Zeolite For Water Treatment

Published by the Australian Institute of High Energetic Materials (ABN: 68 126 426 917)
Available online at http://www.ausihem.org
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Zeolites for water and wastewater treatment: An overview
*
Shoumkova A ,
Rostislaw Kaischew Institute of Physical Chemistry, Bulgarian Academy of Sciences, Bulgaria
Abstract:
Zeolites are natural or synthetic microporous crystalline aluminosilicates, which have unique ion
exchange and sorption properties, and are widely used in a large number of water treatment
processes, such as water softening and purification from ammonia, heavy and radioactive metals. In
the same time, they have been extensively researched for variety of new applications, e.g. as
adsorbents for removal of organic substances, microorganisms and anions, for seawater desalination
membranes and fill materials for reactive permeable barriers.
The objective of this paper is to review the research concerning the application of zeolites in water
and wastewater treatment. The first part of the manuscript gives a brief description of natural and
synthetic zeolites, most often exploited in (waste)water treatment practice. An accent is put on the
synthesis, properties and practical potential of some cost-effective, environmental-friendly zeolites,
obtained on the base of industrial, municipal and agricultural wastes.
The second part of the study is focused on the application of the zeolites in various (waste)water
treatment processes. The discussion confers the general aspects of each application and reviews
some recent studies. The most important experimental results concerning the performance of
zeolites in different water treatment processes are summarized in a table format.
Keywords: zeolites, zeolitization, water treatment, wastewater purification, waste utilization.
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1. INTRODUCTION
The extremely fast growth of the world population in the last century, in addition to the industrial
revolution, reflected in a considerable rise in both fresh water consumption and wastewater
production. Fresh water demand has already exceeded supply, and currently special treatment is
more and more often required in order to obtain drinking water of high qualityas well as to produce
environmentally acceptable effluents.
Water from natural, industrial, municipal or agricultural origin may contain variety of suspended,
dissolved, colloidal or emulsified organic and inorganic impurities, some of which could be
successfully separated out, using special class of inorganic compounds, called “zeolites” (from the
Greek “ζέω” = "boil" and “λίθος” = "stone").
*
Title and name of the corresponding author: Chem. Eng. Dr. Annie Shoumkova
Postal address: Bulgaria, Sofia 1113, “Acad. G. Bonchev” Str., bl.11
Telephone (incl. country code): +359 2 9792598; +359 887 946122
Fax (optional): +359 2 9712688
E-mail: [email protected]; [email protected]
Copyright © Australian Institute of High Energetic Materials – All rights reserved

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Zeolites are crystalline microporous aluminosilicates, built up of a 3-dimentional framework of

[SiO4]4- and [AlO4]5- tetrahedra, linked by sharing oxygen atoms [1], and weakly bonded (readily
exchangeable) cations and water molecules in the pores and voids of the structure. Cations sorption
is determined by the uncompensated negative charge, resulting from the substitution of Si (IV) by
Al (III) in the tetrahedra. Cation exchange capacity (CEC) is a measure of the number of cations per
unit weight available for exchange, usually expressed as milliequivalents per gram of material. As a
rule, the greater the Al content (i.e. the more extra framework cations needed to balance the charge),
the higher CEC of the zeolite [2]. The sorption capacity and selectivity for water and/or other
molecules are defined by zeolite porosity, pore size distribution, and specific surface. The
composition of zeolites can be represented by the general formula Mx/n[(AlO2)x(SiO2)y].zH2O,
where n is the charge of the cation M, and the values of x, y and z depend on the type of zeolite [3].
The number of naturally occurring zeolite types is about 40 [4], but owing to the artificially
synthesized zeolites, almost 200 [5] unique frameworks have been identified so far.
Due to their unique properties, zeolites have found a broad range of industrial applications as
catalysts, adsorbents, molecular sieves and ion exchangers with a growing global market, estimated
of about 4 million tonnes for 2010. They have been used in a large number of water treatment
processes such as water softening and purification from ammonia, heavy metals, radioactive species,
dissolved or emulsified organic substances, toxic anions, odour and solids. Thousands of scientific
articles, books, patents and technical notes, dealing with different aspects of zeolite utilization in
(waste)water treatment processes, were published in the last few decades, but still numerous
laboratory researches and pilot-plant studies are ongoing.
The general objective of the current paper is to overview the state-of-the-art knowledge concerning
the use of different kinds of zeolites in (waste)water treatment processes and to summarize the most
important properties of natural, synthetic and waste-derived zeolites, relevant to these applications,
in order to facilitate their comparison and give an outstanding point that could assist the right choice
of materials for practical purposes.
2. METHODOLOGY
The study was done on the base of a review of over 300 scientific articles, published in the last 10-
15 years and available through the international scientific databases. Books, patents, commercial
articles and company documentation were not reviewed and were mentioned only in a few
occasions. The reproduction of details of some of the reference articles was consciously avoided in
order to prevent the overlapping of the content of the present paper with those of the already
published papers reviewing similar topics, as well as to keep the volume of the article in reasonable
limits. Instead, an attempt to summarize and compare the most important properties of natural,
synthetic and waste-derived zeolites (which are usually discussed in separate studies) was made.
For this purpose, the data reported in different researches were generalized, recalculated (if
necessary) to obtain the same dimension, and summarized in a table format. Since most of the
reviewed studies have been carried out at more or less different conditions (i.e. system parameters,
measurement/analytical methodology and equipment, etc.), these data should not be used for direct
comparison, but rather as an outstanding point for the evaluation of the potential for the application
of different zeolites in variable (waste)water treatment processes.
The first part of the manuscript gives a brief description of natural and synthetic zeolites, most often
exploited in (waste)water treatment practice. Their composition, occurrence or methods for
production as well as some physical properties, such as theoretical or measured cation exchange
capacities, are presented. An accent is put on the synthesis, properties and practical potential of

