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

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

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

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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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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 pollutants: cations (mainly by an ion-exchange

isomerization via rotation about the C–C bonds. process, with the participation of the remaining
This brings one or more gauche bonds to countercations from both external and internal surface
trans bonds in the alkyl chains. The third DTA peak area), anions (by ion-exchange on the quaternary
at 261.3 °C occurs commonly with DTG peak and ammonium groups belonging to the surfactant
results from the melting, evaporation and pyrolysis of molecules organized as admicelles or bilayers) and
the surfactant. In the case of Na/ HDTMA–chabazite organic compounds (by partition of the organics
two broad DTG peaks occur in 100–150 and 350–450 intro the hydrophobic phase created on the external
ºC ranges. First of them is associated with broad DTA zeolite surface by the surfactant tail groups), as
peak in 100–150 ºC range and is a consequence of presented in Fig. 3 (Bowman, 2006).
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 Fig. 3. Schematic diagram of sorption mechanisms for
anions, cations, and nonpolar organics on SMZ
and easy pyrolysis of HDTMA impossible.
In the FTIR spectra of Na/HDTMA–
3.1. Application of modified zeolites to remove
chabazitethere three are groups of bands originating
anionic contaminants
from the zeolite matrix: 400–1200, 1640–1650, 3000–
4000 cm-1. The first group of bands results from
Campos et al. (2007) studied the removal of
stretching sceletal vibrations and within aluminium–
inorganic anion (chromate CrO42-) from drinking
silicon tetraeders, whereas the second and third group
water contaminated with Cr on a HDTMA modified
of bands appear as a consequence of deformation and
zeolite (96% mordenite) at pH values of 4.9-5.3.
stretching vibrations in water molecules. In turn the
According to Bowman et al. (1995), sorption
bands: 715–740, 1420–1480, 2800–3000 cm-1 are
of inorganic anions on cationic surfactant-modified
specific for surfactant molecules. The rocking δr nand
zeolite has been attributed to the formation of a
scissoring δs vibrations in methylene group preserve surface-anion complex. To sorb anions and form a
an essentially unchanged position during the complex, the modified surface must possess
surfactant concentration increase in equilibrium positively charged exchange sites. These sites are
aqueous phase and in zeolite phase. In pure HDTMA formed when positively charged surfactant head
spectrum the bands responsible for these vibrations groups are presented to the surrounding solution in
are splitted. The singlet character of these bands in the form of a bilayer or patchy bilayer. The positively
Na/HDTMA–chabazite is related to the fact that alkyl charged head groups are balanced by counter ions,
tails of adsorbed alklyammonium cations are poorly and the sorption or exchange of the other anionic
packed on the chabazite surface, so probably a liquid constituents involves the replacement of weakly held
like structure of adsorbed surfactant molecules counter ions by more strongly held counter ions. Li et
occurs. al. (1998) studied counter ion effects on the sorption
From the DRIFT spectra of chabazite and of cationic surfactant on natural zeolite and found that
Na/HDTMA–chabazite ( Majdan et al., 2006) found a the HDTMA-Br and HDTMA-Cl formed complete
small shift of T–O–T band, associated with stretching bilayers on the zeolite, whereas HDTMA-HSO4
vibration in Si–O–Al subunits, to higher frequency showed less than full bilayer formation (Campos et
for Na/HDTMA–chabazite. They concluded that that al., 2007).
the replacement of the small Na ion by large The HDTMA-modified zeolite showed
HDTMA cation results in the relaxation in Si–O–Al significant removal of chromate from aqueous
stretching vibrations and the shift of T–O–T band to solution. The results showed that the maximum
higher frequency. percentage adsorption was 93%.
Li (2006) studied the removal of chromate
3. Environmental applications of SMZ for water from contaminated groundwater using surfactant-
purification modified zeolite as permeable barrier. The zeolite was
modified with hexadecyltrimethylammonium
Surfactant –modified zeolites are able to bromide (HDTMA-Br) at a liquid to solid ratio of 3:1
simultaneously eliminate three different categories of

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 Surfactant-modified natural zeolites for environmental applications

