Environmental Engineering and Management Journal March/April 2008, Vol.7, No.

2, 149-161
http://omicron.ch.tuiasi.ro/EEMJ/

“Gh. Asachi” Technical University of Iasi, Romania

______________________________________________________________________________________________

SURFACTANT-MODIFIED NATURAL ZEOLITES FOR

ENVIRONMENTAL APPLICATIONS IN WATER PURIFICATION

Roxana Elena Apreutesei, Cezar Catrinescu∗, Carmen Teodosiu

Department of Environmental Engineering and Management, Faculty of Chemical Engineering, “Gheorghe Asachi”
Technical University of Iasi, 71A Bd. D. Mangeron, 700050 Iasi, Romania

Abstract

This paper presents an overview of research related to use of surfactant modified natural zeolites (SMZ) in water and wastewater
treatment. The most common natural zeolite, widely used as starting material is clinoptilolite, but other natural zeolites have also
been used (chabasite, heulandite, mordenite). In the first part, the preparation methods and the influence of process parameters on
the final product properties is reviewed. The discussion is focused on the influence of surfactant concentration in the water phase
related to the external cation exchange capacity of the zeolite. The physical-chemical characterization of raw and modified
zeolites by using relevant analytical methods (XRD, SEM, thermal analysis, FTIR spectroscopy, DRIFTS) is also presented. Thus,
an integrated view of the relation between the structure and the behavior of the modified-zeolites, covering both the compositional
and the structural aspects, can be obtained. Following surfactant modification process, the chemistry of zeolite surface is greatly
changed, allowing zeolites to sorb not only cations and polar organics but also nonpolar organics and anions, for which untreated
zeolites have little or no affinity. Consequently, the area of application of natural zeolites in water and wastewater treatment is
greatly extended.
The most relevant applications of surfactant-modified zeolites for the removal of anionic (chromate, phosphate, arsenate), cationic
(mercury, cadmium), organic pollutants (BTEX, chlorophenol, perchloroethylene, fulvic acids, dyes, pesticides, ionisable organic
solutes, PAHs) and microorganisms are reviewed.
The data reported in the literature suggest that naturally occurring zeolites modified with cationic surfactants can be considered as
potential sorbents for the removal of the most important categories of pollutants from polluted waters.

Key words: surfactant-modified zeolites, adsorption, water treatment, regeneration

1. Introduction chemically modified clays to retain toxic chemicals

Adsorption is an efficient and economically
feasible process for separation and purification,
playing an important role for the remove different
classes of pollutants from water and wastewater.
Activated carbon is the most common adsorbent for
the adsorption process because it has a high surface
area and a high adsorption capacity, but it is
expensive and necessitates regeneration. The need for
an alternative low-cost easily available adsorbent has
encouraged the search for new adsorbents. Many
studies have been performed to find suitable
adsorbents, including organic-inorganic hybrid
materials such as organophylic clays and surfactant
modified zeolites. The ability of natural and
and pathogenic microbes at their surface has been
studied extensively (Jaynes and Boyd, 1991; Jaynes
and Vance, 1996; Smith and Jaffe, 1994). In contrast
to clays, zeolites can occur as millimetre or greater
sized particles and are free of shrink–swell behavior.
As a result, zeolites exhibit superior hydraulic
characteristics and are suitable for use in filtration
systems (Lemic et al., 2007).
Zeolites are microporous crystalline
hydrated aluminosilicates, characterized by three-
dimensional networks of tetrahedral TO4 units (T is
Si4+ and Al3+) linked by the sharing of all oxygen
atoms. The partial substitution of Si4+ by Al3+ results
in an excess of negative charges, which is
compensated by extra framework alkali and earth

∗
Author to whom all correspondence should be addressed: email: ccatrine@ch.tuiasi.ro; tel./fax: +40 232 237 594
 Apreutesei et al./Environmental Engineering and Management Journal 7 (2008), 2, 149-161
alkaline cations. These cations are located along with
the water molecules in cavities and channels inside
the aluminosilicate framework. The water molecules
can be reversibly removed or replaced by other
sorbates (Rehákova et al., 2004).
Based on the pore size (the number of T
atoms in the ring openings) zeolites are referred to as
small (8-member ring), medium (10-member ring),
and large (12-member ring) pore zeolites. Based on
the framework Si/Al composition, zeolites are
categorized as: low Si/Al zeolites (Si/Al of less than
2), intermediate Si/Al zeolites (Si/Al=2-5), high Si/Al
zeolites (Si/Al ~ 10 to 100) and pure silica molecular
sieves. The Si/Al ratio is an important characteristic
of zeolites. Generally, by increasing the Si/Al ratio,
the thermal stability, acid strength and hydrophobicity
are increasing, whereas the ion-exchange capacity
decreases. The pure silica molecular sieves have a
neutral framework, are highly hydrophobic and have
no ion-exchange capacity or catalytic activity. The
topology of the zeolite framework is defined by a
unique three-letter code, e.g. HEU for clinoptilolite
which is not related to the composition of the
material. In all, 179 different framework structures
are now known. In addition to having silicon or
aluminium as the tetrahedral atom, other
compositions have also been synthesized, including
the growing category of microporous
aluminophosphates, known as ALPOs (van Bekkum
et al., 2007).
Many zeolites occur naturally as minerals,
and are extensively mined in many parts of the world.
Others are synthetic, and are made commercially for
specific uses or produced by research scientists trying
to understand more about their chemistry.
Zeolites possess three basic properties: ion-
exchange, adsorption and molecular sieving. These
properties are exploited in a wide spectrum of
applications, with a global market of several million
tones per year. Major uses are in catalysis
(petrochemical cracking), ion-exchange (water
softening and wastewater treatment) and in separation
and removal of gases and solvents. Other applications
are in agriculture, animal husbandry and
constructions.
Zeolites contribute to a cleaner, safer
environment in a great number of ways. In fact,
nearly every application of zeolites has been driven
by environmental concerns, or plays a significant role
in reducing toxic waste and energy consumption. In
powder detergents, zeolites replaced harmful
phosphate builders, now banned in many parts of the
world because of water pollution risks. As solid acid
catalysts, zeolites reduce the need for corrosive liquid
acids, and as redox catalysts and sorbents, they can
remove atmospheric pollutants, such as engine
exhaust gases and ozone-depleting CFCs. Moreover,
processes can be carried out in fewer steps,
minimizing unnecessary waste and by-products.
Zeolites can also be used to separate harmful organics
from water, and in removing heavy metal ions,
150
including those produced by nuclear fission, from
water.
A significant number of studies have
suggested that the area of application could be
expanded by functionalization of the zeolite surface.
Surface properties, such as hydrophobicity,
hydrophilicity can be controlled by organic
functionalization of the internal and external surface
of inorganic materials making them more suitable for
different applications. The common surface
functionalization of these inorganic materials is via
adsorption of cationic surfactants, although
functionalization with organophosphorus and
organosilane compounds has also been reported.
Many different applications are foreseen for these
organic-inorganic hybrid materials including
catalysis, sensors, drug delivery and environmental
protection.
Surfactant modified zeolites (SMZ) are
produced by treating zeolites with large cationic
surfactants (quaternary amines). These bulky organic
cations exchange selectively with native inorganic
cations to form a stable, organic-rich coating on the
external surfaces of the zeolite. Surfactant
modification dramatically alters the chemistry of the
zeolites surface, allowing the zeolites to sorb
nonpolar organic solutes and anions, for which
untreated zeolites have little affinity.
In the present paper we have atempted to
review the efforts made in exploring the potential
applications of surfactant modified natural zeolite for
water and wastewater treatment. The reviewd
material to be presented includes: (a) preparation and
characterization of surfactant modified zeolites
(SMZ); (b) SMZ to remove cation contaminants; (c)
SMZ to remove anion contaminants and (d) SMZ to
remove organic contaminants and microorganisms.
2. Synthesis and characterization of surfactant-
modified zeolites for environmental applications
Understanding the mechanism of surfactant
sorption and its subsequent conformation on the
zeolite surface is crucial for the understanding of the
interaction of sorbed surfacant with organic and
inorganic compounds in solution and predicting the
stability of the sorbed surfactant.
Surfactants are water-soluble organic
molecules which have both hydrophilic and
hydrophobic properties. Cationic surfactants have a
positively charged headgroup attached to a
hydrocarbon moiety. Above the critical micelle
concentration (cmc), individual surfactant molecules
self-associate into micellular clusters.
Several cationic surfactants have been used
to prepare SMZ: tetramethylammonium TMA
(Nikashina and Myaosedov, 1999),
tetraethylammonium bromide TEA (Sullivan,
1998) hexadecyltrimethylammonium bromide or
chloride HDTMA (Haggerty and Bowman, 1994),
cetylpyridinium bromide CPB (Nunez, 1998),
octadecyltrimethylammonium OTA (Xi et al.,
 Surfactant-modified natural zeolites for environmental applications