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some cost-effective, environmental-friendly zeolites or zeolitic materials, obtained on the base of

industrial, municipal and agricultural wastes. The second part of the study is focused on the
application of the zeolites in various (waste)water treatment processes, including water softening,
and removal of ammonia, heavy and radioactive metals, phosphates and other anionic species,
dissolved or emulsified organic compounds and dyes, pathogen microorganisms removal, etc. The
discussion confers the general aspects of each application and reviews some recent studies and such,
containing essential results. The most important experimental results concerning the adsorption
capacity, efficiency and selectivity for different water contaminants of natural, synthetic and waste-
derived are compared and summarized in a table format.
3. RESULTS AND DISCUSSION

3.1. Zeolites origin, synthesis and basic properties
3.1.1. Natural zeolites
Natural zeolites are formed by an interaction of volcanic rocks and ash with alkaline underground
water. Since the discovery of the first mineral (stilbite, Na2Ca4Al10Si26O72·30H2O), classified as a
zeolite by the Swedish mineralogist Axel Fredrik Cronstedt in 1756, natural zeolites have been
intensivly explored, investigated and mined.
In naturally occurring zeolites, the cations are mainly of the alkali (Na and K) and alkaline earth (Ca
and Mg) metals. The most common natural zeolites are analcime, chabazite, clinoptilolite, erionite,
faujasite, ferrierite, heulandite, laumontite, mordenite and phillipsite. Their typical formulae and
selected physical properties and theoretical CEC as given by Mumpton [2] are listed in Table 1.
Table 1. Typical formulae, structure type and selected physical properties of some natural zeolites
Structure Void volume, Channel CEC,
Zeolite Representative unit-cell formula
type %* dimensions, Å meq g -1**
Analcime (Na10)(Al16Si32O96).16H2O ANA 18 2.6 4.54
Chabazite (Na2Ca)6(Al12Si24O72).40H2O CHA 47 3.7 x 4.2 3.84
Clinoptilolite (Na3K3)(Al6Si30O72).24H2O HEU 34 3.9 x 5.4 2.16
Erionite (NaCa0.5K)9(Al9Si27O72).27H2O ERI 35 3.6 x 5.2 3.12
Faujasite (Na58)(Al58Si134O384).24H2O FAU 47 7.4 3.39
Ferrierite (Na2Mg2)(Al6Si30O72).18H2O FER 28 4.3 x 5.5 2.33
4.0 x 5.5
Heulandite (Ca4)(Al8Si28O72).24H2O HEU 39 4.4 x 7.2 2.91
4.1 x 4.7
Laumontite (Ca4)(Al8Si16O48).16H2O LAU 34 4.6 x 6.3 4.25
Mordenite (Na8)(Al8Si40O96).24H2O 28 2.9 x 5.7 2.29
MOR
6.7 x 7.0
Phillipsite (NaK)5(Al5Si11O32).20H2O 31 4.2 x 4.4 3.31
PHI 2.8 x 4.8
3.3
Scolecite** Ca2Al2Si3O10.3H2O 3.9 5.10
*Void volume determined from water content. **Theoretical value, calculated from unit-cell formula, *** [6].
The environmental applications of natural zeolites have been widely researched. In the last 1-2
decades several hundred technical papers and scientific articles, including few reviews [7-9], were
devoted to (waste)water treatment by natural zeolites from different deposits. Although
clinoptilolite has relatively low CEC, it has demonstrated high selectivity for NH4+ [7,8,10,11],
some heavy metals [7,12, 13] and radionuclides [14-16] and has become the major natural zeolite