(Li, 2006). The conclusions of the study were that the Ni2+, Zn2+) onto modified zeolite with cysteamine
100% chromate recovery indicates that surfactant- hydrochloride or cysteamine dihydrochloride in
modified zeolite (SMZ) as permeable barrier only acidic pH. The zeolitic minerals are characterized by
retards the chromate migration. Regeneration of SMZ thermo gravimetric analysis, scanning electron
for anion sorption without restoring the surfactant microscopy, X-ray diffraction and FTIR.
bilayer formation is almost impossible due to It has been experimentally showed that the
stripping off of the upper layer, and thus the pretreatment with NaCl on zeolite (before the
counterions, from the HDTMA admicelle formation modification with cysteamine hydrochloride or
as water flows through the columns. The permeable cysteamine dihydrochloride) enhances their ion
reactive barrier has the capacity to reduce chromium exchange ability.
concentration from contaminated groundwater; the It was found that the mercury removal from
adsorption percentage is very low. aqueous solution (without any content of havy
Bowman (2003) studied the applications of metals) is from 80 to 90%. The removal of mercury
surfactant modified zeolites as permeable barrier for by modified pretreated zeolite from mixed metal
the removal of environmental contaminants from solution is lower, about 42%, because of the
water, using a natural clinoptilolite (74% purity) competition of copper, nickel and zinc for the
modified with HDTMA-Cl. The use of SMZ as a exchange sites intro the zeolite network.
sorbent was evaluated in a permeable barrier at Ćurković et al., (1997) were able to remove
laboratory scale for the removal of chromate from Pb2+ and Cd2+ from water using a modified
contaminated groundwater. Pilot tests showed that clinoptilolite treated with NaCl. They found removal
SMZ permeable barrier was very effective for efficiencies of 90 and 70%, respectively.
removing chromate from groundwater. Chromate was Haggerty and Bowman (1994) showed that
fully retained by the barrier, with no detectable the sorption of small, selectively bound hydrated
concentrations down gradient. cations such as Cs+ is little reduced by HDTMA
Research on the use of cationic surfactant treatment. Sorption of larger, less selectively retained
modified zeolite to remove phosphate, PO4+ has cations such as Sr2+ and La3+ is greatly reduced.
been carried out. It was reported that surfactant These hard cations are probably exchanging with
modified zeolite using cethylpyridinium chloride cations on the zeolite's internal surfaces, to which
could remove phosphate ranging from 50% to 90% access is limited by the HDTMA coating. "Sorption"
depending upon variables such as concentration of of Pb2+ is much less affected by surfactant treatment,
cethylpyridinium chloride on the preparation of probably due to specific surface interactions and/or
surfactant modified zeolite; the initial phosphate precipitation of lead hydroxides on the external
concentration, contact time and initial pH influence zeolite surface.
on the adsorption of phosphate using SMZ
(Widiastuti et al., 2008). 3.3. Application of modified zeolites to remove
Another investigation of the use of cationic organic contaminants
surfactant zeolite to remove arsenate, ArO43- was
reported by Macedo-Miranda and Olguín (2007) who BTEX removal
showed that by modifying the adsorption The study of Ranck at al. (2005) evaluates
characteristics of the natural zeolite using lanthanum, the effectiveness of surfactant-modified zeolite
hexadecyltrimethylammonium and iron compounds (SMZ) for the removal of benzene, toluene,
will improve the arsenic adsorption capacities. The ethylbenzene and xylenes (BTEX) from water. The
results suggested that the arsenic retention depends on long-term effectiveness of SMZ for BTEX removal
the precedence of zeolitic material, the nature of was investigated along with changes in sorption
arsenic chemical species, pH as well as the properties for long-term use. The zeolite used in this
characteristics of modified natural zeolites. The study was a natural clinoptilolite-rich tuff from St.
modified zeolite has good characteristics for potential Cloud mine, New Mexico. The zeolite was modified
treatment of As(III) or As(V) polluted waters. with HDTMA-Cl.
Other anions, e.g. SO42- and SeO42- have The BTEX mobility in laboratory columns
been removed by using surfactant modified zeolites of SMZ was studied so as to decrease water solubility
by Bowman et al. (1995). and to increase Kow (octanol-water partition
coefficient). The most soluble compound, benzene,
3.2. Application of modified zeolites to remove began to elute at 8 pore volumes, while the least
cationic contaminants soluble compounds, ethyl benzene and xylenes, began
to elute at 50 pore volumes. After treating 4.500 pore
Research work on the removal of mercury volumes of water in the column system over 10
and cadmium from water by modified surfactant sorption/regeneration cycles, no significant reduction
zeolite shows that large quantities of these elements in the sorption capacity of the SMZ for BTEX was
are sorbed. observed. The mean Kds (linear sorption coefficient)
Gebremedhin-Haile et al., (2003) have determined in the column experiments ranged from
studied the mercury sorption from aqueous solutions 18.3 L/kg for benzene to 95.0 L/kg for p- and m-
in the presence and absence of heavy metals (Cu2+, xylene.

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 Apreutesei et al./Environmental Engineering and Management Journal 7 (2008), 2, 149-161

Laboratory columns were upscaled to create solutions by a Mexican clinoptilolite-heulandite