2005; Schulze-Makuch et al., 2002) ethylhexadecyl- stability, modified clinoptilolite prepared with
dimethylammonium (Nunez, 1998) and 4- surfactant solutions above the cmc and above the
methylpyridinium (Schulze-Makuch et al., 2004.), ECEC seems to be the most stable and has the fastest
benzyltetradecyldimethylammonium chloride sorption time. When solution concentrations fall
BDTDA (Kuleyin, 2007), below the cmc, HDTMA sorbed as a bilayer will still
benzyltrimethylammonium chloride BTMA, be stable as evidenced by negative values of the
stearyldimethylbenzylammoniumchloride SDBAC Gibbs free energy of sorption. Fig. 1 presents the
(Lemic et al. 2006). conceptual model of TEA and HDTMA sorption onto
natural clinoptilolite (Sullivan et al., 1998).
Zeolite-surfactant interactions
The zeolite framework structure contains
chanels and/or interconnected voids of discrete size
(in the range 3-20 Å) that allows the mineral to act as
a molecular sieve. Thus, large surfactant molecules
do not have access to the internal surface and sorb
only to the external surface of zeolite. Consequently,
the external cation exchange capacity (ECEC)
characterizes the exchange capacity of the mineral
surface for bulky surfactants.
The sorption of surfactants onto zeolite
surface is governed by two key factors: (1) the initial
concentration of surfactant in solution, as reported to
the cmc and (2) the ECEC of zeolite. Sullivan et al.
(1998) have studied the thermodynamics of TEA and
HDTMA sorption on natural clinoptilolite. Two
systems have been investigated: (a) the monomer
system, where the surfactant concentration was below
cmc and (b) the micellar system, with a surfactant
concentration much above cmc.
Several mechanisms, including ion
exchange, ion pairing, acid-base interaction,
polarization of π electrons, dispersion force, and
hydrophobic bonding, were attributed to the sorption
of cationic surfactants onto solid surfaces. Among
them, ion exchange and hydrophobic bonding were Fig. 1. Conceptual model of TEA and HDTMA sorption
the important ones (Ingram and Ottewill, 1991; Zajac onto natural clinoptilolite.
Sorption of TEA: (A) electrostatic interactions and weak
et al., 1996).
water destructuring. Sorption of HDMTA monomers: (B)
According to Sullivan et al. (1998) the electrostatic and weak water destructuring; (C) electrostatic
sorption of surfactant molecules to clinoptilolite and moderate water destructuring; (D) electrostatic and
occurs as two distinct processes, depending upon the strong water destructuring; (E) electrostatic and strong
degree of sorption. Initially, surfactant is sorbed by water destructuring. Sorption of HDTMA micelles: (F)
cation exchange, and later, surfactant is sorbed by electrostatic and moderate water structuring; (G)
hydrophobic forces. Early sorption is fast for all electrostatic and weak to moderate water destructuring.
systems, and then slows some time after the first half
hour. For the monomer system, it appears that Sorption kinetics of
sorption below the ECEC is in the form of individual hexadecyltrimethylammonium (HDTMA) chloride on
monomers, which may either interact with the a natural clinoptilolite have been investigated by Li
surface, or form coiled tail groups with a limited (1999). In this study, both surfactant and counterions
interaction with the solution. If available surfactant is concentration changes during the sorption process
in a sufficient quantity, a monolayer forms and tail were monitored. In agreement with previous findings
group interactions increase as a small amount of of Bitting and Harwell (Bitting and Harwell, 1987)
surfactant is sorbed as a bilayer, probably in the form the author stated that without counterion information
of patchy bilayers (disperse admicelles). For the the study of surfactant sorption would yield only
micellar system below the ECEC, sorption is in the limited value. The amount of HDTMA sorbed is a
form of admicelles which later rearrange to a function of the initial HDTMA input and the sorption
monolayer (disperse hemimicelles). Above the time. When the initial HDTMA input is less than the
ECEC, micelles sorbing initially may rearrange to the external cation-exchange capacity of the
extent of the ECEC, with the remainder forming clinoptilolite, the HDTMA sorption is fast and
patchy bilayers or admicelles on the surface. At high equilibrium can be established in 1 h. As the initial
loading levels, sorbed micelles are stable and later HDTMA input is greater than the external cation-
may coalesce to a full bilayer. In view of the energy exchange capacity of clinoptilolite, which will result
of the system and prediction of thermodynamic in more than a monolayer HDTMA surface coverage,