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used in (waste)water purification practice [2]. Good selectiveness for NH4+, transition and
radioactive elements has been demonstrated also by mordenite, chabazite and phillipsite [7,12].
World reserves of natural zeolites are not determined but are evaluated to be large [17]. The world
production of natutal zeolites for 2010 is estimated of about 2.75 million tones [17]. China is the
major source, with production of 2.0 million tones, followed by Korea (210 000 t), Japan (150,000
t), Jordan (140 000 t), Turkey (100 000 t), Slovakia (85 000 t), and the USA (59 000 t) [17]. Zeolite
deposits are available also in Cuba, South Africa, Iran, Italy, Hungary, Bulgaria, Argentina,
Australia, Germany, Indonesia, Ukraine, and some other republics from the former U.S.S.R.
Natural zeolites from different deposits may vary widely in purity (from 15-20 up to 90-95%),
chemical composition, crystal size, porosity, pore diameter and other properties, determining their
sorption and ion exchange capacity [9]. The actual CEC values of natural zeolites are usually lower
than calculated. CEC values of clinoptilolite from different deposits are presented in Table 2.
Table 2. CEC of clinoptilolite from different deposits

Country of CEC,
Zeolite Reference
origin meq g-1
Clinoptilolite Australia 1.20 [18]
Clinoptilolite Bulgaria 1.42 [19]
Clinoptilolite + Mordenite Chile 2.05 [20]
Clinoptilolite China 1.03 [21]
Clinoprtilolite China 1.20 [23]
Clinoptilolite Croatia 1.45 [24]
Clinoptilolite + Mordenite Iran 1.20 [25]
Clinoptilolite Romania 1.37 [22]
Clinoptilolite Slovakia 1.17 [26]
Clinoptilolite Turkey 1.6-1.8 [27]
Clinoptilolite Turkey 1.84 [28]
Clinoptilolite + Mordenite Turkey 1.65 [29]
Clinoptilolite Ukraina 0.64 [30]
Clinoptilolite Ukraina 1.63 [31]
The main advantages of natural zeolites are their low price and availability, however they could not
gain the commercial water treatment niche-market of the synthetic forms, possessing tailored
composition, structure and properties.
3.1.2. Synthetic zeolites
Synthetic zeolites are generally produced by alkali treatment of silica and alumina – bearing row
materials of synthetic, natural or waste origin. The first synthetic zeolite, ZK-5 (Na2Al2Si4-6O12-
16.6H2O), unknown as natural mineral, was obtained in the late 1940s by Richard Barrer who
investigated the conversion of minerals under the action of strong salt solutions at high temperatures
(≈170÷ 250°C) [31]. Later, Milton pioneered the use of more reactive starting materials, enabling
milder reaction conditions and leading to the discovery of zeolite A [32] which has become the
most important synthetic zeolite, commercially used as a water softener in detergent industry, in
radioactive waste treatment, and in the purification of industrial wastewaters. The formulae,
structure type and CEC of some of the most important synthetic zeolites are given in Table 3.
Conventional zeolite synthesis involves the hydrothermal (HT) crystallization of aluminosilicate
gels or solutions in the presence of cations and basic environment (pH>10). The crystallization is
usually carried out in closed systems at increased temperature and duration varying from few hours
to several days. The type, yield, purity and disperse composition of the obtained zeolite is affected