a field-scale SMZ treatment system. The field-scale zeolites, modified with the surfactant
system was tested at a natural gas produced-water hexadecyltrimethylammonium bromide (HDTMA-
treatment facility. It was observed a greater sorption Br), using batch and packed-bed (column)
of BTEX in the field column than predicted from the configurations. The effects of pH, contact time and
laboratory results. In the field column, initial benzene concentration of 4-chlorophenol on the adsorption
breakthrough occurred at 10 pore volume and toluene process by the surfactant modified zeolites were
breakthrough began at 15 pore volume, and no examined. The sorption of 4-chlorophenol was not
breakthrough of ethylbenzene or xylenes occurred affected by the pH range from 4 to 9.5. Thus, 4-
throughout the 80 pore volume experiment. chlorophenol retention reached equilibrium in about
The results of this investigations show that 18 h and the rate of 4-chlorophenol adsorption by the
SMZ completely removes BTEX from produced modified zeolites was faster in the first 10 h than
water up to a compound-specific capacity, and that later. The experimental data were modeled by using:
SMZ can be regenerated via air sparging without loss pseudo-first order, pseudo-second order, fractional
of sorption capacity. Field-scale tests supported power and Elovich models. Although, the last three
laboratory column test data showed greater sorption gave correlation coefficients higher than 0.96, the
of BTEX from produced water that was observed in pseudo-second order model was the best to describe
the laboratory columns. The results of this study the reaction rate. The experimental data followed a
along with the low cost of SMZ suggest that linear isotherm which is characteristic for sorption of
surfactant modified zeolites may have use in cost- organic solutes by the partition mechanism. The
effective produced-water treatment systems. results of this study showed that the surfactant
Altare et al. (2007) studied the removal of modified zeolites could be considered as pontetial
volatile organic compounds such as benzene, toluene, adsorbent for 4-chlorophenol removal from aqueous
ethylbenzene and p-, m-, and o-xylene (BTEX) from solutions.
oil and gas-field wastewaters using surfactant- Kuleyin (2007) studied the adsorption
modified zeolite (SMZ). The cationic surfactant used characteristics of phenol and 4-chlorophenol by a
was hexadecyltrimethylammonium (HDTMA). surfactant-modified zeolite. It was used a
Laboratory column studies were used to investigate clinoptilolite zeolite modified with HDTMA- Br
how different airflow rates impact regeneration of (hexadecyltrimethylammonium bromide) and
BTEX-saturated SMZ and to perform long-term tests benzyltetradecyl ammonium chloride (BDTMA).
to determine the chemical and physical stability of Batch studies were performed to evaluate the
SMZ in a water treatment system. effects of various experimental parameters such as
Varying the airflow rate from 1.3 to 10 pore contact time, adsorbent dose, initial concentration and
volumes (PV) per minute did not significantly affect temperature on the removal of phenol and 4-
BTEX removal rates. Rather, BTEX removal was chlorophenol. The sorption kinetics was tested for
controlled by the total mumber of PV that passed intraparticle diffusion, Elovich and pseudo-second
through the SMZ bed, suggesting only minor kinetic order reaction and rate constants of kinetic models
effects on regeneration. BTEX sorption and SMZ were calculated. Equilibrium isotherms for the
regeneration profiles varied little over 50 adsorption of phenol and 4-chlorophenol were
sorption/regeneration cycles. Each cycle consisted of analyzed by Freundlich, Langmuir and Tempkin
BTEX sorption from 100 PV of produced water isotherm models. Freundlich isotherm was found to
followed by regeneration with approximately 2000 best represent the data for phenol and 4-chlorophenol
PV of air. A weakly decreasing trend was observed adsorption.
for the BTEX distribution coefficients (Kd), Adsorption kinetics was found to follow
indicating only a small loss in the sorption affinity second order kinetic model. The increase in initial
after 50 cycles. The sorption affinity for BTEX was concentration of phenol and 4-chlorophenol resulted
maintained even though 20% of the original in an increase in the adsorption by the surfactant
surfactant was washed off the SMZ by 5000 PV of modified zeolite. The adsorption of phenol and 4-
produced water. The hydraulic conductivity of the chlorophenol on surfactant modified zeolite is
SMZ decreased by roughly 30% after 50 cycles. Most favorably influenced by an increase in the
of the hydraulic permeably loss is most likely caused temperature.
by particle attrition. The conclusions of the study showed that
The results of this study suggest that surfactant-modified zeolite is an effective sorbent for
surfactant modified zeolite is an effective sorptive the removal of phenol and 4-chlorophenol from
medium for removing volatile organics from oil-and aqueous solution. It was also found that 4-
gas-field wastewaters. It offers a low-cost and easily chlorophenol showed a higher dsorption capacity than
regenerable option for producers who want or need to phenol on surfactant-modified zeolite.
treat their produced water.
Perchloroethylene removal
Chlorophenol removal In the study of Li and Bowman (1998) a
Cortés – Martínez et al. (2007) investigated natural zeolite was modified with a cationic surfactant
the removal of 4- chlorophenol from aqueous to achieve different fractional organic carbon contents

