zn Acid zinc Synthetic zeolite 50 6.0/ 2.5 66 [81]
wastewater Room temp.
Zn Aqueous Na-bentonite 100 6/22 10 100 [82]
Ca-bentonite 100
Na-bentonite 100
Ca-bentonite 100
Zn Multi Synthetic Zeolite (synthetic MAP) 0.5 3.2/– 10 96.8 [84]
(Pb, Cu, Zn, solution Zeolite (natural mordenite) 41.8
Cd)
Zn Multi Motorway Zeolite (natural mordenite) 0.5 7.1/– 10 96.5 [84]
(Pb, Cu, Zn, stormwater 10.1
Cd)
Zn Aqueous Vermiculite 320 6/25 10 75.3 [97]
Bentonite 82.4
Zeolite 49.3
Zn Aqueous Zeolite 4A 25–100 6.5/30 25 97–87 [105]
Zeolite 13X 94.9–78.8
Bentonite 92.4–72.0
Zn Aqueous Bentonite 100 6/25 10 ≈66 [108]
40 ≈80
Zn Aqueous Serbian clinoptilolite 100–600 6/25 1 13–26 [125]
Zn Aqueous Bentonite – 5/20 10 33.9 [126]
Zn Acidic mine Natural zeolite 49 2.2 20 23.4 [129]
water 41 5.5 93.6
Weakly acidic
mine water
Zn Aqueous Vermiculite 16.35 2.0/25 20 36.42 [146]
Acid treated vermiculite 18.42
Zn Aqueous Heated (110 ◦ C) bentonite 58.22 3.32/30 0.25 13.9 [153]
Heated (200 ◦ C) bentonite 4.54/30 0.50 19.9
0.5 mol L−1 H2 SO4 2.88/30 0.25 11.2
bentonite 2.29/30 0.25 8.2
2.5 mol L−1 H2 SO4
bentonite
 S. Malamis, E. Katsou / Journal of Hazardous Materials 252–253 (2013) 428–461 447

Table 10 (Continued)

Metal Solution/ Adsorbent C0 (mg L−1 ) pH/T (◦ C) Adsorbent Removal Reference

Wastewater concentration (g L−1 ) efficiency (%)

Zn Aqueous Montmorillonite 0.059 6.5/25 2.5 49 [155]

HyA-montmorillonite ∼100
HAS-montmorillonite ∼100
Zn Aqueous Zeolite 50 6/Room temp. 10 58 [163]
NaCl-zeolite 93
Zn Multi (Pb, Cd, Zeolite 50 6/Room temp. 10 18 [163]
Cu, Zn, Ni) NaCl-zeolite 55
a
Mixed metal solution.

adsorption capacity (qe ). On the contrary, the pseudo-first-order

Fig. 2. Diagrammatic representation of stages (ii) and (iii) of the diffusion of metal
ions in the adsorbent [220].
rate was slow with only 10–20% of the adsorption occurring dur-
ing the first 30 min. The experimental kinetics data fitted well
to the pseudo-first-order and to the external diffusion models
and thus external diffusion was more important than intraparti-
cle diffusion. Ijagbemi et al. [42] found that the rate constant of
the pseudo-second-order model decreased with increasing initial
metal concentration and thus more time was required to reach
equilibrium. The authors also examined the intraparticle diffusion
model and identified two distinct plots indicating that intraparticle
diffusion was not the only rate limiting mechanism. They applied
Boyd’s model and concluded that film diffusion is also important
at least to some extent. Gupta and Bhattacharyya [44] compared
the experimental data with various kinetic models and found that
the pseudo-second-order model closely matched the experimental
data and could provide a reasonable prediction for the equilibrium
model could not adequately predict qe , despite its high correla-
tion with the experimental data. The application of the intraparticle
diffusion model showed that this mechanism was important; the
authors also concluded that liquid film diffusion was influential in
the process of nickel adsorption on natural and modified montmo-
rillonite [44,47]. Trgo et al. [204] used the homogeneous diffusion
model and Vermeulen’s approximation to determine Deff for zinc
adsorption on Na-modified clinoptilolite and found that it was
of the order of 10−12 m2 s−1 and was independent of the initial
metal concentration, while it decreased with increasing adsorp-
tion time. The authors identified two linear areas for both models.
The first area was associated with diffusion through the mineral
macropores, while the second area was associated with diffusion
through the crystal lattice. Taparcevska et al. [189] applied the
parabolic diffusion model and Vermeulen’s approximation on their
experimental data of zinc adsorption on clinoptilolite and found
an effective diffusion coefficient that was two orders of magni-
tude higher than that obtained by Trgo et al. [204] and concluded
that Deff depended on initial metal concentration. Rajic et al. [120]
found that the adsorption process on clinoptilolite involved film
diffusion, intraparticle diffusion and cation exchange. Two distinct
adsorption regions were identified; the first one corresponding
to film diffusion characterized by high diffusion rates and the
second one to intraparticle diffusion having lower diffusion rate.
The authors also mentioned that the pseudo-second-order model
closely matched the experimental results. Sen and Gomez [63] con-
cluded that the kinetics of zinc adsorption on bentonite was a
two-stage process involving a rapid adsorption of the metal ions
on the mineral’s external surface followed by intraparticle diffu-
sion. The two-stage adsorption process has also been observed
by Stojakovic et al. [125]. Katsou et al. [96,97] found that the
adsorption of zinc and nickel on zeolite, bentonite and vermicu-
lite followed a three-stage diffusion process, where external mass
transfer was dominant at the early stages and intraparticle diffu-
sion at the later stages of the process. The authors found that Deff
was of the order of 10−13 –10−14 m2 s−1 and its value followed the
order vermiculite > bentonite > zeolite. A three-stage diffusion pro-
cess has also been identified by Ijagbemi et al. [56] for nickel uptake
by Na-montmorillonite and acid modified montmorillonite, with
limited contribution of mass transfer and boundary layer diffusion.
Taparcevska et al. [189] found that the increase of metal concen-
tration until a certain point is not accompanied by a decrease in the
effective diffusion coefficient. Other researchers did not find a clear
trend between Deff and metal concentration [63,204]. The effect of
competing ions and of the adsorbate type on the effective diffusion
coefficient has not been documented.

Table 11a
Reaction kinetic models.

Model Non-linear equation Linear equation Model parameters Reference

−k1 t
Pseudo-first-order qt = qe (1 − e ) ln(qe − qt ) = ln qe − k1 t qe , k1 [192]
Pseudo-second-order qt = q2e k2 t/(1 
+ qe k2 t)   2 qe ) + t/qe
t/qt = 1/(k 2
qe , k2 [193]
Elovich qt = (1/ˇe )ln ˛ˇe t + 1 qt = ln ˛ˇe /ˇe + ln t/ˇe ˛, ˇe [194,195]
 448
Table 11b

S. Malamis, E. Katsou / Journal of Hazardous Materials 252–253 (2013) 428–461

Diffusion models.

Model Equation Model parameters Reference

Intraparticle qt  0.5
= kid t  kid [196]
External mass transfer ln (C0 − Cs ) / (Ct − Cs ) = kf am t; am = 6ma / (dp b ) kf , am , Cs [187,197,198]
 0.5
F ≤ 0.85 ⇒ Bt = 2 − 2 F/3 − 2 1 − F/3 ;
Reichenberg F > 0.85 ⇒ Bt = −0.4977 − ln (1 − F); Deff [199,200]
B = 2 Deff /r 2 ; F = qt /qe
 
∞
   
Boyd F = 1 − 6/2 1/n2 exp −n2 Bt [201]

n=1   0.5
Non-linear: F = 1 − exp
 −
2 2
Deff t /r
Vermeulen   Deff [202]
Linear: ln 1/ 1 − F 2 = 2 Deff t/r 2
   
Homogeneous diffusion model (t→∞) ln 1 − qt /qe = ln 6/2 − Deff 2 t/r 2 Deff [203]
 0.5  √ −1  1.5
Parabolic diffusion Original formula F = 4−0.5 Deff t/r 2 − Deff t/r 2 − 3  Deff t/r 2 Deff [204,205]
−0.5
   0.5
Parabolic diffusion Simplified formula F/t = 4 2
Deff / r t − Deff /r
2
Deff [204,205]
Liquid film diffusion ln (1 − F) = −kfd t kfd [201]

∞
 
F =1− ai exp −bi t/ ;  = r /Deff ;
2

Homogeneous diffusion Deff [204–206]

i=0
Spherical particles and t → t0 ⇒ F = 6−0.5 Deff
0.5 0.5
t /r
 
Spherical particles and t → t∞ ⇒ ln(1 − F) = ln 6/2 − 2 Deff t/r 2
Film diffusion equation Df = 0.23rqe ı/t1/2 Df [98,207,208]
Pore diffusion equation Dp = 0.03r 2 /t1/2 Dp [98,207,208][63,209]
Table 12
Applications of reaction kinetic models on nickel and zinc adsorption on zeolite, bentonite and vermiculite.

Metal Mineral C0 (mg L−1 )/pH/T Experimental qe Pseudo-first-order Pseudo-second-order Elovich Equilibrium Reference
(◦ C) (mg g−1 ) time (h)

Predicted qe R2 Predicted qe R2 R2
(mg g−1 ) (mg g−1 )
Ni Clinoptilolite 50/–/23 3.56 0.9998 0.9585 3–3.33 [40]
NaCl clinoptilolite 4.19 1.000 0.8876
HCl and NaCl clinoptilolite 4.22 0.9775 0.9642
Ni Montmorillonite 50/6/25 1.52 2.56 0.887 1.53 0.998 [42]
100/6/25 3.11 4.36 0.721 3.15 0.999
200/6/25 5.68 5.66 0.583 5.70 0.998
300/6/25 5.61 6.05 0.688 5.62 0.999

S. Malamis, E. Katsou / Journal of Hazardous Materials 252–253 (2013) 428–461

Ni Montmorillonite 50/5.7/30 15.70 12.69 0.97 16.52 0.99 0.99 3 [44,47]
ZrO-montmorillonite 7.43 13.32 0.96 9.00 0.99 0.99
TBA-montmorillinite 6.38 11.71 0.97 8.00 0.99 0.99
Ni Calcined Bofe bentonite 50/5.3/20 ≈1.8 0.35 0.9009 1.80 0.9971 2.5 [49]
Ni 50/6.5/25 7.54 5.04 0.988 7.81 0.999 0.975 3.83 [56]
Na-montmorillonite 75/6.5/25 8.29 7.84 0.860 8.37 0.999 0.985
100/6.5/25 10.04 9.75 0.998 10.18 0.999 0.987
Ni Acid modified montmorillonite 50/6.5/25 4.57 3.77 0.972 4.95 0.999 0.981 [56]
75/6.5/25 7.09 5.44 0.978 7.47 0.999 0.984
100/6.5/25 7.31 8.32 0.979 7.61 0.999 0.988
Ni GMZ Na-bentonite 6.0/6.4/30 4.56 0.9997 24 [68]
Ni (Co, Cr, Cu, Zn, Ni) Zeolite 4A 50/3/25 7.59 7.63 0.963 [92]
100/3/25 3.98 3.87 0.942
50/4/25 11.51 10.49 0.956
100/4/25 6.14 4.95 0.989
Ni Zeolite 320/6/25 6.08 4.12 0.9046 6.51 0.9993 0.9792 2 [96]
Bentonite 9.52 5.72 0.9831 10.02 0.9995 0.9732 2
Vermiculite 16.42 5.99 0.9499 16.81 0.9998 0.8726 2
Ni Clinoptilolite 25/7/20 1.61 0.174 1.60 0.9998 [98]
25/7/40 1.58 0.15 1.59
25/7/60 1.56 0.12 1.58
Ni Chitosan–clinoptilolite composite 4109/5/25 375.9 536.9 0.940 416.8 0.999 24 [99]
Ni Na-bentonite 50/–/25 13.02 0.9844 13.66 0.9967 3.33 [101]
Ni Zeolitic tuff 100/6/25 1.9 0.964 2.23 0.988 >24 [120]
100/6/35 3.1 0.988 3.35 0.990
100/6/45 3.8 0.978 4.11 0.991
100/6/55 4.9 0.990 5.20 0.989
Ni Zeolitic tuff 200/6/25 2.5 0.974 2.78 0.992 >24 [120]
200/6/35 4.0 0.996 4.35 0.990
200/6/45 5.4 0.984 5.61 0.993
200/6/55 6.9 0.992 7.18 0.988
Ni Zeolitic tuff 300/6/25 3.0 0.998 3.31 0.999 >24 [120]
300/6/35 4.9 0.984 5.12 0.991
300/6/45 6.0 0.987 6.27 0.990
300/6/55 8.3 0.992 8.47 0.995
Ni Zeolitic tuff 400/6/25 3.3 0.989 3.57 0.992 >24 [120]
400/6/35 5.2 0.990 5.36 0.997
400/6/45 6.2 0.962 6.42 0.990
400/6/55 8.9 0.978 9.15 0.989
Ni Bentonite 200/–/25 ≈9 0.56 0.06 9.19 0.99 0.5 [123]
Ni Montmorillonite acid-activated 50/5.7/30 15.7 12.7 0.97 16.5 0.99 0.99 3 [142]
montmorillonite 17.3 12.9 0.96 18.1 0.99 0.99
Ni Activated carbon – zeolite composite 500/–/25 115.63 65.74 [174]
(type 1)

449
 450
Table 12 (Continued)

Metal Mineral C0 (mg L−1 )/pH/T Experimental qe Pseudo-first-order Pseudo-second-order Elovich Equilibrium Reference
(◦ C) (mg g−1 ) time (h)