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by the nature and pretreatments of the reactants, composition of the reaction mixture (Si/Al ratio,
presence of seeds or templates, pH of the system), pre-reaction seeding, heating regime, pressure,
preliminary or post-heating ageing, hydrodynamic conditions, etc. [33-36].
Table 3. Typical formulae, structure type and selected physical properties of some synthetic zeolites
Channel dimension, CEC,
Zeolite Representative unit-cell formula Structure type
Å meq g-1*
Zeolite NaA Na12 Al12Si12O48.27H2O LTA 4.2 5.48
Zeolite NaX Na86Al86Si106O384.264H20 FAU 7.4 4.73
Zeolite NaY Na20Al20.Si48O136.89H2O FAU 7.4 3.26
Zeolite NaP Na2Al2Si2-5O8-14.5H2O GIS 3.51
Zeolite NaP1 Na6Al4Si4O24.4H2O GIS 2.6 7.37
ZSM-5 NanAlnSi96–nO192.16H2O, 0<n<27 MFI 5.3 x 5.6; 5.1 x 5.5 2.07
Cancrinite Na6Ca2Al6Si6O24(CO3)2.2H2O CAN 5.9 9.19
Hydroxisodalite Na6Al6.Si6O25.4H2O SOD 2.3
*Theoretical value, calculated from unit-cell formula.
The preparation of zeolites from chemical sources of Si and Al (e.g. colloidal SiO2, Na2SiO3,
Na2Al2O4, Al(OH)3) is expensive, but has the advantage to produce materials of high-purity, with
precisely engineered chemical and physical properties, suitable for some specific applications in
pharmacy, electrochemistry, photochemistry, nanotechnologies as well as for academic research
purposes. For multi-ton, industrial production of zeolites, some cheaper natural materials such as
clay minerals, sand, volcanic ash and natural zeolites are commonly used as Si or Si-Al sources.
3.1.2.1. Synthetic zeolites from natural materials
Since the principal raw materials used to manufacture zeolites are silica and alumina, which are
among the most abundant mineral components on earth, the potential to supply raw materials for
zeolites synthesis is virtually unlimited.
Clay minerals, such as kaolin [37-41], illite [42], smectite [43, 44], interstratified illite–smectite
[45], montmorillonite [46,47], bentonite [48,49], perlite [50-51] have been used frequently for
zeolites synthesis, due to their high contents of silicon and aluminum, which easily dissolve and
form zeolite under alkaline conditions [52]. The zeolitization is realized via HT methods and
typically includes the application of suitable pretreatments (e.g. grinding, acid washing, calcination,
fusion with additives) of the starting materials.
A variety of zeolites (A [38,53,54], X [53-56], LSX [37,39], N [47], P [41] etc.) has been
synthesized using kaolin as an aluminosilicate source. It is usually first calcinated (at 550-950°C) in
order to obtain the more reactive metakaolin, which is then subjected to alkali HT treatment for
zeolite crystallization [41,57,58]. Similar methods have been applied for the synthesis of zeolites
(NaY and NaP) from natural mordenite [53] and NaP1 [58,59] and NaA [60] from natural diatomite.
Zeolites NaP, NaX, NaP and NaA with high CEC were obtained by fusion of low-grade natural
clinoptilolite [52,61], halloysite [62] and illite [42] with NaOH prior to hydrothermal treatment.
Another approach in the utilization of natural minerals for zeolite production is based on chemical
treatments, aiming at the conversion of Si- and/or Al- ingredients of the rocks into alkaline silicates
and aluminates, and subsequent HT synthesis of zeolites from these solutions [61]. Zeolite ZSM-5
with high specific surface area has been successfully synthesized from Korean serpentine as a
source of amorphous Si [63]. Pure NaA zeolite has been prepared from a mixture of metasilicate
and aluminate solutions, prepared by alkaline dissolution of Tunisian sand and aluminium scraps,
respectively [64].

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The main disadvantages of most of the methods for zeolite synthesis from natural minerals are the
application of high energy-consumption processes like grinding, calcination and fusion, and the
landscape-destructive effect of raw materials mining. The last is avoided when zeolites are
synthesized from waste materials, having the additional advantage of zero or even negative price.
3.1.2.2. Synthetic zeolites from waste materials
3.1.2.2.1. Zeolites from coal fly ash (CFA)
Over 500 million tones of CFA are generated every year in the world as a by-product of coal
combustion in thermal power plants [65]. More than 65% of this fine-powdered waste is disposed of
in landfills and ash ponds creating serious problems with air and water pollution. On the other hand,
CFA contain significant amount of crystalline and amorphous aluminosilicates that could be utilized
for zeolite production. Since the initial study on the conversion of CFA into zeolite, published in
1985 by Höller and Wirsching [66], a large number of scientific articles have been devoted to the
development and optimization of HT methods for CFA zeolitization. Generally, these methods are
based on alkaline activation of CFA (with or without preliminary fusion with alkali) aiming at he
dissolution of Al and Si - bearing phases, and precipitation of zeolites [1,67-76]. In most studies,
the CFA activation is carried at temperatures in the range 100 - 200 ºC, conversion time 3 - 48 h,
alkali concentration 0.5 - 5 M and liquid/solid ratio 1 - 20 ml g-1 [1]. They have demonstrated that,
at different treatment conditions, more than 15 types of zeolite (e.g. NaA, NaX, NaY, NaP1, K-
chabazite, Linde F, etc. [1,67,68,72]) could be synthesized, and that the type and the yield of zeolite
obtained, are strongly influenced by chemical and mineralogical composition the CFA used [77].
CEC of CFA-derived zeolite material varies in a large range and depends upon the type, form (Na-
exchanged, K-exchanged, etc.), purity and content of the zeolite in it. The experimental CEC values
reported for some CFA-derived zeolites are presented in Table 4.
Table 4. Measured CEC of some CFA-derived zeolite materials
CEC,
Zeolite Conversion method Reference
meq g-1
Sodalite Direct HT treatment 0.3 [1]
Analcime Direct HT treatment 0.6 [1]
Linde F Direct HT treatment 1.9 [1]
KM Direct HT treatment 1.9 [1]
Herschelite Direct HT treatment 2.1 [1]
NaP1 Direct HT treatment 2.7 [1]
NaP1 Obtained from supersaturated silicon and aluminium alkali
4.5 [79]
extracts from fused CFA
NaA Obtained from supersaturated silicon and aluminium alkali
4.4 [79]
NaA Obtained from silicon and aluminium alkali extracts of CFA 1.8 [80]
NaA Fusion with alkali prior to HT treatment ≈ 3.5 [81]
NaA Obtained from silicon and aluminium alkali extracts of CFA ≈ 5.7 [81]
Blend of NaA and K-A Direct HT treatment 1.1 [82]
Blend of NaA and NaX Obtained from silica extracts from CFA 4.7 [1]
Blend of NaA and NaX Obtained from Si-Al extracts from fused CFA 4.6 [83]
NaX Room temperature synthesis 2.5 [84]
NaX Fusion with alkali prior to HT treatment 2.2 [85]
NaX Obtained from supersaturated silicon and aluminium alkali
3.2 [79]
NaX Fusion with alkali prior to HT treatment ≈ 3.2 [81]
NaX Obtained from silicon and aluminium alkali extracts of CFA ≈ 5.0 [81]
Blend of NaX, HS, and HT treatment of low-calcium CFA 2.8 [86]