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 Surfactant-modified natural zeolites for environmental applications

and different surfactant molecule configurations on modification process were constructed under different
the surface. The sorption of perchloroethylene (PCE) conditions by plotting the normalized effluent
by the surfactant modified zeolite was found to be concentration (C/C0) versus time or bed volumes
dependent on the bound surfactant molecule (BV). Optimization studies show that 3g/l of
configuration as well as on the fractional organic HDTMA-Br dosage at flow rate of 0.025l/min
carbon content. The sorption of PCE on SMZ is due showed the best performance. Examination of the dye
to partitioning of PCE into the organic phase formed removal under the optimum modification condition
by the surfactant on the zeolite surface. The PCE reveals that the black dye gives the highest
sorption coefficient on SMZ is a function of the breakthrough point among the three dyes tested. This
surfactant loading and resultant organic phase is ascribed to the hydrophobic/hydrophilic match of
density. the zeolite surface with the dye molecule, which
PCE is most efficiently sorbed by SMZ depends upon the way zeolite is modified with
when surfactant is present at or below full monolayer HDTMA-Br.
coverage; at higher surfactant loading levels, PCE Comparison of the dye adsorption by
sorption appears limited by a reduced effective modified zeolite in a fixed bed at optimum conditions
volume and an increased density of the hydrophobic indicated the order of dye removal by modified
core of the sorbed surfactant bilayer, resulting in a zeolite in the following manner: black>yellow>red.
decreased koc (distribution coefficient). The greater Surface coverage calculations demonstrate that the
hydrophobicity of the monolayer- versus the bilayer- most uitable orientation of the HDTMA-Br
modified surface may also add to the greater PCE adsorption on the zeolite surface is the formation of
sorption efficiency exhibited by the monolayer bilayer. The bilayer formation favors the interactions
system. The results from this research indicate that of anionic dye groups and HDTMA-Br covered
for removal of PCE from water, the most economical cationic zeolite surface, as proposed by the authors of
treatment would be to produce a monolayer, rather this study.
than a full bilayer, of HDTMA on the zeolite surface. Karadag et al. (2007) studied the adsorption
of Reactive Black 5 (RB 5) and Reactive Red 239
Fulvic acids removal (RR 239) aqueous solution onto surfactant-modified
Modification of zeolite (clinoptilolite) zeolite with cetyltrimethylammonium bromide
surface with a quaternary ammonium, HDTMA, to (CTAB) in batch system.
improve the removal efficiency of fulvic acids (FA) Experiments were performed at different
was investigated by Wang et al. (2006). The conditions such as initial dye concentration, contact
experiment consisted of modifying the clinoptilolite time, temperature, and pH. CTAB modification
with HDTMA followed by adsorption and desorption covered the zeolite surface with positive charges, and
of FA in the column. The effects of relevant the adsorption capacity of zeolite increased. The
parameters, such as HDTMA loading leves, FA flow adsorption capacity of Reactive Red 239 was found to
rate and eluant concentration were examined. be two times higher than reactive Blue 5 due to the
Optimization studies showed that the SMZ bed with hydrophilicity of the dye molecules (6.36 and 3.84).
HDTMA loading of 120% of ECEC at a flow rate of The Langmuir and Freundlich adsorption models
5 bed volumes/h had the best performance and the were applied to describe the equilibrium isotherms at
volume of 23 bed volumes of 30% ethanol solution different temperatures, and Freundlich model agrees
with the feed flow rate of 5 bed volumes/h was very well with the experimental data. The calculated
sufficient for complete regeneration of SMZ and maximum adsorption capacity increased with
desorption of FA. Measurements of Zeta potential of increasing initial dye concentration, but there is no
SMZ indicate that a monolayer formation is the most linear relationship with pH and temperature. The
viable packing that enables maximum removal of FA. equilibrium adsorption capacity of RB 5 showed a
FA adsorption on SMZ surfaces is largely maximum at pH 7, but the adsorption capacity of RB
due to the hydrophobic interaction and hydrogen 5 at equilibrium was not influenced by the pH
bonding while FA desorption depends on hydrogen various.
bonding. Partition and mass transfer also play an
important role in the adsorption and desorption of FA. Ionizable organic solutes removal
Sorption of ionizable organic solutes on a
Dyes removal clinoptilolite-rich zeolitic tuff modified with
Benkli et al. (2005) studied the removal of hexadecyltrimethylammonium bromide (HDTMA-
azo dyes using zeolites (clinoptilolite) modified with Br) was studied by Li et al. (2000). The sorption of
quaternary amine, hexadeciltrytrymethylammonium benzene and its ionizable analogues phenol and
bromide (HDTMA-Br), in a zeolite fixed bed. A aniline by surfactant-modified zeolite, prepared at
series of adsorption tests were conducted to find out different HDTMA surface coverage, was affected by
the uptake of three types of reactive dyes: CI Reactive solution pH. All of the isotherms were linear and
Black 5, Red 239 and Yellow 176. Each run consisted could be described by a distribution coefficient (Kd).
of modifying zeolite with HDTMA-Br in the column At neutral pH, the Kd values of benzene, phenol, and
followed by removal of color from the modified aniline on SMZ increased with HDTMA loading up
zeolite bed. The breakthrough curves for the to monolayer coverage of 100 mmol/kg. Beyond