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the time for HDTMA sorption to reach equilibrium rise to a two-dimensional channel system parallel to
increases exponentially. The HDTMA sorption (010) responsible for a layer- like structure (Fig. 2)
maximum on clinoptilolite increases logarithmically (Armbruster , 2001).
with mixing time. The counterion solution Besides clinoptilolite, mordenite (Campos et
concentration data suggest that at the initial stage al., 2007), stilbite (Li et al., 200) and chabazite
HDTMA molecules sorb on the zeolite via micelle (Majdan et al., 2006) have also been used for the
forms, which is manifested by a decrease in chloride preparation of SMZ. It is also important to note that
solution concentration with time. When HDTMA the XRD patterns of SMZ showed only differences in
solution concentration is depleted to less than its the intensity of the diffraction peaks, but no changes
critical micelle concentration, the adsorbed micelles in their position were observed in comparison with
(admicelles) rearrange themselves to a more stable the starting materials.
monolayer or bilayer configuration, which is reflected
by an increase in counterion solution concentration
due to the desorption of chloride from admicelles.
The time required for the surface rearrangement
increases exponentially as the HDTMA input
increases. The data of HDTMA sorption kinetics were
fitted to different kinetic models, and the parabolic
diffusion model fits the data best for the HDTMA
sorption, counterion sorption at the initial stage, and
counterion desorption at the rearrangement stage.
Thus, the sorption of HDTMA on clinoptilolite
surfaces is diffusion controlled.
Different experimental conditions, reported
in the literature, for the preparation of SMZ are
summarized in Table 1. It is worthwhile mentioning
that a significant number of recent studies (Macedo-
Fig. 2. Columnar model of the twodimensional channel
Miranda and Olguin, 2007; Majdan et al., 2006; arrangement parallel to (010) in HEU frameworks.
Kuleyin, 2007) have suggested that a pre-treatment of The dark gray columns parallel to [001] represent eight- and ten-
the starting zeolite-containing material with membered ring channels. These channels are cross-linked by the
concentrated NaCl solution, in order to reach a final light gray eight-membered ring channels running parallel to [100]
and [102]
homoionic or near homoionic Na+ form of the
zeolites, may enhance their ion exchange abilities,
For these SMZ, the total CEC varies
e.g. by improving the effective cation exchange
between 800 and 2200 meq/g, with an ECEC in the
capacity (Diaz-Nava et al., 2005).
range of 70 – 110 meq/g.
Most of the papers dealing with the use of
The specific surface area for the natural
SMZ for pollutant removal contain only limited
clinoptilolite is low (10-40 m2/g). Following surface
information on the physical-chemical characterization
modification, a further decrease in the surface area is
of sorbents. Usually, data on the phase composition,
usually observed and this is attributed to the sorption
BET surface area and (E)CEC are provided. As
of surfactant on the external area of the mineral. For
presented in Table 1, XRD data is used to identify the
example, the specific surface area of natural and
phase composition and the purity of raw zeolite-
surfactant modified Mexican zeolitic tuffs (Cortés-
containing material. Most of the studies have used
Martínez et al. , 2007) were 20.56 and 10.76 m2/g,
zeolitic tuffs containing clinoptilolite as the major
which show clearly that the surface area of the SMZ
component (60-90 % wt.) with the remaining being
is smaller, almost in 50%, than that of the natural
mainly feldspars, clays, glass, and quartz. Heulandite,
zeolite (NaZ). The SEM images showed
having the same framework topology (HEU) as
morphologies characteristic of clinoptilolite, which
cliniptilolite but a ratio Si/Al smaller that 4.0, is also
occurred as euhedral plates and laths, whose crystals
present in some minerals, such as the Mexican
display characteristic monoclinic symmetry, and
zeolitic tuff (Cortés-Martínez et al., 2004; Cortés-
many are coffin-shaped, and cubic-like crystals.
Martínez et al. 2007, Macedo-Miranda and Olgiun,
After the zeolites were treated with a
2007) . This is a special case where zeolites are
surfactant solution, a thin cover was frequently found
distinguished solely on the basis of the framework
in some regions of the surface of the natural zeolite
Si/Al ratio. The structural topology of the tetrahedral
(Macedo-Miranda and Olgium, 2007). The TG, DTG
HEU framework is well understood and possesses
and DTA curves for different zeolites, surfactants and
C2/m space group symmetry with oblate channels
SMZ are presented in some recent articles (Majdan et
confined by ten-membered (7.5 × 3.1 Å) and eight-
al, 2006; Lemic et al., 2007). In the DTA spectrum of
membered tetrahedral rings (4.6 × 3.6 Å) parallel to
pure HDTMA three endothermic DTA peaks are
the c-axis.
noticed.
Additional eight-membered ring channels
(4.7 × 2.8 Å) running parallel to [100] and [102]
cross-link the former channels within (010), giving

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 Surfactant-modified natural zeolites for environmental applications

Table 1. Experimental conditions and applications of SMZ

Zeolitic tuff Phase Characteristics Surfactant Characterization Applications

composition modification methods
(XRD analysis)
CEC ECEC Surface Particle Density
area size
Clinoptilolite from
Winston, New 74% 800 meq/kg 70-110 13.3- 0.15- HDTMA-Br, Removal of:
Mexico (Bowman, clinoptilolite meq/kg 15.7 1.4 mm 99% purity - chromate
2003 ) 5% smectite m2/g HDTMA-Cl - bacteria and
10% quartz (20 ml/5 g viruses
10% feldspar zeolite) - BTEX
1% illite - perchlorethylene
Clinoptilolite from 70-90 15.7 - tapping-mode - ionizable
Winston, New meq/kg m2/g Atomic Force organic solutes
Mexico (Sullivan Microscopy; - 4-chlorophenol
et al., 1997 ) - high- resolution - arsenic
Thermogravimetric
Analysis
Clinoptilolite from
Beocin Mine, 80% 1390-1570 75-78 0-3 SDBAC Thermal analysis : Removal of:
Serbia and clinoptilolite mmol/kg mmol/kg mm 80% TG, DTG, DTA. - atrazine
Montenegro 20% impurities 19% propan- - lindane
(Lemic et al., ( feldspar, 2-ol - diazinone
2006, Lemic et al., quartz, 1% water - PAHs
2007) carbonate)
Clinoptilolite from 2.15
Enli Mining, 92% purity 1.9-2.2 meq/g 11.80 g/cm3 HTAB Removal of azo dyes
Turkey (Benkli et m2/g density; in fixed-bed reactor
al., 2005) 1.30
g/cm3
apparent
density
Mordenite, Brazil
(Campos et al., 96% mordenite 2.29 meq/g 14.6 EHDDMA Removal of chromate
2007) m2/g and HDTMA
Clinoptilolite from
Manisa, Turkey 92% purity 1.9-2.2 meq/g 11.8 2.15 CTAB-Br, FT-IR analysis Removal of Reactive
(Karadag et al., m2/g g/cm3 99% purity SEM analysis Black 5 and Reactive
2007) density Red 239
Clinoptilolite from
Zlatokop, 85% 1420mmol/kg 182-198 37- oleylamine TG, DTA, DDTA Removal of
Yugoslavia clinoptillolite mmol/kg 40.3 mycotoxins
(Tomosevic- 15% impurities m2/g
Canovic et al., (pyrite, quartz,
2003) feldspar)
Clinoptilolite from 40-50% purity
Croatia (Curkovic 50-60% 12.055 0.1-2 Removal of cadmium
et al., 1997) impurities m2/g mm and lead
(illite,
montmorilonite,
feldspar,
calcite, quartz,
halite)
Clinoptilolite from 60% Removal of fulvic
China (Wang et clinotilolite 160-180 0.096 12.5 HDTMA-Br acids in a fixed-bed
al., 2006) 40% mordenite, mmol/100g mmol/g m2/g 99% purity reactor
quartz
Chabazite from
USA (Majdan et 80% purity 2.5 meq/g 520 1.74g/cm3 HDTMA-Br -Thermal analysis: Removal of
al., 2006) m2/g DTA, DTG, chromates
DRIFT, FTIR, -
XRD