Predicted qe R2 Predicted qe R2 R2
(mg g−1 ) (mg g−1 )
Ni (Ni, Pb) Vermiculite Variable/5.0/20 ≈12.6 0.9379 13.04 0.9940 0.8729 1 [176]
Ni (Ni, Ag) ≈14.2 0.9522 14.23 0.9931 0.8549
Ni (Ni, Cd) ≈8.9 0.9269 9.01 0.9967 0.8405
Ni (Ni, Ag, Pb) ≈12.6 0.9917 12.77 0.9932 0.8878
Ni (Pb, Ni, Cd) ≈8.5 0.5206 8.73 0.9998 0.5762
Ni (Ag, Ni, Cd) ≈9.0 0.9350 9.16 0.9986 0.4768
Ni (Ag, Ni, Cd, Pb) ≈7.8 0.9634 8.09 0.9987 0.7921
Zn Cankiri bentonite 20/8/23 3.6 0.377 0.9211 3.60 0.9998 0.17 [61]
100/8/23 19.6 1.116 0.8162 19.60 0.9999
160/8/23 31.6 2.298 0.8411 31.64 1.000
Zn Bentonite 30/6.76/30 7.5 7.97 0.9852 1.33 [63]

S. Malamis, E. Katsou / Journal of Hazardous Materials 252–253 (2013) 428–461

40/6.76/30 10.0 9.89 0.9765
50/6.76/30 47.2 47.17 0.9958
Zn Bentonite 30/3.81/30 11.8 11.93 0.9847 1.33 [63]
30/6.76/30 47.4 46.95 0.9954
30/7.69/30 28.8 28.49 0.9978
Zn (Co, Cr, Cu, Zn, Ni) Zeolite 4A 50/3/25 26.58 30.14 0.997 [92]
100/3/25 9.22 10.54 0.975
50/4/25 40.38 41.17 1.000
100/4/25 19.59 20.10 0.997
Zn Zeolite 320/6/25 15.76 13.23 0.9803 18.35 0.9951 0.8565 2 [97]
Bentonite 26.36 15.76 0.9901 27.10 0.9988 0.9479 1
Vermiculite 24.08 10.05 0.8850 24.21 0.9993 0.9825 1
Zn Zeolite 4A Low value 0.9975 1.5 [105]
Zeolite 13X 25/6.5/30 0.9963
Bentonite 0.9964
Zn Zeolite A 500/–/25 158.87 0.947 263.29 0.993 0.75 [124]
500/–/40 185.03 0.927 355.67 0.991
500/–/60 207.91 0.941 402.54 0.995
Zn Na-clinoptilolite 100/6/25 ≈5.6 0.995 6.67 0.998 >24 [125]
100/6/35 ≈6.5 0.985 8.30 0.996
100/6/45 ≈7.6 0.980 8.81 0.994
100/6/55 ≈8.3 0.998 8.71 0.999
Zn Na-clinoptilolite 200/6/25 ≈8.0 0.987 9.98 0.995 >24 [125]
200/6/35 ≈10.3 0.983 12.50 0.996
200/6/45 ≈11.5 0.997 13.87 0.998
200/6/55 ≈11.8 0.998 12.7 0.999
Zn Na-clinoptilolite 300/6/25 ≈9.7 0.909 12.0 0.985 >24 [125]
300/6/35 ≈11.8 0.996 14.3 0.998
300/6/45 ≈13.0 0.994 15.9 0.998
300/6/55 ≈13.6 0.969 13.9 0.999
Zn Na-clinoptilolite 400/6/25 ≈10.0 0.941 12.1 0.990 >24 [125]
400/6/35 ≈12.8 0.993 14.1 0.999
400/6/45 ≈14.0 0.996 15.5 0.999
400/6/55 ≈14.8 0.999 15.2 0.999
Zn Bentonite 200/5.5/28 16.36 16.18 0.9996 1 [154]
Sulphate-modified bentonite 17.17 17.21 0.9997
Phosphate-modified bentonite 17.50 17.76 0.9996
Zn Bentonite 300/5.5/28 24.48 26.11 0.9941 1 [154]
Sulphate-modified bentonite 26.19 26.95 0.9948
Phosphate-modified bentonite 26.63 28.01 0.9953
Zn Natural zeolite 50/const./25 ≈0.8 0.169 0.244 [210]
100/const./25 ≈1.7 0.385 0.267
120/const./25 ≈2.0 0.616 0.623
150/const./25 ≈2.7 0.762 0.766
180/const./25 ≈2.7 0.897 0.899
200/const./25 ≈2.0 0.945 0.950
250/const./25 ≈2.3 0.980 0.980
 S. Malamis, E. Katsou / Journal of Hazardous Materials 252–253 (2013) 428–461 451

Table 13
Intraparticle diffusion model and effective diffusion coefficients for nickel and zinc adsorption on zeolite, bentonite and vermiculite.

Metal Adsorbent C0 (mg L−1 )/pH/T Intraparticle diffusion Deff (m2 s−1 ) Model Reference
(◦ C)

R2 k (mg g−1 min−1/2 )

Ni Clinoptilolite 0.9650 44.45 [40]

NaCl clinoptilolite 0.8997 64.12
HCl and NaCl 0.9762 68.42
clinoptilolite
Ni Montmorillonite 50/5.7/30 0.95 0.417 [44,47]
ZrO-montmorillonite 0.95 0.436
TBA-montmorillinite 0.94 0.400
Ni Calcined Bofe 50/5.3/20 0.9557 0.0245 [49]
bentonite
Ni 50/6.5/25 0.978 0.122/0.118/0.020 [56]
Na-montmorillonite 75/6.5/25 0.987 0.429/0.204/0.031
100/6.5/25 0.987 0.738/0.384/0.036
Ni Acid modified 50/6.5/25 0.981 0.285/0.259/0.046 [56]
montmorillonite 75/6.5/25 0.984 0.334/0.311/0.052
100/6.5/25 0.989 0.584/0.343/0.058
Zn Bentonite 30/6.76/30 7.33 × 10−13 Film diffusion [63]
40/6.76/30 1.10 × 10−13 equation
50/6.76/30 1.41 × 10−12
Ni Zeolite 320/6/25 0.998/0.961/0.983 0.7/0.3/0.1 5.57 × 10−14 Vermeulen [86]
Bentonite 0.999/0.889/0.909 1.3/0.4/0.2 6.77 × 10−14
Vermiculite 0.990/0.957/0.947 3.0/1.1/0.1 7.18 × 10−14
Zn Zeolite 320/6/25 0.961/0.983/0.977 1.3/1.9/0.6 [87]
Bentonite 0.987/0.974/0.946 4.2/1.6/0.4
Vermiculite 0.980/0.986/0.966 5.5/1.3/0.3
Ni Clinoptilolite 25/7/20 2.5 × 10−13 [98]
25/7/40 2.3 × 10−13 Pore diffusion
25/7/60 2.0 × 10−13 equation
Ni Clinoptilolite 25/7/20 3.1 × 10−13 [98]
25/7/40 2.4 × 10−13 Film diffusion
25/7/60 1.9 × 10−13 equation
Ni Chitosan-clinoptilolite 4109/5/25 0.942 6.04 [99]
composite
Ni Zeolitic tuff 100/6/25 0.999 0.0272 [120]
100/6/35 0.958 0.0372
100/6/45 0.999 0.0370
100/6/55 0.929 0.0336
Ni Zeolitic tuff 200/6/25 0.974 0.0367 [120]
200/6/35 0.938 0.0390
200/6/45 0.999 0.0351
200/6/55 0.922 0.0361
Ni Zeolitic tuff 300/6/25 0.957 0.0373 [120]
300/6/35 0.926 0.0493
300/6/45 0.972 0.0383
300/6/55 0.960 0.0358
Ni Zeolitic tuff 400/6/25 0.997 0.0337 [120]
400/6/35 0.967 0.0330
400/6/45 0.989 0.0297
400/6/55 0.944 0.0328
Zn Zeolite A 500/-/25 0.999 26.54 1.83 × 10−12 [124]
500/-/40 0.993 30.79 2.34 × 10−12
500/-/60 0.998 33.34 3.05 × 10−12
Zn Na-clinoptilolite 100/6/25 0.999 0.0932 [125]
100/6/35 0.999 0.0590
100/6/45 0.999 0.0590
100/6/55 0.991 0.0827
Zn Na-clinoptilolite 200/6/25 0.997 0.136 [125]
200/6/35 0.999 0.161
200/6/45 0.986 0.153
200/6/55 0.972 0.123
Zn Na-clinoptilolite 300/6/25 0.957 0.107 [125]
300/6/35 0.991 0.165
300/6/45 0.995 0.228
300/6/55 0.999 0.0745
Zn Na-clinoptilolite 400/6/25 0.986 0.116 [125]
400/6/35 0.991 0.140
400/6/45 0.980 0.174
400/6/55 0.984 0.0961
Ni Montmorillonite 50/5.7/30 0.95 0.42 [142]
Acid-activated 0.95 0.42
montmorillonite
Zn Clinoptilolite 50/5–7/25 0.57 × 10−12 Vermeulen [189]
100/5–7/25 0.35 × 10−12
150/5–7/25 0.25 × 10−12
250/5–7/25 0.13 × 10−12
452 S. Malamis, E. Katsou / Journal of Hazardous Materials 252–253 (2013) 428–461

Table 13 (Continued)

Metal Adsorbent C0 (mg L−1 )/pH/T Intraparticle diffusion Deff (m2 /s) Model Reference
(◦ C)

R2 k (mg g−1 min−1/2 )

Zn Clinoptilolite 50/5–7/25 3.33 × 10−12 Parabolic [189]

100/5–7/25 2.40 × 10−12 diffusion
150/5–7/25 2.25 × 10−12
250/5–7/25 0.63 × 10−12
Zn Na-modified 194.8/5.56/23 3.83 × 10−14 Vermeulen [204]
clinoptilolite 396.1/5.36/23 6.22 × 10−14
490.5/5.42/23 5.70 × 10−14
600.5/5.33/23 3.08 × 10−14
718.7/5.26/23 3.58 × 10−14
Zn Na-modified 194.8/5.56/23 4.30 × 10−14 Homogeneous [204]
clinoptilolite 396.1/5.36/23 7.17 × 10−14 diffusion
490.5/5.42/23 6.23 × 10−14
600.5/5.33/23 4.68 × 10−14
718.7/5.26/23 4.45 × 10−14

Allen et al. [220] also attributed the initial stage of adsorption to
external mass transfer through the boundary layer surrounding the
particles, while the following stages represented intraparticle dif-
fusion into the branched porous network of the adsorbent particle
[42,63,120,221–224]. The diffusion mechanism depends on several
parameters including the structure and the type of adsorbent, the
physicochemical properties of the adsorbent and adsorbate, as well
as, other conditions that may affect the process performance.
7. Isotherms
Sorption isotherm is the equation or curve that connects the
metal concentration that has been adsorbed on the solid phase with
metal concentration in the solution at equilibrium for specific tem-
perature. The application of experimental data on equations that
describe the isotherms is valuable, since it results in the prediction
of the system’s performance and the optimisation of adsorbent use.
Sorption equilibrium provides fundamental physicochemical data
for evaluating the applicability of sorption processes as a unit oper-
ation. Sorption equilibrium is usually described by an isotherm
equation whose parameters express the surface properties and
affinity of the sorbent, at a fixed temperature and pH. Hence, an
accurate mathematical description of the equilibrium isotherm,
which is based on a correct adsorption mechanism, is essential
for the effective design of adsorption systems [20]. Equilibrium
models can be classified into empirical and mechanistic models.
Empirical models cannot represent the mechanisms of the sor-
bate uptake but can be used to predict the experimental results,
while the mechanistic models can represent the system mecha-
nisms [116,225,226]. Therefore, mechanistic models describe the
underlying interactions that take place between the metal ions in
the solution and the charged surface. Empirical models are usually

Table 14
Equilibrium models.