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traces of NaP and NaA

Blend of NaP and calcium HT treatment of high-calcium CFA 0.7 [86]
silicate hydrate
Blend of unnamed zeolite, Direct HT treatment 1.2 [82]
ZSM18, LTL and erionite
3.1.2.2.2. Zeolites from municipal solid waste incineration ash (MSWIA)

MSWIA have been also researched [87-92] as potential starting materials for the synthesis of
zeolites, due to their high specific surface and the content of SiO2 and Al2O3, even though in less
quantity than in CFA. One of the first reports on the zeolitization of MSWIA was published by
Yang and Yang [91] who applied HT alkaline processing, very similar to that used for CFA
activation. The zeolites formed were mainly gismondine and unnamed sodium alumina silicate
hydrate. Small quantity of NaX was also detected in some samples but CEC of the produced
materials did not exceed 0.64 meq g-1. Successful synthesis of zeolites NaA, NaP and sodalite from
the MSWIA by fusion prior HT treatment was also reported [90] but the CEC obtained was again
unsatisfactory (maximum 1.09 meq g-1). Later, the investigations of Sallam [87] confirmed that the
direct HT treatment of MSWIA is inefficient in producing of zeolites of commercial quality, but the
application of preliminary fusion under optimized conditions could considerably increase the CEC
of the final product - a blend of NaA, sodalite and unnamed zeolite - up to value of 2.45 meq g-1,
which is within the commercial range.
3.1.2.2.3. Zeolites from oil shale ash (OSA)
Since 2004, several studies dealing with zeolite synthesis from OSA, a high-volume by-product fly
ash from oil shale processing, have been published [93-95]. Shawabkeh et al. [93] first reported the
synthesis of zeolite (NaP1) by HT treatment of OSA. The activation was performed at different
temperatures (25-160°C) using 8 M NaOH. The maximum CEC of 1.66 meq g-1 was obtained at the
highest temperature 160 °C and treatment time 24 h. The linead increase of the CEC with
temperature rise indicated that it could be improved by furher optimization of the treatment
conditions. Purified (milled, calcinated and acid-washed) OSA was used as a raw material for
synthesis of zeolites by alkaline fusion (at 350°C) followed by two different crystallization
procedures – refluxing and HT treatment, both realized at 100°C [94]. The largest amount of
crystalline zeolites (≈ 92%) has been obtained at 2 h 30 min of and at 12 h respectively. In both
procedures, the synthesis products were mainly composed of NaX zeolite, whose content was
influenced by the crystallization time, and of NaA zeolite, with a practically constant content,
limited by the content of Al2O3 in OSA.
3.1.2.2.4. Zeolites from rice husk ash (RHA)
Pure, high-grade zeolites could be synthesized from silica-rich (85-98% SiO2) RHA generated
during the burning of rice husk (RH), one of the largest agricultural wastes with annual world
production of about 120 million tonnes. The composition of RHA and its zeolitization behaviour
depend mainly on calcination temperature. As a rule, the complete RH burning at high temperatures
(800-1000°C) produces white, carbon-free, low-reactive crystalline SiO2, while the incomplete
roasting at lower temperatures (500-700°C) yields in a so called carbonized RHA, containing
carbonaceous material and highly reactive amorphous SiO2 [96], which is more easily dissolvable in
alkaline medium. For this reason, carbonized RHA is the preferred starting material for preparation
of alkaline silicate solution, which is then mixed with standard aluminate solution and processed via
classic HT methods to produce the desired zeolite. The main RHA-derived zeolites are NaA, [97-
103], NaX, [98,104,105], NaY, [98,106-108], ZSM-5, [109-114], ZSM-48 [114], and zeolite-beta
[115,116]. Measured CEC values of some zeolites, obtained from RH are presented in Table 5.