Clinoptilolite from 0.8576- 20.56- 1.7- HDTMA-Br SEM analysis Removal of 4-

Mexico (Cortez- 0.0464 meq/g 10.76 1.18 57.6 ml/32 g chlorophenol
Martinez et al., , m2/g mm zeolite
2007)

The two peaks appearing at: 68.6 and 100.7 °C are in the alkyl chains of surfactant. This is probably the
probably the result of some structural rearrangements process of “kink” formation known as chain melting,

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which is based on the introduction of conformational
isomerization via rotation about the C–C bonds.
This brings one or more gauche bonds to
trans bonds in the alkyl chains. The third DTA peak
at 261.3 °C occurs commonly with DTG peak and
results from the melting, evaporation and pyrolysis of
the surfactant. In the case of Na/ HDTMA–chabazite
two broad DTG peaks occur in 100–150 and 350–450
ºC ranges. First of them is associated with broad DTA
peak in 100–150 ºC range and is a consequence of
dehydration of the modified zeolite samples. The
second DTG peak results from pyrolysis of HDTMA
adsorbed on the chabazite. The peak is broad as a
consequence of different forms of surfactant present
in the chabazite structure like: monomers, micelles
and its different ability to decomposition. The shift of
the temperature of pyrolysis from 261.3 ºC for pure
HDTMA to 350–450 ºC for chabazite samples is the
evidence that there is lack of pure, unbound HDTMA
in the chabazite structure. The strong evidence for
this fact is also the absence of a sharp endothermic
peak resulting from chain melting in the zeolite
samples. There is a strong interaction of HDTMAC
cations through electrostatic and Van der Waals
forces with the zeolite network, which makes melting
and easy pyrolysis of HDTMA impossible.
In the FTIR spectra of Na/HDTMA–
chabazitethere three are groups of bands originating
from the zeolite matrix: 400–1200, 1640–1650, 3000–
4000 cm-1. The first group of bands results from
stretching sceletal vibrations and within aluminium–
silicon tetraeders, whereas the second and third group
of bands appear as a consequence of deformation and
stretching vibrations in water molecules. In turn the
bands: 715–740, 1420–1480, 2800–3000 cm-1 are
specific for surfactant molecules. The rocking δr nand
scissoring δs vibrations in methylene group preserve
an essentially unchanged position during the
surfactant concentration increase in equilibrium
aqueous phase and in zeolite phase. In pure HDTMA
spectrum the bands responsible for these vibrations
are splitted. The singlet character of these bands in
Na/HDTMA–chabazite is related to the fact that alkyl
tails of adsorbed alklyammonium cations are poorly
packed on the chabazite surface, so probably a liquid
like structure of adsorbed surfactant molecules
occurs.
From the DRIFT spectra of chabazite and
Na/HDTMA–chabazite ( Majdan et al., 2006) found a
small shift of T–O–T band, associated with stretching
vibration in Si–O–Al subunits, to higher frequency
for Na/HDTMA–chabazite. They concluded that that
the replacement of the small Na ion by large
HDTMA cation results in the relaxation in Si–O–Al
stretching vibrations and the shift of T–O–T band to
higher frequency.
3. Environmental applications of SMZ for water
purification
Surfactant –modified zeolites are able to
simultaneously eliminate three different categories of
154
pollutants: cations (mainly by an ion-exchange
process, with the participation of the remaining
countercations from both external and internal surface
area), anions (by ion-exchange on the quaternary
ammonium groups belonging to the surfactant
molecules organized as admicelles or bilayers) and
organic compounds (by partition of the organics
intro the hydrophobic phase created on the external
zeolite surface by the surfactant tail groups), as
presented in Fig. 3 (Bowman, 2006).
Fig. 3. Schematic diagram of sorption mechanisms for
anions, cations, and nonpolar organics on SMZ
3.1. Application of modified zeolites to remove
anionic contaminants
Campos et al. (2007) studied the removal of
inorganic anion (chromate CrO42-) from drinking
water contaminated with Cr on a HDTMA modified
zeolite (96% mordenite) at pH values of 4.9-5.3.
According to Bowman et al. (1995), sorption
of inorganic anions on cationic surfactant-modified
zeolite has been attributed to the formation of a
surface-anion complex. To sorb anions and form a
complex, the modified surface must possess
positively charged exchange sites. These sites are
formed when positively charged surfactant head
groups are presented to the surrounding solution in
the form of a bilayer or patchy bilayer. The positively
charged head groups are balanced by counter ions,
and the sorption or exchange of the other anionic
constituents involves the replacement of weakly held
counter ions by more strongly held counter ions. Li et
al. (1998) studied counter ion effects on the sorption
of cationic surfactant on natural zeolite and found that
the HDTMA-Br and HDTMA-Cl formed complete
bilayers on the zeolite, whereas HDTMA-HSO4
showed less than full bilayer formation (Campos et
al., 2007).
The HDTMA-modified zeolite showed
significant removal of chromate from aqueous
solution. The results showed that the maximum
percentage adsorption was 93%.
Li (2006) studied the removal of chromate
from contaminated groundwater using surfactant-
modified zeolite as permeable barrier. The zeolite was
modified with hexadecyltrimethylammonium
bromide (HDTMA-Br) at a liquid to solid ratio of 3:1
 Surfactant-modified natural zeolites for environmental applications
(Li, 2006). The conclusions of the study were that the
100% chromate recovery indicates that surfactant-
modified zeolite (SMZ) as permeable barrier only
retards the chromate migration. Regeneration of SMZ
for anion sorption without restoring the surfactant
bilayer formation is almost impossible due to
stripping off of the upper layer, and thus the
counterions, from the HDTMA admicelle formation
as water flows through the columns. The permeable
reactive barrier has the capacity to reduce chromium
concentration from contaminated groundwater; the
adsorption percentage is very low.
Bowman (2003) studied the applications of
surfactant modified zeolites as permeable barrier for
the removal of environmental contaminants from
water, using a natural clinoptilolite (74% purity)
modified with HDTMA-Cl. The use of SMZ as a
sorbent was evaluated in a permeable barrier at
laboratory scale for the removal of chromate from
contaminated groundwater. Pilot tests showed that
SMZ permeable barrier was very effective for
removing chromate from groundwater. Chromate was
fully retained by the barrier, with no detectable
concentrations down gradient.
Research on the use of cationic surfactant
modified zeolite to remove phosphate, PO4+ has
been carried out. It was reported that surfactant
modified zeolite using cethylpyridinium chloride
could remove phosphate ranging from 50% to 90%