Isotherm Equation Linear Form Model Parameters Reference

Langmuir qe = qm KL Ce / (1 + KL Ce ) Ce /qe = 1/ (qm KL ) + Ce /qm KL , qm [227]

  [228]
Freundlich qe = KF Ce1/nF ln qe = ln KF + 1/nF ln Ce KF ,nF [229]
Langmuir-Freundlich qe = qm KLF C
1/nLF
e  + KLF Ce LF )
/ (1 1/n
KLF , qm , nLF [226,230]
qe = qm exp −ˇε2 ;
Dubinin–Radushkevich (DR)    −0.5 lnqe = lnqm − ˇε2 ˇ, qm [231]
ε = RT ln 1 + 1/Ce ; E = 2ˇ
     
Temkin qe = RT/b ln (ACe ) qe = RT/b ln A + RT/b ln Ce A, b [232]
ns ns
Sips qe = qm (as Ce ) / (1 + (as Ce ) ) ns , qm , aS [20]
  [230]
Redlich–Peterson qe = KR Ce / (1 + ˛R CeˇR ) ln KR Ce /qe − 1 = ln ˛R + ˇR ln Ce KR , ˛R , ˇR [233]
1    
Toth qe = KT Ce /(AT + CeTa ) ⁄T a ln qe /KT = ln Ce − 1/T ln (AT + CeTa ) AT , KT , Ta [234]
nK
Khan qe = qm bK Ce / (1+ bK Ce )    bK , qm , nK [235]
p p−1
Radke–Prausnitz qe = ˛RP rRP Ce / ˛RP + rRP Ce ln 1/qe − 1/ (˛RP Ce ) = − ln rRP − p ln Ce ˛RP , rRP , p [236]
 
Generalized qe = qm Ceng / (K + Ceng ) ln qm /qe − 1 = ln K − ng ln Ce K, ng [237]
BBET Ce qm Ce
 1   B −1   Ce 
BET qe = = + B BET qm Csb , BBET , qm [238]
   
(Csb −Ce )[(1+(BBET −1)Ce )/Csb ]
nFH   BBET qm
(Csb −Ce )qe BET Csb

Flory–Huggins /C0 = 1/ KFH 1 −  log /C0 = log KFH + nFH log(1 − ) , nFH , KFH [211,239]

     1 − Ce /C0
= 
Frumkin KFF Ce =  exp −f / 1 −  ln qe / (Ce (qF − qe )) = ln KFF + 2fqe /qF f, KFF , [240,241]

N

Competitive Redlich–Peterson qe,i = KR,i Ce,i 1+ ˇR,i

˛R,i Ce,i KR,i , ˛R,i , ˇR,i [233,242]

 i=1


N

Competitive Langmuir qe,i = qm,i KL,i Ce,i 1+ KL,i Ce,i KL,i , qm,i [229]

 i=1


N

Competitive combined qe,i = 1/ni

qm,i KL,i Ce,i 1+ 1/ni
KL,i Ce,i ni , KL,i , qm,i [232]
Langmuir–Freundlich
i=1
 S. Malamis, E. Katsou / Journal of Hazardous Materials 252–253 (2013) 428–461 453

Table 15
Summary of isotherms investigation for nickel and zinc adsorption on zeolite, bentonite and vermiculite.

Metal Metal Sorbent C0 (mg L−1 ) Dosage pH/T (◦ C) qm (mg g−1 ) Isotherm Reference
(g L−1 )

Ni Single Natural zeolite 12.5–200 10 7–8/23 8.7 (L) L [40]

Conditioned zeolite 10.8 (L)
Ni Single Montmorillonite 50–300 20 6/25 12.89 (L) L [42]
Ni Single Montmorillonite 10–50 2 5.7/30 21.14 (L) L, F [44,47]
ZrO-montmorillonite 10.45 (L)
TBA-montmorillonite 8.50 (L)
Ni Single Montmorillonite 10–250 2 31.05 (L) L, F [44,47]
ZrO-montmorillonite 5.7/30 31.44 (L)
TBA-montmorillonite 30.67 (L)
Ni Single Turkish zeolite 1–100 8 5–6/20 119.7 (L) L, F [48]
Ni Single Calcined Bofe bentonite 3–200 10 5.3/20 2.875 (L) L [49]
5.3/40 3.072 (L)
5.3/50 3.047 (L)
5.3/75 3.893 (L)
Ni Single Ukraine clinoptilolite 10–800 2.5 6.2/25 13.03, 15.55 (E, L) L, F [52]
Ni Single Jordanian zeolitic tuff 50–400 1–8 4/20 25.59, 22.30 (L, E) L [53]
(phillipsite)
Ni Single Turkish clinoptilolite 50–3000 50 5/25 8.21, 8.24 (E, L) F, L [54]
Ni Single Na-montmorillonite 50–100 6 6.5/25 10.65, 9.345 (L, DR) RP [56]
Acid modified 11.02, 8.566 (L, DR) DR
montmorillonite
Ni Single GMZ Na-bentonite 0.5 6.4/30 14.38; 104.47 (L, L, DR, F [68]
6.4/45 DR)
6.4/60 14.44; 108.00 (L,
DR)
14.61; 112.69 (L,
DR)
Ni Single Natural zeolite 10–200 2.5 6/22 2.00 (L) L [81]
Synthetic zeolite 20.07 (L) L
Ni Single Na-bentonite 10–150 2.5 6/22 24.2 (L) L [82]
Ca-bentonite 10 6.32 (L)
Ni Single Natural vermiculite 10–100 2.5 19.3 (L) L, F [83]
Exfoliated vermiculite 10 6/22 5.91 (L)
Ni Single Zeolite 10–500 10 16.86, 9.83 (L, DR) L [96,97]
Bentonite 6/25 19.92, 11.96 (L, DR)
Vermiculite 25.51, 20.91 (L, DR)
Ni Single Heated (350 ◦ C) clay 10–200 0.5 5/20 80.9 (L) L [86]
Ternary containing 23.3 (L)
(Ni, Cu, Zn) montmorillonite and
hydromica
Ni Multi (Co, Commercial zeolite 4A 50–300 each 5 3/25 7.9 (L) L [92]
Cr3+ , Cu, Coal fly ash prepared metal 8.96 (L) L
Zn, Ni) zeolite 4A
Ni Single Zeolite 0.1–100 15 7/20 3.28 (L) [98]
7/40 2.97 (L) L
7/60 2.65 (L)
Ni Single Chitosan-clinoptilolite 147–5869 10 5/25 466.03 (L) L [99]
Ni Single Bentonite 50–300 25 3/30 4.31 (L) L [100]
Ni Single Na-montmorillonite 0.6 5.8/20 3.82 (L) L [102]
5.8/37 7.04 (L)
5.8/67 10.56 (L)
Ni Single Natural zeolitic tuff 100–600 10 6/25 4.48, 16.64 (L, S) S [120]
6/35 6.15, 6.43 (L, S)
6/45 7.04, 6.52 (L, S)
6/55 10.42, 10.71 (L, S)
6/65 11.44, 11.46 (L, S)
Ni Single Bentonite 108–427 15 5/25 819.7, 155.1 (L, DR) L [122]
Ni Single Natural bentonite 40–2000 10 –/20 25 (L) L [123]
–/40 27 (L)
–/60 33 (L)
Ni Single Montmorillonite 10–250 2 5.7/30 28.4 (L) L, F [142,145]
Acid-activated 29.5 (L)
montmorillonite
Ni Single Montmorillonite 10–250 2 5.7/30 21.1 (L) L, F [143]
Acid-activated 21.3 (L)
montmorillonite
Ni Single Montmorillonite 10–250 2 5.7/30 28.4 (L) L, F [144]
TBA-montmorillonite 19.7 (L)
Ni Multi (Cd, Vermiculite 5–500 60 4.5/25 0.32 (L) L [166]
Cr, Cu, Ni,
Pb, Zn)
Ni Single Activated carbon-zeolite 9-293 2 25 70.43 (L) L [174]
composite (type 1) 62.22 (L)
Activated carbon-zeolite
composite (type 2)
454 S. Malamis, E. Katsou / Journal of Hazardous Materials 252–253 (2013) 428–461

Table 15 (Continued)

Metal Metal Sorbent C0 (mg L−1 ) Dosage pH/T (◦ C) qm (mg g−1 ) Isotherm Reference
(g L−1 )

Ni Single Zeolitized vermiculite 29–2935 6–8/22 16.5 (L) L [251]

Clinoptilolite 2.3 (L) L
Zn Single Zeolite–Portland cement 50–1600 40 8/25 12.85 (L) L [11]
mixture
Zn Single Turkish clinoptilolite 50–3000 50 5/25 8.21, 8.24 (E, L) F, L [54]
Zn Single Na-enriched bentonite 12.5–200 1.0 4/25 57.4, 54 (L, E) L [58]
Natural bentonite 30.7, 24 (L, E)
Zn Single Croatian zeolitic tuff 37–659 10 5.3–5.5/25 13.5, 13.1 (DR, DR, MDR [59]
MDR)
Zn Single Gordes zeolite 2.5–20 1 4/25 6.60 (L) F [60]
Bigadic zeolite 4/25 3.59 (L)
Zn Single Cankiri bentonite 20–160 5 8/23 80.64 (L) L, F [61]
Zn Single Zeolite 100–400 20 6–7/30 8.75; 0.02 (L, DR) L, DR [62]
Zn Single Bentonite 10–90 0.25 6.76/30 68.49 (L) L [63]
Zn Single Zeolite 5–35 5 6/27 41.84, 62.90 (L, DR) F, DR [64]
Zn Single Turkish zeolite 78.59–1012.78 15 5.6/ 19.49 (L) L [65]
Zn Single Humic acid-immobilized- 10–300 2 9/30 52.93 L [80]
amine-modified
polyacrylamide/bentonite
composite
Zn Single Natural zeolite 10–200 2.5 6/22 3.47 (L) L [81]
Synthetic zeolite 32.42 (L) L
Zn Single Na-bentonite 10–150 2.5 6/22 23.1 (L) L [82]
Ca-bentonite 10 5.75 (L)
Zn Single Heated (350 ◦ C) clay 10–200 0.5 5/20 63.2 (L) L [86]
Ternary containing 26.6 (L)
(Ni, Cu, Zn) montmorillonite and
hydromica
Zn Multi (Co, Commercial zeolite 4A 50–300 each 5 3/25 31.6 (L) L [92]
Cr3+ , Cu, Coal fly ash prepared metal 30.80 (L) L
Zn, Ni) zeolite 4A
Zn Single Vermiculite 327 2.5 5.2/22 86.30, 60.80 (L, E) L [103]
Zn Single Zeolite 10–500 4–16 Not 3.926 (L) L [104]
adjusted/25 4.097 (L)
Not 4.172 (L)
adjusted/35
Not
adjusted/45
Zn Single Zeolite 4A 25–100 25 2.3/30 42.82 (L) L [105]
Zeolite 13X 38.31 (L)
Bentonite 35.17 (L)
Zn Single Natural bentonite 10–750 2 5/20 36.63 (L) L [106]
Composite E20 bentonite 29.67 (L)
Composite A85 bentonite 14.10 (L)
Zn Single Surfactant-modified [107]
montmorillonite 294–2942 2.5 3/25 13.27 (L) L, DR
Surfactant-modified
montmorillonite
Zn Single Bentonite 50–100 5 6/25 9.12 (L) L [108]
Binary 5.80 (L)
(Zn–Pb)
Zn Single Synthetic zeolite A 10–2000 0.5 –/25 165.41, 281.53 (L, F, DR [124]
–/40 DR)
–/60 166.72, 290.61 (L,
DR)
185.68, 293.16 (L,
DR)
Zn Single Serbian natural 100–600 10 6/25 12.0, 170 (L, S) L [125]
clinoptilolite 6/35 15.5, 22.6 (L, S)
6/45 15.8, 19.5 (L, S)
6/55 16.6, 21.7 (L, S)
6/65 16.8, 17.5 (L, S)
Zn Single Bentonite 300 0.1–10 4.5/20 52.91 (L) L [127]
4.5/40 33.11 (L)
4.5/80 25.77 (L)
Zn Single Clinoptilolite 10 4/25 46.22 (L) L [149]
Na-clinoptiloloite 51.19 (L)
Ca-clinoptilolite 43.09 (L)
Zn Single Clinoptilolite 0–500 20 –/20 3.15 (L) L [151]
Philipsite 1.70 (L)
Chabazite 7.98 (L)
Analcime 3.67 (L)
Bentonite 3.08 (L)
Zn Single Clinoptilolite 1–5 4.54, 4.58 (L, E) L [152]
Na-clinoptilolite 8.14, 8.17 (L, E)
 S. Malamis, E. Katsou / Journal of Hazardous Materials 252–253 (2013) 428–461 455

Table 15 (Continued)

Metal Metal Sorbent C0 (mg L−1 ) Dosage pH/T (◦ C) qm (mg g−1 ) Isotherm Reference
(g L−1 )

Zn Single Heated (110 ◦ C) treated 10–140 1 8/30 3.32 (L) [153]

bentonite 0.5 7.9/30 4.54 (L) L
Heated (200 ◦ C) treated 3.7/30 2.88 (L)
bentonite 3.5/30 2.29 (L)
H2 SO4 (0.5 mol L−1 ) treated 1
bentonite 1
H2 SO4 (2.5 mol L−1 ) treated
bentonite
Zn Multi Vermiculite 5–500 60 4.5/25 2.64 (L) L [166]
(Cd–Cr–Cu–Ni–Pb–Zn)
Zn Single Zeolite 10–500 4–16 Not 3.93 (L) [175]
Binary (Cd, adjusted/25 2.02 (L) L
Zn) 0.881 (L)
Binary (Pb,
Zn)
Zn Single Natural zeolite 50–250 15 Constant/25 3.644, 4.077 (L, LF) LF [210]
Zn Single Natural aluminosilicate 0–1000 187.0 (L) L [219]
and carbonate 1 <7.1/25
Zn Single Clinoptilolite 33–3269 6–8/22 18.0 (L) L [251]
2.5 (L)
Zn Single Zeolite NaY 3–98 4.5/30 92.51 (L) F [252]
Zn Single Zeolite 261–6538 40 5.5/room 96.11 (L) L [253]
temp.