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A synthesis of pure zeolite NaA from silicate solution, obtained by direct leaching of RH at 150°C
in autoclave, was also reported [96]. The obtained solution was mixed with standard Al-solution
and subjected to HT crystallization for 5 h at 100°C in autoclave.
Table 5. CEC of some RHA-derived zeolites

CEC,
Zeolite HT treatment conditions Reference
meq g-1
NaA 3 h at 90 °C in autoclave 5.79 [104]
NaX 6 h at 90 °C in autoclave 4.61 [104]
NaY 24 h ageing, seeding, 22 h at 100 °C 3.15 [98,107]
3.1.2.2.5. Zeolites from other wastes

Synthesis of zeolite NaP1 having high CEC from paper sludge ash and diatomite was reported by
Wajima et al. [117]. Conversion of waste porcelain into Zeolite-13X with high specific surface area
(412 m2 g-1) was achieved by alkali fusion at 600° C (6 h) followed by HT treatment at 80° C (12 h)
[118]. The prospects for the utilization of several other industrial wastes, such as cupola slag
[3,119] and exhausted fluid cracking catalysts [120,121] for the synthesis of valuable zeolites
(ZSM-5, NaA, NaX) have been also considered as technically feasible and environmentally
appropriate alternative to their disposal. In addition, some municipal solid wastes such as non-
recyclable glass and thin-walled aluminium scrap (i.g. Al-foils and cans) which recycling is usually
less effective also could be utilized as Si- and Al-sources in zeolite synthesis.
Regardless of their origin, zeolites have found broad range of (waste)water treatment applications,
related to their unique native or designed properties. The CEC and selectivity are definitely the most
important characteristics of zeolites, because a substantial part of (waste)water treatment processes
are based on the selective sorption of metal cations, ammonium or polar organic compounds. In
addition, cation exchange properties of zeolites can be exploited to modify their surface chemistry
such that other classes of compounds can also be retained [122].
3.1.3. Modified natural and synthetic zeolites
An interesting class of materials, extending the area of application of zeolites in (waste)water
treatment, is surfactant-modified zeolites (SMZ) [8,122], which combine the cation sorption
properties, typical for zeolites, with the ability to sorb anionic species (e.g. arsenates, chromates,
iodides, nitrates, phosphates, perchlorates, antimonates) and non-polar organics (e.g. benzene,
toluene, ethylbenzene, and xylenes (BTEX), phenoles, pesticides, herbicides, dyes, etc.) for which
untreated zeolites have little or no affinity [8,123,124]. The most frequently used modifying agents
are quaternary amines (e.g. hexadecyltrimethylammonium (HDTMA), cetyltrimethylammonium
bromide (CTMA), octadecyldimethylbenzyl ammonium (ODMBA), N-cetylpyridinium (CPD),
benzyltetradecyl ammonium (BDTDA), stearyldimethylbenzylammoniumchloride (SDBAC), etc.),
which form on the zeolite surface a bilayer-like structure [8]. The positive surface charge provides
sites for sorption of anions, whereas the organic-rich surface layer provides a partitioning medium
for sorption of non-polar organic compounds [8]. Although the modified zeolites have anion
exchange properties, they keep the ability to adsorb inorganic cations. It is because the modifiers
are relatively large molecules, which remain on the external surface of the zeolite crystal and do not
enter the zeolite channels [125], where the local surface charge remains negative. Similar anion
sorption properties are demonstrated by polymer-modified zeolites (e.g. by polyhexamethylene-
guanidine) [8,126,127] and metal cation-modified zeolites [128-130]. The SMZ are stable in water

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and aggressive chemical solutions [122]. Their relatively low cost makes them a viable alternative
to other commercial adsorbents such as activated carbon and ion exchange resins. The most relevant
applications of natural SMZ were reviewed in [123].
3.2. (WASTE)WATER TREATMENT APPLICATIONS OF ZEOLITES