depending upon variables such as concentration of
cethylpyridinium chloride on the preparation of
surfactant modified zeolite; the initial phosphate
concentration, contact time and initial pH influence
on the adsorption of phosphate using SMZ
(Widiastuti et al., 2008).
Another investigation of the use of cationic
surfactant zeolite to remove arsenate, ArO43- was
reported by Macedo-Miranda and Olguín (2007) who
showed that by modifying the adsorption
characteristics of the natural zeolite using lanthanum,
hexadecyltrimethylammonium and iron compounds
will improve the arsenic adsorption capacities. The
results suggested that the arsenic retention depends on
the precedence of zeolitic material, the nature of
arsenic chemical species, pH as well as the
characteristics of modified natural zeolites. The
modified zeolite has good characteristics for potential
treatment of As(III) or As(V) polluted waters.
Other anions, e.g. SO42- and SeO42- have
been removed by using surfactant modified zeolites
by Bowman et al. (1995).
3.2. Application of modified zeolites to remove
cationic contaminants
Research work on the removal of mercury
and cadmium from water by modified surfactant
zeolite shows that large quantities of these elements
are sorbed.
Gebremedhin-Haile et al., (2003) have
studied the mercury sorption from aqueous solutions
in the presence and absence of heavy metals (Cu2+,
Ni2+, Zn2+) onto modified zeolite with cysteamine
hydrochloride or cysteamine dihydrochloride in
acidic pH. The zeolitic minerals are characterized by
thermo gravimetric analysis, scanning electron
microscopy, X-ray diffraction and FTIR.
It has been experimentally showed that the
pretreatment with NaCl on zeolite (before the
modification with cysteamine hydrochloride or
cysteamine dihydrochloride) enhances their ion
exchange ability.
It was found that the mercury removal from
aqueous solution (without any content of havy
metals) is from 80 to 90%. The removal of mercury
by modified pretreated zeolite from mixed metal
solution is lower, about 42%, because of the
competition of copper, nickel and zinc for the
exchange sites intro the zeolite network.
Ćurković et al., (1997) were able to remove
Pb2+ and Cd2+ from water using a modified
clinoptilolite treated with NaCl. They found removal
efficiencies of 90 and 70%, respectively.
Haggerty and Bowman (1994) showed that
the sorption of small, selectively bound hydrated
cations such as Cs+ is little reduced by HDTMA
treatment. Sorption of larger, less selectively retained
cations such as Sr2+ and La3+ is greatly reduced.
These hard cations are probably exchanging with
cations on the zeolite's internal surfaces, to which
access is limited by the HDTMA coating. "Sorption"
of Pb2+ is much less affected by surfactant treatment,
probably due to specific surface interactions and/or
precipitation of lead hydroxides on the external
zeolite surface.
3.3. Application of modified zeolites to remove
organic contaminants
BTEX removal
The study of Ranck at al. (2005) evaluates
the effectiveness of surfactant-modified zeolite
(SMZ) for the removal of benzene, toluene,
ethylbenzene and xylenes (BTEX) from water. The
long-term effectiveness of SMZ for BTEX removal
was investigated along with changes in sorption
properties for long-term use. The zeolite used in this
study was a natural clinoptilolite-rich tuff from St.
Cloud mine, New Mexico. The zeolite was modified
with HDTMA-Cl.
The BTEX mobility in laboratory columns
of SMZ was studied so as to decrease water solubility
and to increase Kow (octanol-water partition
coefficient). The most soluble compound, benzene,
began to elute at 8 pore volumes, while the least
soluble compounds, ethyl benzene and xylenes, began
to elute at 50 pore volumes. After treating 4.500 pore
volumes of water in the column system over 10
sorption/regeneration cycles, no significant reduction
in the sorption capacity of the SMZ for BTEX was
observed. The mean Kds (linear sorption coefficient)
determined in the column experiments ranged from
18.3 L/kg for benzene to 95.0 L/kg for p- and m-
xylene.
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Laboratory columns were upscaled to create
a field-scale SMZ treatment system. The field-scale
system was tested at a natural gas produced-water
treatment facility. It was observed a greater sorption
of BTEX in the field column than predicted from the
laboratory results. In the field column, initial benzene
breakthrough occurred at 10 pore volume and toluene
breakthrough began at 15 pore volume, and no
breakthrough of ethylbenzene or xylenes occurred
throughout the 80 pore volume experiment.
The results of this investigations show that
SMZ completely removes BTEX from produced
water up to a compound-specific capacity, and that
SMZ can be regenerated via air sparging without loss
of sorption capacity. Field-scale tests supported
laboratory column test data showed greater sorption
of BTEX from produced water that was observed in
the laboratory columns. The results of this study
along with the low cost of SMZ suggest that
surfactant modified zeolites may have use in cost-
effective produced-water treatment systems.
Altare et al. (2007) studied the removal of
volatile organic compounds such as benzene, toluene,
ethylbenzene and p-, m-, and o-xylene (BTEX) from
oil and gas-field wastewaters using surfactant-
modified zeolite (SMZ). The cationic surfactant used
was hexadecyltrimethylammonium (HDTMA).
Laboratory column studies were used to investigate
how different airflow rates impact regeneration of
BTEX-saturated SMZ and to perform long-term tests
to determine the chemical and physical stability of
SMZ in a water treatment system.
Varying the airflow rate from 1.3 to 10 pore
volumes (PV) per minute did not significantly affect
BTEX removal rates. Rather, BTEX removal was
controlled by the total mumber of PV that passed
through the SMZ bed, suggesting only minor kinetic
effects on regeneration. BTEX sorption and SMZ
regeneration profiles varied little over 50
sorption/regeneration cycles. Each cycle consisted of
BTEX sorption from 100 PV of produced water
followed by regeneration with approximately 2000
PV of air. A weakly decreasing trend was observed
for the BTEX distribution coefficients (Kd),
indicating only a small loss in the sorption affinity
after 50 cycles. The sorption affinity for BTEX was
maintained even though 20% of the original
surfactant was washed off the SMZ by 5000 PV of
produced water. The hydraulic conductivity of the
SMZ decreased by roughly 30% after 50 cycles. Most
of the hydraulic permeably loss is most likely caused
by particle attrition.
The results of this study suggest that
surfactant modified zeolite is an effective sorptive
medium for removing volatile organics from oil-and
gas-field wastewaters. It offers a low-cost and easily
regenerable option for producers who want or need to
treat their produced water.
Chlorophenol removal