L = Langmuir.
E = Experimental.
F = Freundlich.
DR = Dubinin–Radushkevich.
MDR = Modified Dubinin–Radushkevich.
S = Sips.
RP = Redlich–Peterson.

based on simple mathematical relationships between the liquid
phase equilibrium concentration and the solid phase equilibrium
concentration [14]. Table 14 [20,211,226–242] summarizes the
main two and three parameter isotherm models that have been
applied for the investigation of nickel and zinc adsorption on min-
erals. The assumptions on which these equations are based have
been mentioned in several works [20,45,116,211,239,243–250].
Isotherm models have also been developed to describe competitive
adsorption when more than one type of heavy metals is present
in the solution. These models can be simple equations that are
associated with the individual parameters only (i.e. non-modified
models) and more complex models exploiting the individual model
parameters together with suitable correction factors (modified
adsorption models) [161,213].
Table 15 [11,40,42,44,47–49,52–54,56,58–65,68,80–83,86,92,
98–100,102–108,120,122–125,127,142–145,149,151–153,158,166,
174,175,210,219,251–253] summarizes the equilibrium studies
concerning adsorption of nickel and zinc ions on natural and
modified minerals in single and multi-metal systems. The Table
lists the experimental conditions, the maximum adsorption
capacity and the isotherm model that provides the best fit to
the experimental data. Usually, the Langmuir and the Freundlich
models are the more frequently applied models. Oter and Akcay
[54] found that the Langmuir and the Freundlich isotherm models
could adequately describe the adsorption of nickel and zinc ions
on Turkish clinoptilolite. El-Kamash et al. [124] mentioned that
both Freundlich and Dubinin–Radushkevich (DR) models provided
adequate fit for the adsorption of zinc on synthetic zeolite A, while
the values of the mean energy of adsorption E were in the range
of 8–16 kJ mol−1 , indicating that ion exchange was the prevailing
mechanism. Other researchers have also reported values of E in the
range of 8–16 kJ mol−1 [62,64,68,107]. Donat et al. [100] found that
the Langmuir model provided the best fit to the experimental data,
while the application of the DR model showed that E was in the
range of ion exchange (8–16 kJ mol−1 ). Other equilibrium studies
have shown that adsorption is physical with E taking values lower
than 8 kJ mol−1 [40,56,61,96,122]. Purna Chandra Rao et al. [105]
found that the isotherm shapes for zinc adsorption on zeolite
4A, zeolite 13X and bentonite were identical indicating a similar
sorption process. Several studies showed that the Langmuir model
provided the best fit to the experimental data [63,96,104,151,175]
other studies showed that the Freundlich was the most suitable
model [60,252] and some studies showed that both the Langmuir
and Freundlich models could adequately predict the experimental
data [44,52,54,83,142,144]. The high correlation of both the Lang-
muir and the Freundlich models with experimental data can be
interpreted as a possible monolayer and heterolayer formation of
metallic compounds on the mineral surface [254]. The majority
of research studies examine two-parameter equations, since the
complexity of three parameter equations limits their application.
Perić et al. [59] investigated the performance of various isotherms
(Langmuir–Freundlich, Toth, DR, modified DR, Redlich–Peterson
and Lineweawer–Burk) for the adsorption of zinc on natural zeolite
and found that the best fit to the experimental results was provided
by the models that assume that the metal ions bind first at the
energetically most favourable sites, with multi-layer adsorption
taking place subsequently. Rajic et al. [120] found that the Sips
isotherm best described the equilibrium data for nickel adsorp-
tion on natural zeolite for a wide range of temperatures since
it accounts for heterogeneity. Stojakovic et al. [125] also found
a good correlation between the experimental data and the Sips
isotherm for zinc adsorption on natural clinoptilolite. However,
the authors concluded that the Langmuir model could describe
better the experimental data since it gave a better prediction of
the maximum adsorption capacity compared to the Sips model.
The latter model also could not adequately describe the changes
in qm due to temperature increase. Katsou et al. [96] examined
several equilibrium models (Langmuir, Freundlich, Temkin, DR)
and concluded that the Langmuir isotherm provided the best fit
to the experimental data concerning the adsorption of nickel on
zeolite, bentonite and vermiculite. Meshko et al. [210] studied the
adsorption isotherms of Langmuir, Freundlich, Redlich–Peterson
456 S. Malamis, E. Katsou / Journal of Hazardous Materials 252–253 (2013) 428–461

and Langmuir–Freundlich of zinc ions on clinoptilolite and con- ai parameter that depends on the shape of the adsorbent
cluded that the Langmuir–Freundlich equation provided the am specific area of the adsorbent (m2 m−3 )
best fit to the experimental data. Finally, Ijagbemi et al. [56] aS Sips isotherm constant (L g−1 )
applied the isotherm models of Langmuir, Freundlich, Temkin, AT Toth isotherm constant (L mg−1 )
Redlich–Peterson, Florry–Huggins and DR to describe the equilib- B time constant
rium sorption of nickel on Na-montmorillonite and acid modified b constant related to the heat of adsorption in the Temkin
montmorillonite and concluded that Redlich–Peterson provided model (J mol−1 )
the best fit to the experimental data for Na-montmorillonite and BBET BET adsorption constant related to the energy of interac-
DR for acid treated montmorillonite. As it is seen from Table 13, the tion with the surface
maximum adsorption capacity concluded by the different studies bi parameter that depends on the shape of the adsorbent
for the same adsorbent and metal has significant differences and bk Khan isotherm constant
depends on various parameters. These parameters include solu- Ce liquid phase equilibrium metal concentration (mg L−1 )
tion pH, temperature, adsorbent’s concentration, grain size, initial Ce,i equilibrium concentration of solute i
metal concentrations, the adsorbent’s origin and its composition, Cs metal concentration at the surface of the adsorbent
the application of modified or natural adsorbents, the presence (mg L−1 )
of other cations, the liquid phase characteristics, the isotherm Csb saturation concentration of the metal corresponding to
employed to determine qm . Usually, the presence of other cations monolayer saturation (mg L−1 )
in the solution results in the reduction of qm compared to the one Ct liquid phase metal concentration at time t (mg L−1 )
obtained for each metal in single metal solutions [86,108,174]. C0 initial metal concentration in the solution (mg L−1 )
Furthermore, in most studies the system’s equilibrium is examined Deff effective diffusion coefficient (m2 s−1 )
using the linear forms of the isotherm models. The application Df film diffusion coefficient (m2 s−1 )
of the non-linear forms can provide different estimated for the Dp pore diffusion coefficient (m2 s−1 )
maximum adsorption capacity. Currently, there is no comparative dp average particle size of adsorbent (m)
study applying both linear and non-linear two-parameter isotherm E mean energy of sorption per mole of adsorbate for the DR
equations for the adsorption of Ni and Zn on minerals. model (kJ mol−1 )
Ea Arrhenius activation energy (kJ mol−1 )
8. Conclusions F fractional attainment of equilibrium at time t
f interaction coefficient of the Frumkin equation
Adsorption and ion exchange using natural and modified min- K saturation constant of Generalized isotherm (mg L−1 )
erals is effective for the removal of nickel and zinc ions from water ka adsorption rate constant
and wastewater. Extensive studies have been conducted in order to Keq equilibrium adsorption constant
evaluate the impact of several parameters on adsorption. The above KF Freundlich constant (mg1−1/n L1/n g−1 )
analysis has shown that the adsorbate type, solution pH, metal con- kf mass transfer coefficient between bulk solution and solid
centration and ionic strength as well as the adsorbent type and surface (m min−1 )
concentration are usually the most influential parameters. Solution kfd rate of liquid film diffusion (min−1 )
temperature, mineral grain size and agitation speed also seem to KFH Flory-Huggins equilibrium constant
affect the process. The presence of other ions in the solution and/or KFF equilibrium constant of Frumkin equation
certain wastewater compounds adversely impact on the process. kid constant of intraparticle diffusion (mg g−1 min−1/2 )
The chemical and/or thermal modification of natural minerals KL Langmuir constant (L mg−1 or L mol−1 )
can increase its adsorption capacity. However, mineral modifica- KLF Langmuir-Freundlich isotherm constant (L mg−1 )
tion is not always associated with increased metal uptake since KL,i Langmuir constant for single solute i (L mg−1 )
some cases have been reported where modified minerals exhibited KR Redlich–Peterson isotherm constant (L g−1 )
an inferior performance compared to natural ones. The influence KR,i Redlich–Peterson isotherm constant derived for a single
of a wide pool of parameters on adsorption is also reflected by solute i (L g−1 )
the variability in the mineral adsorption capacities for zinc and KT Toth isotherm constant (L mg−1 )
nickel uptake in the summarized scientific works. Several stud- k1 rate constant of the pseudo-first-order model (min−1 )
ies use the pseudo-first-order and pseudo-second-order kinetics k2 rate constant of the pseudo-second-order model
in order to model the adsorption kinetics, with most studies con- (g mg−1 min−1 )
cluding that the pseudo-second-order model is in close agreement ma adsorbent concentration (g L−1 )
with experimental data. Diffusion models such as the intraparticle N number of data points
diffusion model, external mass transfer and Vermeulen’s approxi- n ascending integer number
mation have also been applied and the effective diffusion coefficient nF Freundlich affinity constant
has been determined. The latter usually lies within the range of nFH Flory–Huggins isotherm exponent
10−12 –10−14 m2 s−1 . In terms of equilibrium examination the Lang- ng cooperative binding constant of Generalized isotherm
muir isotherm model is in several cases in good agreement with the ni Freundlich affinity constant for a single solute i
experimental data, while the Freundlich model has also been found nK Khan isotherm exponent
to fit the experimental data in several cases. Some researchers nLF Langmuir–Freundlich isotherm exponent
have also successfully applied other isotherm models, such as the ns Sips isotherm exponent
Temkin and DR models to predict the adsorption equilibrium. p Radke-Prausnitz isotherm exponent
qe solid phase equilibrium metal concentration (mg g−1 )
qe,i solid phase equilibrium concentration of solute i (mg g−1 )
Nomenclature qF theoretical monolayer saturation capacity (mg g−1 )
qm maximum adsorption capacity (mg g−1 )
qm,i maximum adsorption capacity for single solute i (mg g−1 )
A equilibrium binding constant of Temkin model (L mg−1 ) qt solid phase concentration of metal at time t (mg g−1 )
Aa pre-exponential factor, Arrhenius constant R universal gas constant (Jmol−1 K−1 )
 S. Malamis, E. Katsou / Journal of Hazardous Materials 252–253 (2013) 428–461 457