3.2.1. Water softening
The largest commercial market of synthetic zeolites, estimated of about 1.3 million tons per annum,
is as water softening “builder” in detergent formulations. In 1973 the German company “Henkel”
patented formulations incorporating zeolite NaA as a water softener [131]. In 1978 “Procter and
Gamble” introduced zeolite NaA in its laundry detergents [132], and nowadays, most of the
commercial washing powders, contain zeolite, instead of harmful phosphates, banned in many parts
of the world because of the risk of water eutrophication [133]. Zeolite NaA does not contribute to
the eutrophication potential of surface waters and is nontoxic to freshwater and marine aquatic
communities [134]. Moreover, some zeolites, for example, zeolites, obtained from high-calcium
CFA or in Ca-exchanged forms, have been successfully applied for elimination of phosphate
contamination via precipitation of Ca-phosphates [135-137]. Zeolite A possesses high affinity for
exchange of Na+ with the “hard” Ca2+ ions in a broad range of pH values [138]. However, whilst
calcium ions diffuse relatively easily into the interstices of zeolite A, the smaller magnesium ions
are impeded by a hydrate shell [139], and are therefore incorporated more slowly [140,141]. At
higher temperatures, when the hydrate shell of the Ca2+ ion is gradually removed, the rate of
exchange increases. Similar behaviour was reported for zeolite NaP when tests were performed at
room temperature, whereas, at 60◦C the affinity of the material toward Mg2+ increased to acceptable
levels [142]. Due to its larger pore diameter of 0.74 nm, zeolite X has significantly higher
magnesium binding capacity compared to zeolite A and zeolite P [139] and was successfully
introduced into detergents market 14 years ago [143]. Other zeolites, such as zeolite 13X [144] and
clinoptilolite [145, 146], have been also reported for use in detergent formulations. The experiments
of Culfaz et al. [146] showed that zeolite A and zeolite X were more effective in cleaning than
clinoptilolite at low temperatures, while all these builders had the same effectiveness at high
temperatures. A relatively new and effective zeolite for water softening applications is so called
zeolite AX. It represents a co-crystallite comprised of 80% zeolite X and 20% zeolite A, which has
Ca2+ and Mg2+ exchange properties better than those of a blend of the pure zeolites [147].
Since detergent ingredients have to be pure, synthetic zeolites, obtained from chemical reagents or
high-grade natural row materials are commonly used for this purpose. Nevertheless, some recent
studies have demonstrated that sоme waste-derived zeolites, obtained by appropriate technology,
could compete the commercial products in this application. For example, Hui and Chao [148]
succeeded to obtain single-phase zeolite 4A (NaA) samples in pure form with a high crystallinity
(up to 95%) by applying step-change of synthesis temperature during HT treatment of CFA. The
calcium binding capacity of these zeolite 4A samples and the commercial detergent grade zeolite
4A (Valfor 100) were tested for usage as a detergent builder (see Table 6). The results show that
Table 6. Ca2+ sorption properties of commercial and CFA-derived NaA according [148]*
Zeolite Zeolite origin Ca2+conc., mg l-1 Ca2+ sorption, mg g-1 Ca2+ removal, %
NaA Commercial 40 40 100
NaA CFA- derived 40 37-41 100
NaA Commercial 80 76 100
NaA CFA- derived 80 57-75 82-94
* Some values are recalculated and/or rounded.

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zeolite 4A obtained from CFA behaved similarly as the commercial one in removing calcium ions
during the washing cycle. Moreover, the leaching tests performed for evaluation of the toxicological
safety of the synthesized materials showed that CFA-derived 4A samples leached the same
elements as the commercial one with the concentrations in the same order of magnitude.
Alongside their main function (that of softening water) zeolites also have other proven effects in the
laundering process. Zeolite A, for instance, promotes the inhibition of graying through
heterocoagulation with dirt particles. Zeolites can remove dyes from the washing liquor by
heterocoagulation and adsorption. In conjunction with the relatively low sodium concentration
associated with zeolite as compared with soluble builders, this leads to a reduced risk of dyes
discolouring other items [139].
The main disadvantage of the use of zeolites in as water softener in detergent formulations, is that
since zeolites are insoluble in water they lead to increase in sewage sludge mass. Experimental
measurements and model calculations have shown that zeolite A typically accounts for an increase
of approximately 10% in the dry mass of the sewage sludge [139]. However, field studies have
indicated that zeolite-based detergents do not cause any increase in the volume of sewage sludge,
which is more important with respect to sludge handling and disposal. On the contrary, in the
presence of zeolite A the sedimentation and dehydration properties of the sludge are improved
which can facilitate the operation of the sewage treatments plants [149].
Due to the advantageous builder properties of zeolites combined with their human and
environmental safety, they have been included in an extensive range of detergent formulations
[139]. In Europe, the USA, Japan and several regions of East Asia, zeolites have almost entirely
replaced phosphates [150]. Zeolites are widely used in industrial water softening systems and in
domestic “on the tap” filters, since the “hard” cations-loaded zeolite could be easily regenerated by
treatment with concentrated sodium solutions.
3.2.2. Ammonia removal
Another industrial application of zeolites is for separation of ammonia from drinking or wastewater.
The term ammonia includes the non-ionized (NH3) and ionized (NH4+) species. Ammonia in the
environment originates from metabolic, agricultural and industrial processes and from water
disinfection with chloramine. Natural levels in groundwater and surface water are usually below 0.2
mg l-1 [151] but intensive rearing of farm animals can give rise to much higher levels in surface
water. Ammonia in water is an indicator of possible bacterial, sewage and animal waste pollution.
Ammonia may have harmful effect on human and animal health [125], it contributes to the
eutrophication and oxygen depletion in receiving waters [9], and in addition attacks the rubber
components of water plumbing systems. In the Guidelines for drinking-water quality of the World
Health Organization (WHO) [151], no health-based guideline value for ammonia is recommended,
but the it is stated that ammonia could cause taste and odour problems at concentrations above 35
and 1.5 mg l-1 respectively. Existing methods and technologies for the removal of this
pollutant/contaminant, i.e. biological [152] (biological filter, biological contact oxidation, etc.) and
physicochemical [153,154] (air stripping, break-point chlorination and ion exchange, etc.), are
constantly being adapted and improved, but still some limitations in these methods exists. For
example, biological filter is very effective for ammonia removal, however it is sensitive to
temperaure and climat conditions, it requires high costs for construction of the filter and there is a
higher risk to safety during the subsequent processing [23]. The traditional ion exchange using ion
exchange resins also has high running costs and has been limited to application in smaller quantities,
because ammonia could be exchanged by other high-valence ions presented in wastewater [23].
Compared with the above-mentioned methods, safety, low cost, and high affinity for NH4+ are three