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 Apreutesei et al./Environmental Engineering and Management Journal 7 (2008), 2, 149-161

monolayer coverage, further increases in HDTMA adsorption indexes (AI) of both pesticides increased
loading did not increase the Kd values of the solutes at with increasing adsorbent concentration. In the case
pH 7.0, where all species exist primarily in their of diazinone the sorption was related to the amount of
neutral forms. The Kd values were consistent with the surfactant on the mineral surface and to the
relative octanol-water partition coefficients of the concentration of diazionone in solution. For effective
three compounds, indicating that sorption of the adsorption of this pesticide onto an SMZ , it is
neutral species was primarily by partitioning into the necessary for the SDBAC/diazinon ratio to be higher
bound HDTMA organic pseudo phase. than 25. The adsorption capacities, calculated by
Phenol sorption by SMZ treated to bilayer fitting the experimental data to the Langmuir–
coverage increased as the pH, and hence fraction of Freundlich equation, were 2.0 µmol/g (atrazine), 4.4
anionic phenolate, increased. The counterion balance µmol/g (diazinone) and 3.4 µmol/g (lindan). At lower
indicated that the increased retention of phenol was initial concentrations of pesticide solution, a linear
due partially to anion exchange of phenolate from dependence existed between the amount adsorbed and
bromide, the same mechanism responsible for the equilibrium concentration of pesticide. The linear
sorption of inorganic anions by SMZ. In contrast, adsorption coefficients (Kd) were much higher for
decrease in pH resulted in reduced aniline sorption lindan and diazinone 0.654 and 0.502 µmol-1dm3 in
due to a lower concentration of the neutral species contrast to atrazine (0.025). Column experiments
and repulsion of the positively charged anilinium confirmed the efficiency of the OZs for pesticide
from SMZ treated to bilayer coverage. Sorption of sorption. Column experiments showed that at
benzene, phenol and aniline by SMZ followed linear volumetric flow of 6 cm3/ min, the breakthrough
sorption isotherms in the pH range of 3.6-11.2. points (at C/C0 =0.1) were 560 bed volume (BV) for
The results of the study demonstrate that lindane and 620 for diazinone.
SMZ are effective in sorbing ionizable organic
compounds in addition to hydrophobic nonionic PAHs removal
compounds. When solution pH is such that the neutral Sorption of polycyclic aromatic
form of an ionizable species dominates, no sorption hydrocarbons (PAHs) on organo-zeolites was
enhancement occurs in treating the SMZ beyond investigated by Lemić et al. (2007) to determine
monolayer coverage. At pH values where ionized sorbent-sorbate interaction. The hydrophobic
species are important, sorption to SMZ at bilayer character of the surface of the organo-zeolites was
coverage will be enhanced or depressed depending studied using water vapor adsorption experiments.
upon the ionic charge. For solutes such as aniline that The zeolite was modified using
protonate at low pH, optimal sorption may occur at stearyldimethylbenzylammoniumchloride (SDBAC)
submonolayer coverages of SMZ, where some cation solutions of four initial concentrations: 50, 75, 100
exchanges sites of the zeolite still remain avaible to and 150 mmol/dm3 in order to achieve
sorb other cationic species. SDBAC/external cation exchange capacity (ECEC)
rations of 0.67, 1.0, 1.33 and 2.0. Water adsorption
Pesticides removal decreased with increasing
Systematic adsorption tests were carried out stearyldimethylbenzylammoniumchloride (SDBAC)
by Lemic et al. (2006) to determine the efficiency of loading up to 75 mmol/kg, which is related to
SMZ for removal of atrazine, lindane and diazinone increasing sorbate hydrophobicity.
from water. The hydrophobic character of SMZ- In this study, the sorption values of
pesticide interactions was confirmed by measuring fluorene, phenanthrene, benz[a]anthracene,
the amount of pesticides sorbed on zeolite samples fluoranthene and pyrene on the surface modified
modified with 25, 50, 75 and 150 mmol of zeolites were determined. The adsorption was studied
stearyldimethylbenzylammoniumchloride under batch and column conditions. In order to
(SDBAC)/kg of zeolite. The effects of adsorbent determine the influence of the adsorbent size on the
particle size, solid content in the suspension and the adsorption of PAHs, zeolites with different particle
initial pesticide concentration in the solutions were size were modified in the same manner using a 100
also investigated. The amount of atrazine sorbed mmol/dm3 SDBAC solution concentration. The
decreased with increasing particle size, which is maximal amount of SDBAC sorbed on the zeolite
associated with the reduction of the specific surface. surface was 123 mmol/kg, which is 164% of the
The sample with the smallest particle size (0-0.4 mm) ECEC value of the zeolite.
was the most effective for the adsorption of atrazine Adsorption efficiency of the organo-zeolites
(42.3 µmol/kg), but these particles were found to be of different particle size with the same surfactant
too small for application in filtration systems. loading for the PAH compounds was determined on
Previous studies of the sorption of different samples of organo-zeolites. The adsorption
contaminants by organo-minerals indicated that the index of sample OZ I 100 (OZ - organo-zeolite; I –
increase of adsorption efficiency with increasing particle size 0.0-0.4 mm; 100 – mmol of surfactant/kg
concentration of adsorbent in the suspension was not of zeolite) were greatest (98% without losses) for all
linear (Bouffard and Duff, 2000; Dakovic´ et al., the PAH compounds. With increasing the particle
2003). Similiar results were obtained for the size, the adsorption efficiencies decreased. The
adsorption of atrazine and lindane on the SMZs. The difference was significant, especially in the case of