r radius of the adsorbent particle considered to be spherical [10] D.W. O’Connell, C. Birkinshaw, T.F. O’Dwyer, Heavy metal adsorbents pre-
(m) pared from the modification of cellulose: a review, Bioresour. Technol. 99
(2008) 6709–6724.
rRP Radke–Prausnitz isotherm constant (L mg−1 ) [11] Y.S. Ok, J.E. Yang, Y.-S. Zhang, S.-J. Kim, D.-Y. Chung, Heavy metal adsorption by
T absolute temperature (K) a formulated zeolite-Portland cement mixture, J. Hazard. Mater. 147 (2007)
t time (min) 91–96.
[12] S.E. Bailey, T.J. Olin, R.M. Bricka, D.D. Adrian, A review of potentially low-cost
Ta Toth isotherm exponent sorbents for heavy metals, Water Res. 33 (1999) 2469–2479.
t1/2 half time for the adsorption process (s or min) [13] R.D. Harter, R. Naidu, An assessment of environmental and solution parameter
˛ initial adsorption rate of Elovich equation (mg g−1 min−1 ) impact on trace-metal sorption by soils, Soil Sci. Soc. Am. J. 65 (2001) 597–612.
[14] H.B. Bradl, Adsorption of heavy metal ions on soils and soils constituents, J.
˛R Redlich–Peterson isotherm constant (L mg−1 )
Colloid. Interface Sci. 277 (2004) 1–18.
˛R,i Redlich–Peterson isotherm isotherm constant for a single [15] G.S. Miguel, S.D. Lambert, N.J.D. Graham, A practical review of the perfor-
solute i (L mg−1 ) mance of organic and inorganic adsorbents for the treatment of contaminated
˛RP Radke-Prausnitz isotherm constant (L g−1 ) waters, J. Chem. Technol. Biotechnol. 81 (2006) 1685–1696.
[16] D. Sud, G. Mahajan, M.P. Kaur, Agricultural waste material as potential adsor-
ˇ constant of the DR model related to the mean energy of bent for sequestering heavy metal ions from aqueous solutions – a review,
sorption (mol2 kJ−2 ) Bioresour. Technol. 99 (2008) 6017–6027.
ˇe desorption constant of Elovich equation (g mg−1 ) [17] S.K.R. Yadanaparthi, D. Graybill, R.V. Wandruszka, Adsorbents for the removal
of arsenic, cadmium, and lead from contaminated waters, J. Hazard. Mater.
ˇR Redlich–Peterson isotherm exponent 171 (2009) 1–15.
ˇR,i Redlich–Peterson isotherm exponent for a single solute i [18] S. Wang, Y. Peng, Natural zeolites as effective adsorbents in water and waste-
ı bounbary layer thickness (m) water treatment, Chem. Eng. J. 156 (2010) 11–24.
[19] Y.-F. Zhou, R.J. Haynes, Sorption of heavy metals by inorganic and organic
G Gibbs free energy of adsorption (kJ mol−1 ) components of solid wastes: significance to use of wastes as low-cost adsor-
G◦ standard Gibbs free energy (kJ mol−1 ) bents and immobilizing agents, Crit. Rev. Environ. Sci. Technol. 40 (2010)
H enthalpy change (kJ mol−1 ) 909–977.
[20] Y.S. Ho, J.F. Porter, G. McKay, Equilibrium isotherm studies for the sorption
H◦ standard enthalpy change (kJ mol−1 ) of divalent metal ions onto peat: copper, nickel and lead single component
S entropy change (J mol−1 K−1 ) systems, Water Air Soil Pollut. 141 (2002) 1–33.
S◦ Standard entropy change (J mol−1 K-1 ) [21] Y.-S. Ho, Review of second-order models for adsorption systems, J. Hazard.
Mater. 136 (2006) 681–689.
ε Polanyi sorption potential of the DR model
[22] C. Gerente, V.K.C. Lee, P. Le-Cloirec, G. McKay, Application of chitosan for the
 degree of surface coverage of adsorbent surface removal of metals from wastewaters by adsorption – mechanisms and models
b adsorbent bulk density (g L−1 ) review, Crit. Rev. Environ. Sci. Technol. 37 (2007) 41–127.
[23] W. Plazinski, W. Rudzinski, A. Plazinska, Theoretical models of sorption kinet-
 the time needed for diffusion of the metal from the adsor-
ics including a surface reaction mechanism: a review, Adv. Colloid Interface
bent’s surface to the exchangeable site (s) Sci. 152 (2009) 2–13.
[24] H. Qiu, L. Lv, B.-c. Pan, Q.-j. Zhang, W.-m. Zhang, Q.-x. Zhang, Critical review
in adsorption kinetic models, J. Zhejiang Univ. Sci. A 10 (2009) 716–724.
Acknowledgements [25] B. Saha, C. Orvig, Biosorbents for hexavalent chromium elimination
from industrial and municipal effluents, Coord. Chem. Rev. 254 (2010)
2959–2972.
[26] O. Abollino, A. Giacomino, M. Malandrino, E. Mentasti, Interaction of metal
ions with montmorillonite and vermiculite, Appl. Clay Sci. 38 (2008) 227–236.
[27] M. Malandrino, O. Abollino, A. Giacomino, M. Aceto, E. Mentasti, Adsorption
of heavy metals on vermiculite: influence of pH and organic ligands, J. Colloid
Interface Sci. 299 (2006) 537–546.
[28] M.K. Doula, A. Ioannou, The effect of electrolyte anion on Cu adsorption-
This research has been co-financed by the European Union (Euro- desorption by clinoptilolite, Micropor. Mesopor. Mater. 58 (2003) 115–130.
pean Social Fund – ESF) and Greek national funds through the [29] P.W. Schindler, B. Fürst, R. Dick, P.U. Wolf, Ligand properties of surface silanol
Operational Program “Education and Lifelong Learning” of the groups. I. Surface complex formation with Fe3+ , Cu2+ , Cd2+ and Pb2+ , J. Colloid
Interface Sci. 55 (1976) 469–475.
National Strategic Reference Framework (NSRF) – Research Fund- [30] N.M. Nagy, J. Kónya, Interfacial Chemistry of Rocks and Soils, CRC Press, Taylor
ing Program: Heraclitus II. Investing in knowledge society through & Francis, New York, 2009.
the European Social Fund. [31] M. Hamidpour, M. Kalbasi, M. Afyuni, H. Shariatmadari, P.E. Holm, H.C.B.
Hansen, Sorption hysteresis of Cd(II) and Pb(II) on natural zeolite and ben-
tonite, J. Hazard. Mater. 181 (2010) 686–691.
[32] W.A. Deer, R.A. Howie, J. Zussman, An Introduction to the Rock-Forming Min-
References erals, Wesley Longman, Hong Kong, 1992, pp. 520–529.
[33] S. Kulprathipanja, Zeolites in Industrial Separation and Catalysis, Wiley-VCH
[1] R.P. Beliles, The lesser metals, in: F.W. Oehme (Ed.), Toxicity of Heavy Metals Verlag GmbH & Co KGaA, Weinheim, 2010.
in the Environment, Part 2, Marcel Dekker, New York, 1978, pp. 547–616. [34] S. Cornelius, J.R. Hurlbut, Mineral, John Wiley & Sons Inc, London, 1963.
[2] N. Akhtar, J. Iqbal, M. Iqbal, Removal and recovery of nickel(II) from aque- [35] K.G. Bhattacharyya, S.S. Gupta, Adsorption of a few heavy metals on natural
ous solution by loofa sponge-immobilized biomass of Chlorella sorokiniana: and modified kaolinite and montmorillonite: a review, Adv. Colloid Interface
characterization studies, J. Hazard. Mater. B 108 (2004) 85–94. Sci. 140 (2008) 114–131.
[3] U. Farooq, J.A. Kozinski, M.A. Khan, M. Athar, Biosorption of heavy metal ions [36] M. Fleischer, J.A. Mandarino, Glossary of Mineral Species, The Mineralogical
using wheat based biosorbents – a review of the recent literature, Bioresour. Record Inc, Tuscon, 1991, p. 27.
Technol. 101 (2010) 5043–5053. [37] M.J. Potter, Vermiculite, US Geological Survey, Minerals Yearbook, 2002, pp.
[4] P.N. Cheremisinoff, Handbook of Water and Wastewater Treatment Technol- 82.1–82.3.
ogy, Marcel Dekker Inc, New York, 1995. [38] C.E. Weaver, Developments in Sedimentology 44, Clays, Muds and Shales,
[5] T. Zoumis, W. Calmano, U. Förstner, Demobilization of heavy metals from Elsevier, Atlanta, 1989, pp. 82–84.
mine wastewaters, Acta Hydrochim. Hydrobiol. 28 (2000) 212–218. [39] G. Xueyi, K. Inoue, Elution of copper from vermiculite with environmentally
[6] A. Dimirkou, Uptake of Zn2+ ions by a fully iron-exchanged clinoptilolite. Case benign reagents, Hydrometallurgy 70 (2003) 9–21.
study of heavily contaminated drinking water samples, Water Res. 41 (2007) [40] S. Çoruh, O.N. Ergun, Ni2+ removal from aqueous solutions using conditioned
2763–2773. clinoptilolites: kinetic and isotherm studies, Environ. Prog. Sustain. Energy
[7] T.A. Kurniawan, G.Y.S. Chan, W.H. Lo, S. Babel, Comparisons of low-cost adsor- 28 (2009) 162–172.
bents for treating wastewaters laden with heavy metals, Sci. Total Environ. [41] B. Erdem, A. Özcan, O. Gök, A.S. Özcan, Immobilization of 2,2 -dipyridyl onto
366 (2006) 409–426. bentonite and its adsorption behavior of copper(II) ions, J. Hazard. Mater. 163
[8] T.A. Kurniawan, G.Y.S. Chan, W.H. Lo, S. Babel, Physico-chemical treatment (2009) 418–426.
techniques for wastewater laden with heavy metals, Chem. Eng. J. 118 (2006) [42] C.O. Ijagbemi, M.-H. Baek, D.-S. Kim, Montmorillonite surface properties and
83–98. sorption characteristics for heavy metal removal from aqueous solutions, J.
[9] V.O. Arief, K. Trilestari, J. Sunarso, N. Indraswati, S. Ismadji, Recent progress Hazard. Mater. 166 (2009) 538–546.
on biosorption of heavy metals from liquids using low cost biosorbents: char- [43] D. Wu, Y. Sui, S. He, X. Wang, C. Li, H. Kong, Removal of trivalent chromium
acterization, biosorption parameters and mechanism studies, Clean Soil Air from aqueous solution by zeolite synthesized from coal fly ash, J. Hazard.
Water 36 (2008) 937–962. Mater. 155 (2008) 415–423.
458 S. Malamis, E. Katsou / Journal of Hazardous Materials 252–253 (2013) 428–461
[44] S.S. Gupta, K.G. Bhattacharyya, Immobilization of Pb(II), Cd(II) and Ni(II) ions
on kaolinite and montmorillonite surfaces from aqueous medium, J. Environ.
Manag. 87 (2008) 46–58.
[45] K. Vijayaraghavan, Y.-S. Yun, Bacterial biosorbents and biosorption, Bio-
technol. Adv. 26 (2008) 266–291.
[46] M.K. Doula, A. Dimirkou, Use of an iron-overexchanged clinoptilolite for the
removal of Cu2+ ions from heavily contaminated drinking water samples, J.
Hazard. Mater. 151 (2008) 738–745.
[47] S.S. Gupta, K.G. Bhattacharyya, Adsorption of Ni(II) on clays, J. Colloid Interface
Sci. 295 (2006) 21–32.
[48] S. Kocaoba, Y. Orhan, T. Akyüz, Kinetics and equilibrium studies of heavy metal
ions removal by use of natural zeolite, Desalination 214 (2007) 1–10.
[49] M.G.A. Vieira, A.F.A. Neto, M.L. Gimenes, M.G.C. da Silva, Sorption kinetics and
equilibrium for the removal of nickel ions from aqueous phase on calcined
Bofe bentonite clay, J. Hazard. Mater. 177 (2010) 362–371.
[50] S.K. Ouki, M. Kavannagh, Performance of natural zeolites for the treatment of
mixed metal-contaminated effluents, Waste Manag. Res. 15 (1997) 383–394.
[51] S.K. Ouki, M. Kavannagh, Treatment of metals-contaminated wastewaters by
use of natural zeolites, Water Sci. Technol. 69 (1999) 115–122.
[52] M. Sprynskyy, B. Buszewski, A.P. Terzyk, J. Namieśnik, Study of the selec-
tion mechanism of heavy metal (Pb2+ , Cu2+ , Ni2+ , and Cd2+ ) adsorption on
clinoptilolite, J. Colloid Interface Sci. 304 (2006) 21–28.
[53] A. Al-Haj Ali, R. El-Bishtawi, Removal of lead and nickel ions using zeolite tuff,
J. Chem. Technol. Biotechnol. 69 (1997) 27–34.
[54] O. Oter, H. Akcay, Use of natural clinoptilolite to improve, water quality: sorp-
tion and selectivity studies of lead(II), copper(II), zinc(II), and nickel(II), Water
Environ. Res. 79 (2007) 329–335.
[55] C. Cabrera, C. Gabaldón, P. Marzal, Sorption characteristics of heavy metal ions
by a natural zeolite, J. Chem. Technol. Biotechnol. 80 (2005) 477–481.
[56] C.O. Ijagbemi, M.-H. Baek, D.-S. Kim, Adsorptive performance of un-calcined
sodium exchanged and acid modified montmorillonite for Ni2+ removal: equi-
librium, kinetics, thermodynamics and regeneration studies, J. Hazard. Mater.
174 (2010) 746–755.
[57] X. Wu, F. Zhao, M. Chen, Y. Zhang, C. Zhao, H. Zhou, Factors affecting the
adsorption of Zn2+ and Cd2+ ions from aqueous solution onto vermiculite,
Adsorpt. Sci. Technol. 26 (2008) 145–155.
[58] A. Kaya, A.H. Ören, Adsorption of zinc from aqueous solutions to bentonite, J.
Hazard. Mater. 125 (2005) 183–189.
[59] J. Perić, M. Trgo, N.V. Medvidović, Removal of zinc, copper and lead by nat-
ural zeolite – a comparison of adsorption isotherms, Water Res. 38 (2004)
1893–1899.
[60] A.H. Ören, A. Kaya, Factors affecting adsorption characteristics of Zn2+ on two