Cortés – Martínez et al. (2007) investigated
the removal of 4- chlorophenol from aqueous
156
solutions by a Mexican clinoptilolite-heulandite
zeolites, modified with the surfactant
hexadecyltrimethylammonium bromide (HDTMA-
Br), using batch and packed-bed (column)
configurations. The effects of pH, contact time and
concentration of 4-chlorophenol on the adsorption
process by the surfactant modified zeolites were
examined. The sorption of 4-chlorophenol was not
affected by the pH range from 4 to 9.5. Thus, 4-
chlorophenol retention reached equilibrium in about
18 h and the rate of 4-chlorophenol adsorption by the
modified zeolites was faster in the first 10 h than
later. The experimental data were modeled by using:
pseudo-first order, pseudo-second order, fractional
power and Elovich models. Although, the last three
gave correlation coefficients higher than 0.96, the
pseudo-second order model was the best to describe
the reaction rate. The experimental data followed a
linear isotherm which is characteristic for sorption of
organic solutes by the partition mechanism. The
results of this study showed that the surfactant
modified zeolites could be considered as pontetial
adsorbent for 4-chlorophenol removal from aqueous
solutions.
Kuleyin (2007) studied the adsorption
characteristics of phenol and 4-chlorophenol by a
surfactant-modified zeolite. It was used a
clinoptilolite zeolite modified with HDTMA- Br
(hexadecyltrimethylammonium bromide) and
benzyltetradecyl ammonium chloride (BDTMA).
Batch studies were performed to evaluate the
effects of various experimental parameters such as
contact time, adsorbent dose, initial concentration and
temperature on the removal of phenol and 4-
chlorophenol. The sorption kinetics was tested for
intraparticle diffusion, Elovich and pseudo-second
order reaction and rate constants of kinetic models
were calculated. Equilibrium isotherms for the
adsorption of phenol and 4-chlorophenol were
analyzed by Freundlich, Langmuir and Tempkin
isotherm models. Freundlich isotherm was found to
best represent the data for phenol and 4-chlorophenol
adsorption.
Adsorption kinetics was found to follow
second order kinetic model. The increase in initial
concentration of phenol and 4-chlorophenol resulted
in an increase in the adsorption by the surfactant
modified zeolite. The adsorption of phenol and 4-
chlorophenol on surfactant modified zeolite is
favorably influenced by an increase in the
temperature.
The conclusions of the study showed that
surfactant-modified zeolite is an effective sorbent for
the removal of phenol and 4-chlorophenol from
aqueous solution. It was also found that 4-
chlorophenol showed a higher dsorption capacity than
phenol on surfactant-modified zeolite.
Perchloroethylene removal
In the study of Li and Bowman (1998) a
natural zeolite was modified with a cationic surfactant
to achieve different fractional organic carbon contents
 Surfactant-modified natural zeolites for environmental applications
and different surfactant molecule configurations on
the surface. The sorption of perchloroethylene (PCE)
by the surfactant modified zeolite was found to be
dependent on the bound surfactant molecule
configuration as well as on the fractional organic
carbon content. The sorption of PCE on SMZ is due
to partitioning of PCE into the organic phase formed
by the surfactant on the zeolite surface. The PCE
sorption coefficient on SMZ is a function of the
surfactant loading and resultant organic phase
density.
PCE is most efficiently sorbed by SMZ
when surfactant is present at or below full monolayer
coverage; at higher surfactant loading levels, PCE
sorption appears limited by a reduced effective
volume and an increased density of the hydrophobic
core of the sorbed surfactant bilayer, resulting in a
decreased koc (distribution coefficient). The greater
hydrophobicity of the monolayer- versus the bilayer-
modified surface may also add to the greater PCE
sorption efficiency exhibited by the monolayer
system. The results from this research indicate that
for removal of PCE from water, the most economical
treatment would be to produce a monolayer, rather
than a full bilayer, of HDTMA on the zeolite surface.
Fulvic acids removal
Modification of zeolite (clinoptilolite)
surface with a quaternary ammonium, HDTMA, to
improve the removal efficiency of fulvic acids (FA)
was investigated by Wang et al. (2006). The
experiment consisted of modifying the clinoptilolite
with HDTMA followed by adsorption and desorption
of FA in the column. The effects of relevant
parameters, such as HDTMA loading leves, FA flow
rate and eluant concentration were examined.
Optimization studies showed that the SMZ bed with
HDTMA loading of 120% of ECEC at a flow rate of
5 bed volumes/h had the best performance and the
volume of 23 bed volumes of 30% ethanol solution
with the feed flow rate of 5 bed volumes/h was
sufficient for complete regeneration of SMZ and
desorption of FA. Measurements of Zeta potential of
SMZ indicate that a monolayer formation is the most
viable packing that enables maximum removal of FA.
FA adsorption on SMZ surfaces is largely
due to the hydrophobic interaction and hydrogen
bonding while FA desorption depends on hydrogen
bonding. Partition and mass transfer also play an
important role in the adsorption and desorption of FA.
Dyes removal
Benkli et al. (2005) studied the removal of
azo dyes using zeolites (clinoptilolite) modified with
quaternary amine, hexadeciltrytrymethylammonium
bromide (HDTMA-Br), in a zeolite fixed bed. A
series of adsorption tests were conducted to find out
the uptake of three types of reactive dyes: CI Reactive
Black 5, Red 239 and Yellow 176. Each run consisted
of modifying zeolite with HDTMA-Br in the column
followed by removal of color from the modified
zeolite bed. The breakthrough curves for the
modification process were constructed under different
conditions by plotting the normalized effluent
concentration (C/C0) versus time or bed volumes
(BV). Optimization studies show that 3g/l of
HDTMA-Br dosage at flow rate of 0.025l/min
showed the best performance. Examination of the dye
removal under the optimum modification condition
reveals that the black dye gives the highest
breakthrough point among the three dyes tested. This
is ascribed to the hydrophobic/hydrophilic match of
the zeolite surface with the dye molecule, which
depends upon the way zeolite is modified with
HDTMA-Br.
Comparison of the dye adsorption by
modified zeolite in a fixed bed at optimum conditions
indicated the order of dye removal by modified
zeolite in the following manner: black>yellow>red.
Surface coverage calculations demonstrate that the
most uitable orientation of the HDTMA-Br
adsorption on the zeolite surface is the formation of
bilayer. The bilayer formation favors the interactions
of anionic dye groups and HDTMA-Br covered
cationic zeolite surface, as proposed by the authors of
this study.