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 Surfactant-modified natural zeolites for environmental applications

sample OZ III 100 (OZ - organo-zeolite; III – particle alters their surface chemistries. Various surfactants
size 0.8-3 mm; 100 – mmol of surfactant/kg of have been employed but the large majority of studies
zeolite), where the adsorption indexes were in the have focused on HDTMA. These large organic
range of 50-83%. The adsorption efficiency of sample cations exchange selectively with native inorganic
OZ II 100 (OZ - organo-zeolite; II – particle size 0.4- cations to form a stable, organic-rich coating on the
0.8 mm; 100 – mmol of surfactant/kg of zeolite) was external surfaces of the zeolite. Surfactant
the greatest for fluorene (83%). modification allows the zeolites to sorb nonpolar
The complete adsorption (losses were less organic solutes and anions, for which untreated
than 2%) for all PAHs, at a given concentration of zeolites have little affinity. In addition, they keep
solution, was achieved on with sample OZ II 75, the their ability to remove cations from water. When a
surface of which was covered with a monolayer of solution of cationic surfactant is mixed with zeolite,
surfactant. By increasing of SDBAC coverage on the the naturally occuring exchangeable cations (K+, Na+,
zeolite surface (bilayer coverage), the adsorption Ca2+ etc) on the external zeolite surfaces are replaced
efficiency to decreased only for fluorene (OZ II 100- by surfactant molecules. The surfactant molecule is
80% and OZ II 150-89%). The study results indicate too large to penetrate the Angstrom-sized internal
that the adsorption on a monolayer SDBAC covered pore spaces of the zeolite. The preparation of SMZ is
zeolite is primarily hydrophobic. For this reason, it governed mainly by the concentration of surfactant in
was investigated the adsorption of PAHs by an solution (as reported to the cmc of the surfactant) and
organo-zeolite under dynamic conditions. by the ECEC of the zeolite. Just as surfactant
The first PAH to appear in the effluent molecules in solution form micelles above the cmc,
solution was fluorine, after 770 bed volumes (2.0 when exposed to a negatively charged zeolite surface
dm3) has passed through the column. Phenanthrene will form admicelles. The sorbed surfactant creates an
and fluoranthene appeared after 1300 bed volumes organic-rich layer on the zeolite surface, and the
and 3800 bed volumes. Pyrene and benz[a]anthracene charge on the surface is reversed from negative to
were not detected in the effluent, after 7700 bed positive. The positive charge on the outward-pointing
volumes had passed through the column. HDTMA headgroups is balanced by anions from
solution, forming an electrical double layer. In
Microorganisms removal addition, organic molecules and microorganisms
Nikashina and Myasoedov (1999) partition into the organic surfactant coating. The
investigated the potential of modified clinoptilolite remaining counter-cations, belonging mainly to the
with amine groups- polyhexamethylene guanidine internal surface area, can participate in the ion-
chloride (PHMG) to trap E. Coli from drinking water. exchange processes to remove cations from aqueous
The investigation results of the modified clinoptilolite solution.
show that the removal was 100%, depending upon the SMZs with surfactant loadings that exceed
filtration flow rate and the particle size of the ECEC show strong affinities for anions such as
modified zeolite. chromate, arsenate, selenate, nitrate, sulfate, and
Another natural zeolite application to adhere iodide. The sorption and retention of anions by
bacteria from water was conducted by Bowman surfactant-modified zeolite was attributed to
(2003). The natural zeolite was modified with surfactant-bilayer formation, on which positive
cationic surfactant (HDTMA). Ability of the charges will develop and surface anion exchange was
surfactant-modified zeolite to remove common the main sorption mechanism. Cation exchange by
pathogens from sewage contaminated water was zeolite is reduced after surfactant treatment. Sorption
determined. Results indicated the complete removal of small, selectively bound hydrated cations such as
of E. Coli and bactericidal in aqueous solution even Cs+ is little reduced while larger, less selectively
at low concentrations. As a result, the organisms are retained cations such as Sr2+ and La3+ is greatly
greatly removed by the surfactant bound to zeolite. reduced. Removal of Pb2+ is much less affected by
The SMZ was also applied to protect drinking water surfactant treatment, probably due to specific surface
wells from viruses and bacteria and to remove viruses interactions and/or precipitation of lead hydroxides on
and bacteria from ground water (Widiastuti et al., the external zeolite surface. Various organic
2008). pollutants (gasoline components benzene, toluene,
and p-xylene, PAH, pesticides, TCE etc) are strongly
4. Conclusions retained by SMZ. The linear sorption isotherms and
the lack of sorption competition among solutes
Zeolites are naturally occurring and suggest a partitioning-type mechanism.
synthetic hydrated alumniosilicates characterized by Various environmental applications have
cage-like structures, high surface areas (hundreds of been studied for different types of SMZ, e.g.: removal
m2/g) and high cation exchange capacities (hundreds of chromate, phosphate, arsenate, mercury, cadmium,
of meq/kg). There are more than 40 distinct natural BTEX, chlorophenol, perchloroethylene, fulvic acids,
zeolites, which occur in massive deposits throughout dyes, pesticides, ionisable organic solutes, PAHs,
the world. The most common natural zeolite is microorganisms. These applications present interest
clinoptilolite. Treatment of natural zeolites with large for water and wastewater treatment with the condition
cationic surfactants (quaternary amines) dramatically