natural zeolites, J. Hazard. Mater. 131 (2006) 59–65.
[61] S. Veli, B. Alyüz, Adsorption of copper and zinc from aqueous solutions by
using natural clay, J. Hazard. Mater. 149 (2007) 226–233.
[62] E. Erdem, N. Karapinar, R. Donat, The removal of heavy metal cations by
natural zeolites, J. Colloid Interface Sci. 280 (2004) 309–314.
[63] T.K. Sen, D. Gomez, Adsorption of zinc (Zn2+ ) from aqueous solution on natural
bentonite, Desalination 267 (2011) 286–294.
[64] H.M. Baker, A.M. Massadeh, H.A. Younes, Natural Jordanian zeolite: removal
of heavy metal ions from water samples using column and batch methods,
Environ. Monit. Assess. 157 (2009) 319–330.
[65] N. Beyazit, I. Peker, O.N. Ergun, Removal of lead and zinc ions from aqueous
solution using Amasya zeolites from Turkey, Int. J. Environ. Pollut. 19 (2003)
160–170.
[66] A.C. Vieira dos Santos, J.C. Masini, Evaluating the removal of Cd(II), Pb(II) and
Cu(II) from a wastewater sample of a coating industry by adsorption onto
vermiculite, Appl. Clay Sci. 37 (2007) 167–174.
[67] A. Katsoyiannis, C. Samara, The fate of dissolved organic carbon (DOC) in the
wastewater treatment process and its importance in the removal of waste-
water contaminants, Environ. Sci. Pollut. Res. Int. 14 (2007) 284–292.
[68] S. Yang, J. Li, Y. Lu, Y. Chen, X. Wang, Sorption of Ni(II) on GMZ bentonite:
effects of pH, ionic strength, foreign ions, humic acid and temperature, Appl.
Radiat. Isot. 67 (2009) 1600–1608.
[69] A. Langella, M. Pansini, P. Cappelletti, B. De Gennaro, M. De Gennaro, C. Colella,
NH4 + , Cu2+ , Zn2+ , Cd2+ and Pb2+ exchange for Na+ in a sedimentary clinoptilo-
lite, North Sardinia, Italy, Micropor. Mesopor. Mater. 37 (2000) 337–343.
[70] D. Ziolko, D. Hala, J.N. Lester, M.D. Scrimshaw, The effectiveness of conven-
tional trickling filter treatment plants at reducing concentrations of copper
in wastewaters, Sci. Total Environ. 407 (2009) 6235–6241.
[71] S. Kempton, R.M. Sterritt, J.N. Lester, Heavy metal removal in primary sedi-
mentation. II. The influence of metal speciation and particle size distribution,
Sci. Total Environ. 63 (1987) 247–258.
[72] M. Karvelas, A. Katsoyiannis, C. Samara, Occurrence and fate of heavy metals
in the wastewater treatment process, Chemosphere 53 (2003) 1201–1210.
[73] K. Lackovic, M.J. Angove, J.D. Wells, B.B. Johnson, Modelling the adsorption of
Cd(II) onto goethite in the presence of citric acid, J. Colloid Inteface Sci. 269
(2004) 37–45.
[74] O. Abollino, M. Aceto, M. Malandrino, C. Sarzanini, E. Mentasti, Adsorption of
heavy metals on Na-montmorillonite. Effect of pH and organic substances,
Water Res. 37 (2003) 1619–1627.
[75] G.M. Naja, V. Murphy, B. Volesky, Biosorption, metals, in: Encyclopedia of
Industrial Biotechnology: Bioprocess, Bioseparation, and Cell Technology,
Wiley, 2010.
[76] B. Volesky, S. Schiewer, Biosorption of metals, in: M. Flickinger, S.W. Drew
(Eds.), Encycl. of Bioprocess Technol., Wiley, New York, 1999, pp. 433–453.
[77] V.J. Inglezakis, A.A. Zorpas, M.D. Loizidou, H.P. Grigoropoulou, The effect of
competitive cations and anions on ion exchange of heavy metals, Sep. Purif.
Technol. 46 (2005) 202–207.
[78] V.J. Inglezakis, A.A. Zorpas, M.D. Loizidou, H.P. Grigoropoulou, Simultaneous
removal of metals Cu2+ , Fe3+ and Cr3+ with anions SO4 2− and HPO4 2− using
clinoptilolite, Micropor. Mesopor. Mater. 61 (2003) 167–171.
[79] P. Papachristou, K.J. Haralambous, M. Loizidou, N. Spyrellis, Studies on the
nickel removal from aqueous solutions, J. Environ. Sci. Health A Environ. Sci.
Eng. 28 (1993) 135–142.
[80] T.S. Anirudhan, P.S. Suchithra, Heavy metals uptake from aqueous solutions
and industrial wastewaters by humic acid-immobilized polymer/bentonite
composite: kinetics and equilibrium modelling, Chem. Eng. J. 156 (2011)
146–156.
[81] E. Álvarez-Ayuso, A. García-Sánchez, X. Querol, Purification of metal electro-
plating waste waters using zeolites, Water Res. 37 (2003) 4855–4862.
[82] E. Álvarez-Ayuso, A. García-Sánchez, Removal of heavy metals from waste
waters by natural and Na-exchanged bentonites, Clays Clay Miner. 51 (2003)
475–480.
[83] E. Álvarez-Ayuso, A. García-Sánchez, Removal of heavy metals from waste
waters by vermiculites, Environ. Technol. 24 (2003) 5615–5625.
[84] S.K. Pitcher, R.C.T. Slade, N.I. Ward, Heavy metal removal from motorway
stormwater using zeolites, Sci. Total Environ. 334 (2004) 161–166.
[85] E. Katsou, S. Malamis, K.J. Haralambous, Industrial wastewater pre-treatment
for heavy metal reduction by employing a sorbent-assisted ultrafiltration
system, Chemosphere 82 (2011) 557–564.
[86] T. Vengris, R. Binkiene, A. Sveikauskaite, Nickel, copper and zinc removal from
waste water by a modified clay sorbent, Appl. Clay Sci. 18 (2001) 183–190.
[87] M. Panayotova, Kinetics and thermodynamics of removal of nickel ions from
wastewater by use of natural and modified zeolite, Fresenius Environ. Bull.
10 (2001) 267–272.
[88] T.G.P. Vásquez, A.E.C. Botero, L.M.S. de Mesquita, M.L. Torem, Biosorptive
removal of Cd and Zn from liquid streams with a Rhodococcus opacus strain,
Minerals Eng. 20 (2007) 939–944.
[89] J.E.B. Cayllahua, R.J. Carvalho, M.L. Torem, Evaluation of equilibrium, kinetic
and thermodynamic parameters for biosorption of nickel(II) ions onto bacte-
ria strain Rhodococcus opacus, Miner. Eng. 22 (2009) 1318–1325.
[90] C.Y. Lin, D.H. Yang, Removal of pollutants from wastewater by coal bottom
ash, J. Environ. Sci. Health A Tox. Hazard. Subst. Environ. Eng. 37 (2002)
1509–1522.
[91] M.I. Ansari, F. Masood, A. Malik, Bacterial biosorption: a technique for reme-
diation of heavy metals in microbes and microbial technology, in: I. Ahmad,
F. Ahmad, J. Pichtel (Eds.), Agricultural Environmental Applications, Springer,
New York, 2011.
[92] K.S. Hui, C.Y.H. Chao, S.C. Kot, Removal of mixed heavy metal ions in waste-
water by zeolite 4A and residual products from recycled coal fly ash, J. Hazard.
Mater. 127 (2005) 89–101.
[93] A. Esposito, F. Pagnanelli, F. Vegliò, pH-related equilibria models for biosorp-
tion in single metal systems, Chem. Eng. Sci. 57 (2002) 307–313.
[94] J. Yang, B. Volesky, Modeling the uranium-proton ion exchange in biosorption,
Environ. Sci. Technol. 33 (1999) 4079–4085.
[95] M.A. Acheampong, R.J.W. Meulepas, P.N.L. Lens, Removal of heavy metals and
cyanide from gold mine wastewater, J. Chem. Technol. Biotechnol. 85 (2010)
590–613.
[96] E. Katsou, S. Malamis, K.J. Haralambous, M. Loizidou, Use of ultrafiltration
membranes and aluminosilicate minerals for nickel removal from industrial
wastewater, J. Membr. Sci. 360 (2010) 234–249.
[97] E. Katsou, S. Malamis, K.J. Haralambous, Examination of zinc uptake in a com-
bined system using sludge, minerals and ultrafiltration membranes, J. Hazard.
Mater. 182 (2010) 27–38.
[98] M.E. Argun, Use of clinoptilolite for the removal of nickel ions from water:
kinetics and thermodynamics, J. Hazard. Mater. 150 (2008) 587–595.
[99] M.V. Dinu, E.S. Dragan, Evaluation of Cu2+ , Co2+ and Ni2+ ions removal from
aqueous solution using a novel chitosan/clinoptilolite composite: kinetics and
isotherms, Chem. Eng. J. 160 (2010) 157–163.
[100] R. Donat, A. Akdogan, E. Erdem, H. Cetisli, Thermodynamics of Pb2+ and Ni2+
adsorption onto natural bentonite from aqueous solutions, J. Colloid Interface
Sci. 286 (2005) 43–52.
[101] Z.-R. Liu, S.-Q. Zhou, Adsorption of copper and nickel on Na-bentonite, Process
Saf. Environ. Prot. 88 (2010) 62–66.
[102] X. Song, S. Wang, L. Chen, M. Zhang, Y. Dong, Effect of pH, ionic strength
and temperature on the sorption of radionickel on Na-montmorillonite, Appl.
Radiat. Isot. 67 (2009) 1007–1012.
[103] M.G. Da Fonseca, M.M. De Oliveira, L.N.H. Arakaki, J.G.P. Espinola, C. Airoldi,
Natural vermiculite as an exchanger support for heavy cations in aqueous
solution, J. Colloid Interface Sci. 285 (2005) 50–55.
[104] M. Minceva, R. Fajgar, L. Markovska, V. Meshko, Comparative study of Zn2+ ,
Cd2+ , and Pb2+ removal from water solution using natural clinoptilolitic zeo-
lite and commercial granulated activated carbon. Equilibrium of adsorption,
Sep. Sci. Technol. 43 (2008) 2117–2143.
[105] G. Purna Chandra Rao, S. Satyaveni, A. Ramesh, K. Seshaiah, K.S.N. Murthy, N.V.
Choudary, Sorption of cadmium and zinc from aqueous solutions by zeolite
4A, zeolite 13X and bentonite, J. Environ. Manag. 81 (2006) 265–272.
[106] A. Mockovčiaková, Z. Orolínová, J. Škvarla, Enhancement of the bentonite
sorption properties, J. Hazard. Mater. 180 (2010) 274–281.
[107] S.-H. Lin, R.-S. Juang, Heavy metal removal from water by sorption using
surfactant-modified montmorillonite, J. Hazard. Mater. 92 (2002) 315–326.
 S. Malamis, E. Katsou / Journal of Hazardous Materials 252–253 (2013) 428–461
[108] P.C. Mishra, R.K. Patel, Removal of lead and zinc ions from water by low cost
adsorbents, J. Hazard. Mater. 168 (2009) 319–325.
[109] B. Bayat, Comparative study of adsorption properties of Turkish fly ashes:
I. The case of nickel(II), copper(II) and zinc(II), J. Hazard. Mater. 95 (2002)
251–273.
[110] L. Nouri, I. Ghodbane, O. Hamdaoui, M. Chiha, Batch sorption dynamics and
equilibrium for the removal of cadmium ions from aqueous phase using wheat
bran, J. Hazard. Mater. 149 (2007) 115–125.
[111] N. Goyal, S.C. Jain, U.C. Banerjee, Comparative studies on the microbial adsorp-
tion of heavy metals, Adv. Environ. Res. 7 (2003) 311–319.
[112] P.R. Puranik, K.M. Paknikar, Biosorption of lead, cadmium and zinc by Cit-
robacter strain MCM B-181: characterization studies, Biotechnol. Prog. 15
(1999) 228–237.
[113] G. Crini, P.-M. Badot, Application of chitosan, a natural aminopolysaccha-
ride, for dye removal from aqueous solutions by adsorption processes using
batch studies: a review of recent literature, Prog. Polym. Sci. 33 (2008)
399–447.
[114] E. Malkoc, Ni(II) removal from aqueous solutions using cone biomass of Thuja
orientalis, J. Hazard. Mater. 137 (2006) 899–908.
[115] V.J. Inglezakis, M.M. Loizidou, H.P. Grigoropoulou, Ion exchange studies on
natural and modified zeolites and the concept of exchange site accessibility,
J. Colloid Inteface Sci. 275 (2004) 570–576.
[116] D. Park, Y.-S. Yun, J.M. Park, The past, present, and future trends of biosorption,
Biotechnol. Bioprocess Eng. 15 (2010) 86–102.
[117] A. Sari, M. Tuzen, Kinetic and equilibrium studies of biosorption of Pb(II) and
Cd(II) from aqueous solution by macrofungus (Amanita rubescens) biomass, J.
Hazard. Mater. 164 (2009) 1004–1011.
[118] G. Uslu, M. Tanyol, Equilibrium and thermodynamic parameters of single and
binary mixture biosorption of lead(II) and copper(II) ions onto Pseudomonas
putida: effect of temperature, J. Hazard. Mater. 135 (2006) 87–93.
[119] Y. Sağ, T. Kutsal, Determination of the biosorption heats of heavy metal
ions on Zoogloea ramigera and Rhizopus arrhizus, Biochem. Eng. J. 6 (2000)
145–151.
[120] N. Rajic, D. Stojakovic, M. Jovanovic, N.Z. Logar, M. Mazaj, V. Kaucic, Removal
of nickel(II) ions from aqueous solutions using the natural clinoptilolite and
preparation of nano-NiO on the exhausted clinoptilolite, Appl. Surf. Sci. 257
(2010) 1524–1532.
[121] M.A. Keane, The removal of copper and nickel from aqueous solution using Y
zeolite ion exchangers, Colloids Surf. A: Physicochem. Eng. Aspects 138 (1998)
11–20.
[122] S.S. Tahir, N. Rauf, Thermodynamic studies of Ni(II) adsorption onto bentonite
from aqueous solution, J. Chem. Thermodyn. 35 (2003) 2003–2009.
[123] N.M. Alandis, O.A. Aldayel, W.K. Mekhemer, J.A. Hefne, H.A. Jokhab, Thermo-