Karadag et al. (2007) studied the adsorption
of Reactive Black 5 (RB 5) and Reactive Red 239
(RR 239) aqueous solution onto surfactant-modified
zeolite with cetyltrimethylammonium bromide
(CTAB) in batch system.
Experiments were performed at different
conditions such as initial dye concentration, contact
time, temperature, and pH. CTAB modification
covered the zeolite surface with positive charges, and
the adsorption capacity of zeolite increased. The
adsorption capacity of Reactive Red 239 was found to
be two times higher than reactive Blue 5 due to the
hydrophilicity of the dye molecules (6.36 and 3.84).
The Langmuir and Freundlich adsorption models
were applied to describe the equilibrium isotherms at
different temperatures, and Freundlich model agrees
very well with the experimental data. The calculated
maximum adsorption capacity increased with
increasing initial dye concentration, but there is no
linear relationship with pH and temperature. The
equilibrium adsorption capacity of RB 5 showed a
maximum at pH 7, but the adsorption capacity of RB
5 at equilibrium was not influenced by the pH
various.
Ionizable organic solutes removal
Sorption of ionizable organic solutes on a
clinoptilolite-rich zeolitic tuff modified with
hexadecyltrimethylammonium bromide (HDTMA-
Br) was studied by Li et al. (2000). The sorption of
benzene and its ionizable analogues phenol and
aniline by surfactant-modified zeolite, prepared at
different HDTMA surface coverage, was affected by
solution pH. All of the isotherms were linear and
could be described by a distribution coefficient (Kd).
At neutral pH, the Kd values of benzene, phenol, and
aniline on SMZ increased with HDTMA loading up
to monolayer coverage of 100 mmol/kg. Beyond
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monolayer coverage, further increases in HDTMA
loading did not increase the Kd values of the solutes at
pH 7.0, where all species exist primarily in their
neutral forms. The Kd values were consistent with the
relative octanol-water partition coefficients of the
three compounds, indicating that sorption of the
neutral species was primarily by partitioning into the
bound HDTMA organic pseudo phase.
Phenol sorption by SMZ treated to bilayer
coverage increased as the pH, and hence fraction of
anionic phenolate, increased. The counterion balance
indicated that the increased retention of phenol was
due partially to anion exchange of phenolate from
bromide, the same mechanism responsible for
sorption of inorganic anions by SMZ. In contrast,
decrease in pH resulted in reduced aniline sorption
due to a lower concentration of the neutral species
and repulsion of the positively charged anilinium
from SMZ treated to bilayer coverage. Sorption of
benzene, phenol and aniline by SMZ followed linear
sorption isotherms in the pH range of 3.6-11.2.
The results of the study demonstrate that
SMZ are effective in sorbing ionizable organic
compounds in addition to hydrophobic nonionic
compounds. When solution pH is such that the neutral
form of an ionizable species dominates, no sorption
enhancement occurs in treating the SMZ beyond
monolayer coverage. At pH values where ionized
species are important, sorption to SMZ at bilayer
coverage will be enhanced or depressed depending
upon the ionic charge. For solutes such as aniline that
protonate at low pH, optimal sorption may occur at
submonolayer coverages of SMZ, where some cation
exchanges sites of the zeolite still remain avaible to
sorb other cationic species.
Pesticides removal
Systematic adsorption tests were carried out
by Lemic et al. (2006) to determine the efficiency of
SMZ for removal of atrazine, lindane and diazinone
from water. The hydrophobic character of SMZ-
pesticide interactions was confirmed by measuring
the amount of pesticides sorbed on zeolite samples
modified with 25, 50, 75 and 150 mmol of
stearyldimethylbenzylammoniumchloride
(SDBAC)/kg of zeolite. The effects of adsorbent
particle size, solid content in the suspension and the
initial pesticide concentration in the solutions were
also investigated. The amount of atrazine sorbed
decreased with increasing particle size, which is
associated with the reduction of the specific surface.
The sample with the smallest particle size (0-0.4 mm)
was the most effective for the adsorption of atrazine
(42.3 µmol/kg), but these particles were found to be
too small for application in filtration systems.
Previous studies of the sorption of
contaminants by organo-minerals indicated that the
increase of adsorption efficiency with increasing
concentration of adsorbent in the suspension was not
linear (Bouffard and Duff, 2000; Dakovic´ et al.,
2003). Similiar results were obtained for the
adsorption of atrazine and lindane on the SMZs. The
158
adsorption indexes (AI) of both pesticides increased
with increasing adsorbent concentration. In the case
of diazinone the sorption was related to the amount of
surfactant on the mineral surface and to the
concentration of diazionone in solution. For effective
adsorption of this pesticide onto an SMZ , it is
necessary for the SDBAC/diazinon ratio to be higher
than 25. The adsorption capacities, calculated by
fitting the experimental data to the Langmuir–
Freundlich equation, were 2.0 µmol/g (atrazine), 4.4
µmol/g (diazinone) and 3.4 µmol/g (lindan). At lower
initial concentrations of pesticide solution, a linear
dependence existed between the amount adsorbed and
the equilibrium concentration of pesticide. The linear
adsorption coefficients (Kd) were much higher for
lindan and diazinone 0.654 and 0.502 µmol-1dm3 in
contrast to atrazine (0.025). Column experiments
confirmed the efficiency of the OZs for pesticide
sorption. Column experiments showed that at
volumetric flow of 6 cm3/ min, the breakthrough
points (at C/C0 =0.1) were 560 bed volume (BV) for
lindane and 620 for diazinone.
PAHs removal
Sorption of polycyclic aromatic
hydrocarbons (PAHs) on organo-zeolites was
investigated by Lemić et al. (2007) to determine
sorbent-sorbate interaction. The hydrophobic
character of the surface of the organo-zeolites was
studied using water vapor adsorption experiments.
The zeolite was modified using
stearyldimethylbenzylammoniumchloride (SDBAC)
solutions of four initial concentrations: 50, 75, 100
and 150 mmol/dm3 in order to achieve
SDBAC/external cation exchange capacity (ECEC)
rations of 0.67, 1.0, 1.33 and 2.0. Water adsorption
decreased with increasing
stearyldimethylbenzylammoniumchloride (SDBAC)
loading up to 75 mmol/kg, which is related to
increasing sorbate hydrophobicity.
In this study, the sorption values of
fluorene, phenanthrene, benz[a]anthracene,
fluoranthene and pyrene on the surface modified
zeolites were determined. The adsorption was studied
under batch and column conditions. In order to
determine the influence of the adsorbent size on the
adsorption of PAHs, zeolites with different particle
size were modified in the same manner using a 100