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 Apreutesei et al./Environmental Engineering and Management Journal 7 (2008), 2, 149-161

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,
References
Journal of Inclusion Phenomena and Macrocyclic
Chemistry, 51, 231-240.
Altare C. R., Bowman R. S., Katz L. E., Kinney K. A.,
Gebremedhin-Haile T., Olguín M.T., Solache-Ríos M.,
Sulivan E. J., (2007), Regeneration and long-term
(2003), Removal of mercury ions from mixed aqueous
stability of surfactant-modified zeolite for removal of
metal solutions by natural and modified zeolitic
volatile organic compounds from produced water,
minerals, Water, Air, and Soil Pollution, 148, 179-200.
Microporous and Mesoporous Materials, 105, 305-
Haggerty G.M., Bowman R.S., (1994), Sorption of
316.
inorganic anions by organo-zeolites, Environmental
Armbruster T., (2001), Clinoptilolite-heulandite:
Science and Technology, 28, 452-458.
applications and basic research. In: Studies in Surface
Ingram B.T. and Ottewill R. H., (1991), Adsorption of
Science and Catalysis 135 Zeolites and Mezoporous
cationic surfactants at interfaces. In: Cationic
Materials at the Dawn of the 21st Century, Galarnau
Surfactants: Physical Chemistry, Rubingh D.N.,
A., di Renzo F., Faujula F., Vedrine J. (Eds.), Elsevier,
Holland P.M., Rubingh R., (Eds.), CRC Press, New
Amsterdam, 13-27.
York, 87-140.
van Bekkum H., Flanigen E.M., Jansen J.C., (2007),
Jaynes W.F., Boyd S.A., (1991), Clay mineral type and
Introduction to Zeolite Science and Practice, Elsevier
organic compound sorption by hexadecyltri-
Publishing House, The Netherlands.
methylammonium-exchanged clays, Soil Sci. Soc. Am.
Benkli Y.E., Can M.F., Turan M., Çelik M.S., (2005),
J., 55, 43-48.
Modification of organo-zeolite surface for the removal
Jaynes W.F., Vance G.F., (1996), BTEX sorption by
of reactive azo dyes in fixed-bed reactors, Water
organo-clays: cosorptive enhancement and equivalence
Research, 39, 487-493.
of interlayer complexes, Soil Sci. Soc. Am. J., 60,
Bitting D. and Harwell J.H., (1987), Effects of counterions
1742-1749.
on surfactant surface aggregates at the
Karadag D., Turan M., Akgul E., Tok S., Faki A., (2007),
alumina/aqueous solution interface, Langmuir, 3, 500-
Adsorption equilibrium and kinetics of Reactive Black
511.
5 and Reactive Red 239 in aqueous solution onto
Bouffard S.C. and duff s.J.B., (2000), Uptake of
surfactant-modified zeolite, J. Chem. Eng. Data, 52,
dehydroabietic acid using organically-tailored zeolites,
1615-1620.
Water Research, 34, 2469-2476.
Kuleyin A., (2007), Removal of phenol and 4-chlorophenol
Bowman R. S., Haggerty G.H., Huddleston R.G., Neel D.,
by surfactant-modified natural zeolite, Journal of
Flynn M., (2003), Sorption of nonpolar organics,
Hazardous Materials, 144, 307-315.
inorganic cations, and inorganic anions by surfactant-
Lemić J., Kovačević D., Tomašević-Čanović M.,
modified zeolites. In: Surfactant - Enhanced
Kovačević D., Stanić T., Pfend R., (2006), Removal of
Remediation of Subsurface Contamination, Sabatini
antrazine, lindane and diazinone from water by organo-
D.A., Knox R.C., Harwell J.H. (Eds.), ACS
zeolites, Water Research, 40, 1079-1085.
Symposium Series 594. American Chemical Society,
Lemić J., Tomašević-Čanović M., Adamović M.,
Washington 54-56.
Kovačević D., Milićević S., (2007), Competitive
Bowman R. S., (2003), Applications of surfactant-modified
adsorption of polycyclic aromatic hydrocarbons on
zeolites to environmental remediation, Microporous
organo-zeolites, Microporous and Mesoporous
and Mesoporous Materials, 61, 43-56.
Materials, 105, 317-323.
Bowman S. R., (2006), Zeolite '06 - 7th International
Li Z., Bowman R. S., (1998), Sorption of Perchloroethylene
Conference on Natural Zeolites, On line at:
by Surfactant-Modified Zeolite as Controlled by
http://www.ees.nmt.edu/bowman/research/SMZ/
Surfactant Loading, Environ. Sci. Technol., 32, 2278-
Campos V., Morais L.C., Buchler P.M., (2007), Removal of
2282
chromate from aqueous solution using treated natural
Li Z., Roy S., Bowman R.S., (1998), Long term chemical
zeolite, Environmental Geology, 52, 1521-1525.
and biological stability of surfactant-modified zeolite,
Cortés_Martínez R., Martínez-Miranda V., Solache-Rios
Environ. Sci. Technol, 32, 2628-2632
M., García-Sosa I., (2004), Evaluation of natural and
Li Z., (1999), Sorption Kinetics of
surfactant-modified zeolites in the removal of
Hexadecyltrimethylammonium on Natural
cadmium from aqueous solutions, Separation Science
Clinoptilolite, Langmuir, 15, 6438-6445.
and Technology, 39, 2711-2730.
Li Z., Burt T., Bowman R. S., (2000), Sorption of ionizable
Cortés_Martínez R., Solace-Ríos M., Martínez-Miranda V.,
organic solutes by surfactant-modified zeolite,
Alfaro-Cuevas R.V., (2007), Sorption Behavior of 4-
Environ. Sci. Technol., 34, 3756-3760.
Chlorophenol from Aqueous Solutions By a
Li Z., (2006), Chromate transport through surfactant-
Surfactant-modified Mexican Zeolitic Rock in Batch
modified zeolite columns, Ground Water Monitoring
and Fixed Bed Systems, Water Air and Soil Pollution,
& Remediation, 3, 117-124.
183, 85-94.
Macedo-Miranda M.G., Olguín M.T., (2007), Arsenic
Ćurković L., Cerjan-Stefanović Š., Filipan T., (1997), Metal
sorption by modified clinoptilolite-heulandite rich
ion exchange by natural and modified zeolites, Water
tuffs, J Incl Phenom Macrocycl Chem, 59, 131-142.
Research, 31, 1379-1382.
Majdan M., Pikus S., Rzączyńska Z., Iwan M., Maryuk O.,
Daković A., Tomašević-Čanović M., Rottinghaus G.,
Kwiatkowski R., Skrzypek H., (2006), Characteristics
Dondur V., Mašić Z., (2003), Adsorption of achratoxin
of chabazite modified by hexadeyltrimethylammonium
A on octadecyldimethyl benzyl ammonium exchanged-
bromide and of its affinity toward chromates, Journal
clinoptilolite heulandite tuff, Colloids and Surfaces B:
of Molecular Structure, 791, 53-60.
Biointerfaces, 30, 157-165.