dynamic and kinetic studies for the adsorption of Fe(III) and Ni(II) ions from
aqueous solution using natural bentonite, J. Dispers. Sci. Technol. 31 (2010)
1526–1534.
[124] A.M. El-Kamash, A.A. Zaki, M.A.E. Geleel, Modelling batch kinetics and ther-
modynamics of zinc and cadmium ions removal from waste solutions using
synthetic zeolite A, J. Hazard. Mater. 127 (2005) 211–220.
[125] D. Stojakovic, J. Hrenovic, M. Mazaj, N. Rajic, On the zinc sorption by the Ser-
bian natural clinoptilolite and the disinfecting ability and phosphate affinity
of the exhausted sorbent, J. Hazard. Mater. 185 (2011) 408–415.
[126] G. Bereket, A.Z. Aroğuz, M.Z. Özel, Removal of Pb(II), Cd(II), Cu(II), and Zn(II)
from aqueous solutions by adsorption on bentonite, J. Colloid Interface Sci.
187 (1997) 338–343.
[127] A. Mellah, S. Chegrouche, The removal of zinc from aqueous solutions by
natural bentonite, Water Res. 31 (1997) 621–629.
[128] S.T. Bosso, J. Enzweiler, Evaluation of heavy metal removal from aqueous
solution onto scolecite, Water Res. 36 (2002) 4795–4800.
[129] U. Wingenfelder, C. Hansen, G. Furrer, R. Schulin, Removal of heavy metals
from mine waters by natural zeolites, Environ. Sci. Technol. 39 (2005)
4606–4613.
[130] V.J. Inglezakis, S.G. Poulopoulos, Adsorption, Ion Exchange and Catalysis:
Design of Operation and Environmental Applications, Elsevier, UK, 2006.
[131] E. Malliou, M. Loizidou, N. Spyrellis, Uptake of lead and cadmium by clinop-
tilolite, Sci. Total Environ. 149 (1994) 139–144.
[132] A. Esposito, F. Pagnanelli, A. Lodi, C. Solisio, F. Vegliò, Biosorption of heavy
metals by Sphaerotilus natans: an equilibrium study at different pH and
biomass concentrations, Hydrometallurgy 60 (2001) 129–141.
[133] J. Tangaromsuk, P. Pokethitiyook, M. Kruatrachue, E.S. Upatham, Cadmium
biosorption by Sphingomonas paucimobilis biomass, Bioresour. Technol. 85
(2002) 103–105.
[134] G.M. Gadd, C. White, L. De Rome, Heavy metal and radionuclide uptake by
fungi and yeasts, in: P.R. Norri, D.P. Kelly (Eds.), Biohydrometallurgy, A. Rowe,
Chippenham, Wilts, UK, 1988.
[135] A. Hammaini, F. González, A. Ballester, M.L. Blázquez, J.A. Muñoz, Biosorption
of heavy metals by activated sludge and their desorption characteristics, J.
Environ. Manag. 84 (2007) 419–426.
[136] J. Wang, C. Chen, Biosorption of heavy metals by Saccharomyces cerevisiae:
a review, Biotechnol. Adv. 24 (2006) 427–451.
[137] W. Wang, H. Chen, A. Wang, Adsorption characteristics of Cd(II) from aqueous
solution onto activated palygorskite, Sep. Purif. Technol. 55 (2007) 157–164.
[138] X. Wu, H. Zhou, F. Zhao, C. Zhao, Adsorption of Zn2+ and Cd2+ ions on vermic-
ulite in buffered and unbuffered aqueous solutions, Adsorpt. Sci. Technol. 27
(2010) 907–919.
459
[139] A. Shukla, Y.-H. Zhang, P. Dubey, J.L. Margrave, S.S. Shukla, The role of sawdust
in the removal of unwanted materials from water, J. Hazard. Mater. 95 (2002)
137–152.
[140] F. Bordas, A. Bourg, Effect of solid/liquid ratio on the remobilization of Cu,
Pb, Cd and Zn from polluted river sediment, Water Air Soil Pollut. 128 (2001)
391–400.
[141] A.A. Türkman, S. Aslan, I. Ege, Treatment of metal containing wastewaters by
natural zeolites, Fresenius Environ. Bull. 13 (2004) 574–580.
[142] K.G. Bhattacharyya, S.S. Gupta, Uptake of Ni(II) ions from aqueous solution by
kaolinite and montmorillonite: influence of acid activation of the clays, Sep.
Sci. Technol. 43 (2008) 3221–3250.
[143] K.G. Bhattacharyya, S.S. Gupta, Influence of acid activation on adsorption of
Ni(II) and Cu(II) on kaolinite and montmorillonite: kinetic and thermody-
namic study, Chem. Eng. J. 136 (2008) 1–13.
[144] K.G. Bhattacharyya, S.S. Gupta, Calcined tetrabutylammonium kaolinite and
montmorillonite and adsorption of Fe(II), Co(II) and Ni(II) from solution, Appl.
Clay Sci. 46 (2009) 216–221.
[145] K.G. Bhattacharyya, S.S. Gupta, Kaolinite and montmorillonite as adsorbents
for Fe(III), Co(II) and Ni(II) in aqueous medium, Appl. Clay Sci. 41 (2008) 1–9.
[146] J.-F. Blais, S. Shen, N. Meunier, R.D. Tyagi, Comparison of natural adsor-
bents for metal removal from acidic effluent, Environ. Technol. 24 (2003)
205–215.
[147] A. Cincotti, A. Mameli, A.M. Locci, R. Orrù, G. Cao, Heavy metals uptake by
Sardinian natural zeolites: experiment and modelling, Ind. Eng. Chem. Res.
45 (2006) 1074–1084.
[148] K. Athanasiadis, B. Helmreich, Influence of chemical conditioning on the ion
exchange capacity and on kinetic of zinc uptake by clinoptilolite, Water Res.
39 (2005) 1527–1532.
[149] S.C. Stefanović, N.Z. Logar, K. Margeta, N.N. Tušar, I. Arčon, K. Maver, J. Kovač,
V. Kaučič, Structural investigation of Zn2+ sorption on clinoptilolite tuff from
the Vranjska Banja deposit in Serbia, Micropor. Mesopor. Mater. 105 (2007)
251–259.
[150] A. Bujnova, J. Lesny, Sorption characteristics of zinc and cadmium by some
natural, modified, and synthetic zeolites, Hung. Electron. J. Sci., Environ. Eng.
(2004) 1–10.
[151] A.S. Sheta, A.M. Falatah, M.S. Al-Sewailem, E.M. Khaled, A.S.H. Sallam, Sorption
characteristics of zinc and iron by natural zeolite and bentonite, Micropor.
Mesopor. Mater. 61 (2003) 127–136.
[152] A. Cincotti, N. Lai, R. Orrú, G. Cao, Sardinian natural clinoptilolites for heavy
metals and ammonium removal: experimental and modelling, Chem. Eng. J.
84 (2001) 275–282.
[153] E.G. Pradas, M.V. Sanchez, F.C. Cruz, M.S. Viciana, M.F. Perez, Adsorption of
cadmium and zinc from aqueous solution on natural and activated bentonite,
J. Chem. Technol. Biotechnol. 59 (1994) 289–295.
[154] B.I. Olu-Owolabi, E.I. Unuabonah, Kinetic and thermodynamics of the removal
of Zn2+ and Cu2+ from aqueous solution by sulphate and phosphate-modified
bentonite clay, J. Hazard. Mater. 184 (2010) 731–738.
[155] U.K. Saha, K. Iwasaki, K. Sakurai, Desorption behavior of Cd, Zn and Pb
sorbed on hydroxyaluminum and hydroxyaluminosilicate-montmorillonite
complexes, Clays Clay Miner. 51 (2003) 481–492.
[156] L. Ćurković, S. Cerjan-Stefanović, T. Filipan, Metal ion exchange by natural and
modified zeolites, Water Res. 31 (1997) 1379–1382.
[157] M.V. Mier, R.L. Callejas, R. Gehr, B.E.J. Cisneros, P.J.J. Alvarez, Heavy metal
removal with Mexician clinoptilolite: multi-component ionic exchange,
Water Res. 35 (2001) 373–378.
[158] S. Cerjan-Stefanović, L. Ćurković, T. Filipan, Metal ion exchange by natural
zeolites, Croat. Chem. Acta 69 (1996) 281–290.
[159] M.J. Zamzow, J.E. Murphy, Removal of metal cations from water using zeolites,
Sep. Sci. Technol. 27 (1992) 1969–1984.
[160] S. Malamis, E. Katsou, K.J. Haralambous, Study of Ni(II), Cu(II), Pb(II), and Zn(II)
removal using sludge and minerals followed by MF/UF, Water Air Soil Pollut.
218 (2011) 81–92.
[161] Z. Aksu, U. Acikel, E. Kabasakal, S. Tezer, Equilibrium modelling of individ-
ual and simultaneous biosorption of chromium(VI) and nickel(II) onto dried
activated sludge, Water Res. 36 (2002) 3063–3073.
[162] D. Mohan, C.U. Pittman, P.H. Steele, Single binary and multi-component
adsorption of copper and cadmium from aqueous solutions on Kraft lignin
– a biosorbent, J. Colloid Interface Sci. 297 (2006) 489–504.
[163] M. Panayotova, B. Velikov, Influence of zeolite transformation in a homoionic
form on the removal of some heavy metal ions from wastewater, J. Environ.
Sci. Health A Tox. Hazard. Subst. Environ. Eng. 38 (2003) 545–554.
[164] C.M. Futalan, C.-C. Kan, M.L. Dalida, K.-J. Hsien, C. Pascua, M.-W. Wan, Compar-
ative and competitive adsorption of copper, lead, and nickel using chitosan
immobilized on bentonite, Carbohydr. Polym. 80 (2010) 891–899.
[165] K.M. Ibrahim, T.N. Ed-Deen, H. Khoury, Use of natural chabazite-phillipsite
tuff in wastewater treatment from electroplating factories in Jordan, Environ.
Geol. 41 (2002) 547–551.
[166] E.F. Covelo, F.A. Vega, M.L. Andrade, Competitive sorption and desorption of
heavy metals by individual soil components, J. Hazard. Mater. 140 (2007)
308–315.
[167] A.A. El-Bayaa, N.A. Badawy, E.A. AlKhalik, Effect of ionic strength on the
adsorption of copper and chromium ions by vermiculite pure clay mineral, J.
Hazard. Mater. 170 (2009) 1204–1209.
[168] H.S. Sherry, A series of advances, in: J.A. Marinsky (Ed.), Ion Exchange, Marcel
Dekker, New York, 1969, p. 89.
460 S. Malamis, E. Katsou / Journal of Hazardous Materials 252–253 (2013) 428–461
[169] D. Caputo, F. Pepe, Experiments and data processing of ion exchange equilibria
involving Italian natural zeolites: a review, Micropor. Mesopor. Mater. 105
(2007) 222–231.
[170] G.V. Tsitsishvili, T.G. Andronikashvilli, G.V. Kirov, L.D. Filizova, Natural Zeo-
lites, Ellis Horwood, Chichester, 1991.
[171] G. Blanchard, M. Maunaye, G. Martin, Removal of heavy metals from waters
by means of natural zeolites, Water Res. 18 (1984) 1501–1507.
[172] V.J. Inglezakis, Design of Ion Exchange Columns Using Natural Minerals as
Packing Materials, Dep. Chem. Eng., PhD Thesis, National Technical University
of Athens, Athens, 2002.
[173] M. Panayotova, B. Velikov, Kinetics of heavy metal ions removal by use of
natural zeolite, J. Environ. Sci. Health A Tox. Hazard. Subst. Environ. Eng. 37
(2002) 139–147.
[174] V.K. Jha, M. Matsuda, M. Miyake, Sorption properties of the activated carbon-
zeolite composite prepared from coal fly ash for Ni2+ , Cu2+ , Cd2+ and Pb2+ , J.
Hazard. Mater. 160 (2008) 148–153.
[175] M. Minceva, L. Markovska, V. Meshko, Removal of Zn2+ , Cd2+ and Pb2+ from
binary aqueous solution by natural zeolite and granulated activated carbon,
Maced. J. Chem. Chem. Eng. 26 (2007) 125–134.
[176] Y. Liu, H. Li, X.-H. Zhu, Competitive adsorption of Ag+ , Pb2+ , Ni2+ , and Cd2+ ions
on vermiculite, Sep. Sci. Technol. 45 (2010) 277–287.
[177] L.H. Gai, S.G. Wang, W.X. Gong, X.W. Liu, B.Y. Gao, H.Y. Zhang, Influence of
pH and ionic strength on Cu(II) biosorption by aerobic granular sludge and
biosorption mechanism, J. Chem. Technol. Biotechnol. 83 (2008) 806–813.
[178] M.W.P. Esparza-Soto, Biosorption of humic and fulvic acids to live activated
sludge biomass, Water Res. 37 (2003) 2301–2310.
[179] E. Eren, A. Tabak, B. Eren, Performance of magnesium oxide-coated bentonite
in removal process of copper ions from aqueous solution, Desalination 257
(2010) 163–169.
[180] G. Dönmez, Z. Aksu, Removal of chromium(VI) from saline wastewaters by
Dunaliella species, Process Biochem. 38 (2002) 751–762.
[181] T. Undabeytia, S. Nir, G. Rytwo, C. Serban, E. Morillo, C. Maqueda, Modeling
adsorption–desorption processes of Cu on edge and planar sites of montmo-
rillonite, Environ. Sci. Technol. 36 (2002) 2677–2683.
[182] M. Trgo, J. Perić, Interaction of the zeolitic tuff with Zn-containing simulated
pollutant solutions, J. Colloid Interface Sci. 260 (2003) 166–175.
[183] J. Lützenkirchen, Ionic strength effects on cation sorption to oxides: macro-
scopic observations and their significance in microscopic interpretation, J.
Colloid Interface Sci. 195 (1997) 149–155.
[184] J. Echeverría, J. Indurain, E. Churio, J. Garrido, Simultaneous effect of pH, tem-
perature, ionic strength, and initial concentration on the retention of Ni on
illite, Colloids Surf. A: Physicochem. Eng. Aspects 218 (2003) 175–187.
[185] C. Jeon, Y. Je Yoo, W.H. Hoell, Environmental effects and desorption charac-
teristics on heavy metal removal using carboxylated alginic acid, Bioresour.
Technol. 96 (2005) 15–19.
[186] J.R. Evans, W.G. Davids, J.D. MacRae, A. Amirbahman, Kinetics of cadmium
uptake by chitosan-based crab shells, Water Res. 36 (2002) 3219–3226.