mmol/dm3 SDBAC solution concentration. The
maximal amount of SDBAC sorbed on the zeolite
surface was 123 mmol/kg, which is 164% of the
ECEC value of the zeolite.
Adsorption efficiency of the organo-zeolites
of different particle size with the same surfactant
loading for the PAH compounds was determined on
different samples of organo-zeolites. The adsorption
index of sample OZ I 100 (OZ - organo-zeolite; I –
particle size 0.0-0.4 mm; 100 – mmol of surfactant/kg
of zeolite) were greatest (98% without losses) for all
the PAH compounds. With increasing the particle
size, the adsorption efficiencies decreased. The
difference was significant, especially in the case of
 Surfactant-modified natural zeolites for environmental applications
sample OZ III 100 (OZ - organo-zeolite; III – particle
size 0.8-3 mm; 100 – mmol of surfactant/kg of
zeolite), where the adsorption indexes were in the
range of 50-83%. The adsorption efficiency of sample
OZ II 100 (OZ - organo-zeolite; II – particle size 0.4-
0.8 mm; 100 – mmol of surfactant/kg of zeolite) was
the greatest for fluorene (83%).
The complete adsorption (losses were less
than 2%) for all PAHs, at a given concentration of
solution, was achieved on with sample OZ II 75, the
surface of which was covered with a monolayer of
surfactant. By increasing of SDBAC coverage on the
zeolite surface (bilayer coverage), the adsorption
efficiency to decreased only for fluorene (OZ II 100-
80% and OZ II 150-89%). The study results indicate
that the adsorption on a monolayer SDBAC covered
zeolite is primarily hydrophobic. For this reason, it
was investigated the adsorption of PAHs by an
organo-zeolite under dynamic conditions.
The first PAH to appear in the effluent
solution was fluorine, after 770 bed volumes (2.0
dm3) has passed through the column. Phenanthrene
and fluoranthene appeared after 1300 bed volumes
and 3800 bed volumes. Pyrene and benz[a]anthracene
were not detected in the effluent, after 7700 bed
volumes had passed through the column.
Microorganisms removal
Nikashina and Myasoedov (1999)
investigated the potential of modified clinoptilolite
with amine groups- polyhexamethylene guanidine
chloride (PHMG) to trap E. Coli from drinking water.
The investigation results of the modified clinoptilolite
show that the removal was 100%, depending upon the
filtration flow rate and the particle size of the
modified zeolite.
Another natural zeolite application to adhere
bacteria from water was conducted by Bowman
(2003). The natural zeolite was modified with
cationic surfactant (HDTMA). Ability of the
surfactant-modified zeolite to remove common
pathogens from sewage contaminated water was
determined. Results indicated the complete removal
of E. Coli and bactericidal in aqueous solution even
at low concentrations. As a result, the organisms are
greatly removed by the surfactant bound to zeolite.
The SMZ was also applied to protect drinking water
wells from viruses and bacteria and to remove viruses
and bacteria from ground water (Widiastuti et al.,
2008).
4. Conclusions
Zeolites are naturally occurring and
synthetic hydrated alumniosilicates characterized by
cage-like structures, high surface areas (hundreds of
m2/g) and high cation exchange capacities (hundreds
of meq/kg). There are more than 40 distinct natural
zeolites, which occur in massive deposits throughout
the world. The most common natural zeolite is
clinoptilolite. Treatment of natural zeolites with large
cationic surfactants (quaternary amines) dramatically
alters their surface chemistries. Various surfactants
have been employed but the large majority of studies
have focused on HDTMA. These large organic
cations exchange selectively with native inorganic
cations to form a stable, organic-rich coating on the
external surfaces of the zeolite. Surfactant
modification allows the zeolites to sorb nonpolar
organic solutes and anions, for which untreated
zeolites have little affinity. In addition, they keep
their ability to remove cations from water. When a
solution of cationic surfactant is mixed with zeolite,
the naturally occuring exchangeable cations (K+, Na+,
Ca2+ etc) on the external zeolite surfaces are replaced
by surfactant molecules. The surfactant molecule is
too large to penetrate the Angstrom-sized internal
pore spaces of the zeolite. The preparation of SMZ is
governed mainly by the concentration of surfactant in
solution (as reported to the cmc of the surfactant) and
by the ECEC of the zeolite. Just as surfactant
molecules in solution form micelles above the cmc,
when exposed to a negatively charged zeolite surface
will form admicelles. The sorbed surfactant creates an
organic-rich layer on the zeolite surface, and the
charge on the surface is reversed from negative to
positive. The positive charge on the outward-pointing
HDTMA headgroups is balanced by anions from
solution, forming an electrical double layer. In
addition, organic molecules and microorganisms
partition into the organic surfactant coating. The
remaining counter-cations, belonging mainly to the
internal surface area, can participate in the ion-
exchange processes to remove cations from aqueous
solution.
SMZs with surfactant loadings that exceed
ECEC show strong affinities for anions such as
chromate, arsenate, selenate, nitrate, sulfate, and
iodide. The sorption and retention of anions by
surfactant-modified zeolite was attributed to
surfactant-bilayer formation, on which positive
charges will develop and surface anion exchange was
the main sorption mechanism. Cation exchange by
zeolite is reduced after surfactant treatment. Sorption
of small, selectively bound hydrated cations such as
Cs+ is little reduced while larger, less selectively
retained cations such as Sr2+ and La3+ is greatly
reduced. Removal of Pb2+ is much less affected by
surfactant treatment, probably due to specific surface
interactions and/or precipitation of lead hydroxides on
the external zeolite surface. Various organic
pollutants (gasoline components benzene, toluene,
and p-xylene, PAH, pesticides, TCE etc) are strongly
retained by SMZ. The linear sorption isotherms and
the lack of sorption competition among solutes
suggest a partitioning-type mechanism.
Various environmental applications have
been studied for different types of SMZ, e.g.: removal
of chromate, phosphate, arsenate, mercury, cadmium,
BTEX, chlorophenol, perchloroethylene, fulvic acids,
dyes, pesticides, ionisable organic solutes, PAHs,
microorganisms. These applications present interest
for water and wastewater treatment with the condition
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of optimized operating parameters that provide Díaz-Nava M.C., Olguín M.T., Solache-Ríos M., Alarcón-
efficient removal rates and affordable costs. Herrera M.T., Aguilar-Elguezabal A., (2005),
Characterization and Improvement of Ion Exchange
Capacities of Mexican Clinoptilolite-rich Tuffs,
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