160
 Surfactant-modified natural zeolites for environmental applications

Nikashina V.A., Myaosedov, (1999), Environmental Smith J.A., Jaffe P.R., (1994), Adsorption selectivity of
applications of modified natural zeolites, Natural organiccation- modified bentonite for nonionic organic
Microporous Materials in Environmental Technology, contaminants, Water, Air, and Soil Pollution, 72, 205-
335-343. 211.
Nunez Y.R., (1998), Removal of phosphates from water Sullivan E.J., Carey J.W., Bowman R.S., (1998),
using tailored zeolites, PhD Thesis, University of Thermodynamics of cationic surfactant sorption onto
Puerto Rico. natural clinoptilolite, Journal of Colloid and Interface
Ranck M.J., Bowman R.S., Weeber J.L., Katz L.E., Science, 206, 369-380
Sullivan E.J., (2005), BTEX Removal from produced Wang S., Gong W., Liu X., Gao B., Yue Q., Zang D.,
water using surfactant-modified zeolite, Journal of (2006), Removal of fulvic acids from aqueous
Environmental Engineering, 131, 434-442. solutions via surfactant modified zeolite, Chem. Res.
Reháková M., Čuvanová S., Dzivák M., Rimár J., Chinese U., 22, 566-570.
Gaval’ová Z, (2004), Agricultural and agrochemical Widiastuti N., Wu H., Ang M., Dong-ke-Zhang, (2008),
uses of natural zeolite of the clinoptilolite type, The potential application of natural zeolite for
Current Opinion in Solid State and Materials Science, greywater treatment, Desalination, 218, 271-280.
8, 397-404. Xi Y, Ding H. H., Frost R.L., (2005), Infrared spectroscopy
Schulze-Makuch D., Pillai S.D., Guan H., Bowman R., of organoclays synthesized with the surfactant
Couroux E., Hielscher F., Totten J., Espinosa I.Y., octadecyltrimethylammonium bromide,
Kretzschmar T., (2002), Surfactant-modified zeolite Spectrochimica Acta Part A: Molecular Biomolecular
can protect drinking water wells from viruses and Spectroscopy, 61, 515–525.
bacteria, EOS, 83, 193-201. Zajac J., Trompette J.L., Partyka S., (1996), adsorption of
Schulze-Makuch D., Bowman R.S., Pillai S., (2004), cationic surfactants on a hydrophilic silica surface at
Removal of Biological Pathogens Using Surfactant- low surface coverages: Effects of the surfactant alkyl
Modified Zeolite, US Patent 7311839. chain and exchangeable sodium cations at the silica
surface, Langmuir, 12, 1357-1367

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