[187] J. Shen, Z. Duvnjak, Adsorption kinetics of cupric and cadmium ions on corn-
cob particles, Process Biochem. 40 (2005) 3446–3454.
[188] R. Shawabkeh, A. Al-Harahsheh, A. Al-Otoom, Production of zeolite from Jor-
danian oil shale ash and application for zinc removal from wastewater, Oil
Shale 21 (2004) 125–136.
[189] J. Taparcevska, L. Markovska, B. Koumanova, V. Meshko, Diffusion models for
adsorption kinetics of Zn2+ , Cd2+ and Pb2+ onto natural zeolite, Water Sci.
Technol. 62 (2010) 1136–1142.
[190] G. McKay, Adsorption of dyestuffs from aqueous solutions with activated
carbon I: equilibrium and batch contact-time studies, J. Chem. Technol. Bio-
technol. 32 (1982) 759–772.
[191] V. Meshko, L. Markovska, M. Mincheva, A.E. Rodrigues, Adsorption of basic
dyes on granular activated carbon and natural zeolite, Water Res. 35 (2001)
3357–3366.
[192] Y.-S. Ho, Citation review of Lagergren kinetic rate equation on adsorption
reaction, Scientometrics 59 (2004) 171–177.
[193] Y.S. Ho, G. McKay, Kinetic models for the sorption of dye from aqueous solu-
tion by wood, J. Environ. Sci. Health B: Process Saf. Environ. Protect. 76 (1998)
183–191.
[194] S.H. Chien, W.R. Clayton, Application of Elovich equation to the kinetics of
phosphate release and sorption in soils, Soil Sci. Soc. Am. J. 44 (1980) 265–268.
[195] D.L. Sparks, Kinetics and mechanisms of chemical reactions at the soil min-
eral/water interface, in: D.L. Sparks (Ed.), Soil Physical Chemistry, CRC Press,
Boca Raton, FL, 1999, pp. 135–192.
[196] E. Guibal, C. Milot, J.M. Tobin, Metal-anion sorption by chitosan beads: equi-
librium and kinetic studies, Ind. Eng. Chem. Res. 37 (1998) 1454–1463.
[197] Z. Cheng, X. Liu, M. Han, W. Ma, Adsorption kinetic character of copper ions
onto a modified chitosan transparent thin membrane from aqueous solution,
J. Hazard. Mater. 182 (2010) 408–415.
[198] G.M. Walker, L. Hansen, J.A. Hanna, S.J. Allen, Kinetics of a reactive dye adsorp-
tion onto dolomitic sorbents, Water Res. 37 (2003) 2081–2089.
[199] D. Reichenberg, Properties of ion-exchange resin in relation to their structure,
III. Kinetics of exchange, J. Am. Chem. Soc. 75 (1953) 589–597.
[200] R. Lagoa, J.R. Rodrigues, Kinetic analysis of metal uptake by dry and gel alginate
particles, Biochem. Eng. J. 46 (2009) 320–326.
[201] G.E. Boyd, A.W. Adamson, L.S. Mayers, The exchange adsorption of ions from
aqueous solutions on organic fly ash, kinetic II, J. Am. Chem. Soc. 69 (1947)
2836–2848.
[202] V.C. Srivastava, I.D. Mall, I.M. Mishra, Characterization of mesoporous rice
husk ash (RHA) and adsorption kinetics of metal ions from aqueous solution
onto RHA, J. Hazard. Mater. B 134 (2006) 257–267.
[203] M.H. Kalavathy, T. Karthikeyan, S. Rajgopal, L.R. Miranda, Kinetic and isotherm
studies of Cu(II) adsorption onto H3 PO4 – activated rubber wood sawdust, J.
Colloid Interface Sci. 292 (2005) 354–362.
[204] M. Trgo, J. Perić, N.V. Medvidović, A comparative study of ion exchange kinet-
ics in zinc/lead-modified zeolite-clinoptilolite systems, J. Hazard. Mater. 136
(2006) 938–945.
[205] C. Aharoni, D.L. Sparks, S. Levinson, I. Ravina, Kinetics of soil chemical reac-
tions: relationship between empirical equations and diffusion models, Soil
Sci. Soc. Am. J. 55 (1991) 1307–1312.
[206] D.L. Sparks, Kinetics of sorption/release reactions on natural particles, in:
P.M. Huang, N. Senesi, J. Buffle (Eds.), Structure and Surface Reactions of Soil
Particles, John Wiley and Sons, London, 1998, pp. 413–448.
[207] C. Namasivayam, R.T. Yamuna, Adsorption of chromium (VI) by a low cost
adsorbent: biogas residual slurry, Chemosphere 30 (1995) 561–578.
[208] T.S. Anirudhan, M. Ramachandran, Adsorptive removal of tannin from aque-
ous solutions by cationic surfactant-modified bentonite clay, J. Colloid
Interface Sci. 299 (2006) 116–124.
[209] M. Doğan, Y. Özdemir, M. Alkan, Adsorption kinetics and mechanism of
cationic methyl violet and methylene blue dyes onto sepiolite, Dyes and
Pigments 75 (2007) 701–713.
[210] V. Meshko, L. Markovska, M. Marinkovski, Experimental study and modelling
of zinc adsorption by granular activated carbon and natural zeolite, Int. J.
Environ. Pollut. 27 (2006) 285–299.
[211] J. Febrianto, A.N. Kosasih, J. Sunarso, Y.-H. Ju, N. Indraswati, S. Ismadji, Equi-
librium and kinetic studies in adsorption of heavy metals using biosorbent: a
summary of recent studies, J. Hazard. Mater. 162 (2009) 616–645.
[212] X.-S. Wang, C. Sun, Removal of copper(II) ions from aqueous solutions using
Na-mordenite, Sep. Sci. Technol. 42 (2007) 1215–1230.
[213] M.Y. Pamukoglu, F. Kargi, Effects of operating parameters on kinetics of
copper(II) ion biosorption onto pre-treated powdered waste sludge (PWS),
Enzym. Microb. Technol. 42 (2007) 76–82.
[214] S. Schiewer, S.B. Patil, Pectin-rich fruit wastes as biosorbents for heavy metal
removal: equilibrium and kinetics, Bioresour. Technol. 99 (2008) 1896–1903.
[215] A.B. Pérez Marín, M.I. Aguilar, V.F. Meseguer, J.F. Ortuño, J. Sáez, M. Lloréns,
Biosorption of chromium (III) by orange (Citrus cinensis) waste: batch and
continuous studies, Chem. Eng. J. 155 (2009) 199–206.
[216] Z. Aksu, A.I. Tatli, O. Tunç, A comparative adsorption/biosorption study of Acid
Blue 161: effect of temperature on equilibrium and kinetic parameters, Chem.
Eng. J. 142 (2008) 23–39.
[217] F. Helfferich, Ion Exchange, Dover Publications, New York, 1995, pp. 166–168.
[218] K.T. Valsaraj, Elements of Environmental Engineering: Thermodynamics and
Kinetics, Lewis Publisher, Boca Raton, Florida, 2000.
[219] Y.S. Al-Degs, M.I. El-Barghouthi, A.A. Issa, M.A. Khraisheh, G.M. Walker, Sorp-
tion of Zn(II), Pb(II), and Co(II) using natural sorbents: equilibrium and kinetic
studies, Water Res. 40 (2006) 2645–2658.
[220] S.J. Allen, G. McKay, K.Y.H. Khader, Intraparticle diffusion of a basic dye during
adsorption onto sphagnum peat, Environ. Pollut. 56 (1989) 39–50.
[221] M.F.F. Sze, G. McKay, An adsorption diffusion model for removal of
parachlorophenol by activated carbon derived from bituminous coal, Environ.
Pollut. 158 (2010) 1669–1674.
[222] B. Koumanova, P. Peeva, S.J. Allen, Variation of intaparticle diffusion param-
eter during adsorption of p-cholorophenol onto activated carbon made from
apricot stones, J. Chem. Technol. Biotechnol. 78 (2003) 582–587.
[223] V. Ponnusami, K.S. Rajan, S.N. Srivastava, Application of film-pore diffusion
model for methylene blue adsorption onto plant leaf powders, Chem. Eng. J.
163 (2010) 236–242.
[224] R. Apiratikul, P. Pavasant, Sorption of Cu2+ , Cd2+ , and Pb2+ using modified
zeolite from coal fly ash, Chem. Eng. J. 144 (2008) 245–258.
[225] B. Volesky, Biosorption process simulation tools, Hydrometallurgy 71 (2003)
179–190.
[226] J. Wang, C. Chen, Biosorbents for heavy metals removal and their future,
Biotechnol. Adv. 27 (2009) 195–226.
[227] I. Langmuir, The constitution and fundamental properties of solids and liquids,
J. Am. Chem. Soc. 38 (1916) 2221–2295.
[228] K.R. Hall, L.C. Eagleton, A. Acrivos, T. Vermeulen, Pore- and solid-diffusion
kinetics in fixed-bed adsorption under constant-pattern conditions, Ind. Eng.
Chem. Fundam. 5 (1966) 212–223.
[229] H.M.F. Freundlich, Uber die adsorption in losungen, J. Phys. Chem. 57 (1906)
385–470.
[230] R. Sips, On the structure of a catalyst surface, J. Chem. Phys. 16 (1948) 490–495.
[231] M.M. Dubinin, The potential theory of adsorption of gases and vapors for
adsorbents with energetically non-uniform surface, Chem. Rev. 60 (1960)
235–266.
[232] M.J. Temkin, V. Pyzhev, Kinetics of ammonia synthesis on promoted iron
catalyst, Acta Physicochem. URSS 12 (1940) 217–256.
[233] O. Redlich, D.L. Peterson, A useful adsorption isotherm, J. Phys. Chem. 63
(1959) 1024.
[234] J. Toth, State equations of the solid gas interface layer, Acta Chem. Acad. Hung.
69 (1971) 311–317.
[235] A.R. Khan, R. Ataullah, A. Al-Haddad, Equilibrium adsorption studies of some
aromatic pollutants from dilute aqueous solutions on activated carbon at
different temperatures, J. Colloid Interface Sci. 194 (1997) 154–165.
 S. Malamis, E. Katsou / Journal of Hazardous Materials 252–253 (2013) 428–461
[236] C.J. Radke, J.M. Prausnitz, Adsorption of organic solutes from dilute aque-
ous solutions on activated carbon, Ind. Eng. Chem. Fundam. 11 (1972)
445–450.
[237] F. Kargi, S. Ozmihci, Biosorption performance of powdered activated sludge
for removal of different dyestuffs, Enzym. Microb. Technol. 35 (2004)
267–271.
[238] S. Bruanuer, P.H. Emmett, E. Teller, Adsorption of gases in multimolecular
layers, J. Am. Chem. Soc. 60 (1938) 309–316.
[239] K. Vijayaraghavan, T.V.N. Padmesh, K. Palanivelu, M. Velan, Biosorption
of nickel(II) ions onto Sargassum wightii: application of two-parameter
and three-parameter isotherm models, J. Hazard. Mater. 133 (2006)
304–308.
[240] T. Grchev, M. Cvetkovska, T. Stafilov, J.W. Schultze, Adsorption of polyacryl-
amide on gold and iron from acidic aqueous solutions, Electrochim. Acta 36
(1991) 1315–1323.
[241] Y. Liu, Y.-J. Liu, Biosorption isotherms, kinetics and thermodynamics, Sep.
Purif. Technol. 61 (2008) 229–242.
[242] J.C. Bellot, J.S. Condoret, Modelling of liquid chromatography equilibrium,
Process Biochem. 28 (1993) 365–376.
[243] S.J. Allen, G. McKay, J.F. Porter, Adsorption isotherm models for basic dye
adsorption by peat in single and binary component systems, J. Colloid Inter-
face Sci. 280 (2004) 322–333.
[244] T.A. Davis, B. Volesky, A. Mucci, A review of the biochemistry of heavy metal
biosorption by brown algae, Water Res. 37 (2003) 4311–4330.
[245] B.A. Shah, A.V. Shah, R.R. Singh, Sorption isotherms and kinetics of chromium
uptake from wastewater using natural sorbent material, Int. J. Environ. Sci.
Technol. 6 (2009) 77–90.
461
[246] U.R. Malik, S.M. Hasany, M.S. Subhani, Sorptive potential of sunflower stem
for Cr(III) ions from aqueous solutions and its kinetic and thermodynamic
profile, Talanta 66 (2005) 166–173.
[247] P. Miretzky, C. Muñoz, A. Carillo-Chavez, Cd(II) removal from aqueous solution
by Eleocharis acicularis biomass, equilibrium and kinetic studies, Bioresour.
Technol. 101 (2010) 2637–2642.
[248] D.H.K. Reddy, K. Seshaiah, A.V.R. Reddy, M.M. Rao, M.C. Wang, Biosorption of
Pb+2 from aqueous solutions by Moringa oleifera bark: equilibrium and kinetic
studies, J. Hazard. Mater. 174 (2010) 831–838.
[249] S.J. Allen, Q. Gan, R. Matthews, P.A. Johnson, Comparison of optimised
isotherm models for basic dye adsorption by kudzu, Bioresour. Technol. 88
(2003) 143–152.
[250] K. Vijayaraghavan, H.Y.N. Winnie, R. Balasubramanian, Biosorption charac-
teristics of crab shell particles for the removal of manganese(II) and zinc(II)
from aqueous solutions, Desalination 266 (2011) 195–200.
[251] C.D. Johnson, F. Worrall, Novel granular materials with microcrystalline active
surfaces-waste water treatment applications of zeolite/vermiculite compos-
ites, Water Res. 41 (2007) 2229–2235.
[252] I.C. Ostroski, M.A.S.D. Barros, E.A. Silva, J.H. Dantas, P.A. Arroyo, O.C.M.A. Lima,
A comparative study for the ion exchange of Fe(III) and Zn(II) on zeolite NaY,
J. Hazard. Mater. 161 (2009) 1404–1412.
[253] P. Castaldi, L. Santona, S. Enzo, P. Melis, Sorption processes and XRD analysis
of a natural zeolite exchanged with Pb2+ , Cd2+ and Zn2+ cations, J. Hazard.
Mater. 156 (2008) 428–434.
[254] M. Achak, A. Hafidi, N. Ouazzani, S. Sayadi, L. Mandi, Low cost biosorbent
“banana peel” for the removal of phenolic compounds from olive mill waste-
water: kinetic and equilibrium studies, J. Hazard. Mater. 166 (2009) 117–125.