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of the attributes that are attracting an increasing focus on the use of zeolite as ion exchanger for
ammonia removal from water.
The removal of ammonia by natural zeolitic materials was widely investigated in the last few
decades and the most important results were reviewed in several papers [7-9,125,155]. They
indicate that clinoptilolite and mordenite are the most effective natural zeolites for ammonia
removal [8,10,11,24,29,156], due to their high selectivity for ammonium ion in the presence of
competing cations (such as K+, Ca2+ and Mg2+), across a wide range of NH4+ concentrations [156].
The maximum ammonia adsorption capacity of natural zeolites from different deposits varies from
2.7 mg g-1 (Chinese clinoptilolite) to 22.9 mg g-1 (Canadian clinoptilolite) [9] and is generally lower
than that of synthetic zeolites (e.g. Na–P [158,159], Na–Y [108,158,160], NaX [162], NaA
[63,161,162]), whose adsorption capacities are typically in the range 20-50 mg g-1. The ammonia
uptake capacity of clinoptilolite could be improved to a certain degree by application of suitable
pre-treatments, such as grinding, sieving, acid washing, heating, and pre-exchange strong Na+
solutions. [20,163]. The last is applied in order to obtain homionic Na-form of the clinoptilolite,
which has higher ammonia exchange capacity than K+ and Ca2+ forms, according to the order of
affinity of clinoptilolite to alkaline and earth-alkaline cations: K+ > NH4+ > Ca2+ > Na+ > Mg2+ [24].
The actual ammonia adsorption capacity and efficiency of NH4+ removal process depend upon the
type of zeolite used, contact time, initial concentration of ammonia, temperature, the amount of
zeolite loading, its particle size and presence of competitive ions [125,155]. The influence of these
factors has been discussed in several researches on the kinetics and equilibrium of ammonia
sorption from model solutions or real effluents [20,62,156,158,160,164-166,207]. Summarized
experimental data for the ammonia adsorption performance of some natural and synthetic zeolites
are presented in Table 7.
Table 7. Ammonia adsorption on some natural and synthetic zeolites
NH4+ Zeolite NH4+ NH4+
Zeolite Zeolite origin conc. dosage sorption removal, Reference*
mg l-1 g l-1 mg g-1 %
Blend of heulandite,
China 80 24 2.9 83 [167]
montmorillonite and illite
Mordenite Nutural 18 80 [168]
Mordenite Powdered 50 2.5 15.3 42 [107]
Mordenite Granulated 50 2.5 14.6 48 [107]
Mordenite New Zealand 10-200 10 1.3-14.4 92-56 [156]
Clinoptilolite New Zealand 10-200 10 1.3-11.9 98-46 [156]
Clinoptilolite Australia 5.8 96-98 [10]
Clinoptilotite Chile 121 2.5 13.4 - [20]
Chile,
Clinoptilotite modified with 121 2.5 18.3 29 [20]
NaCl
Iran, mm-
Clinoptilolite 90-3610 3.3 11.3 88-10 [157]
sized
Iran, nm-
Clinoptilolite 90-3610 3.3 13.3 92-11 [157]
sized
Clinoptilolite China 80 6.1-1.2 83-96 [167]
Clinoptilolite China 250 10 10.5 [160]
Clinoptilolite USA 5.4 18.4 [169]
Clinoptilolite Croatia 130 10 7 61 [11]
Clinoptilolite Croatia 640 10 16.7 [11]
Clinoptilolite Croatia 800 17.7 75 [24]
Clinoptilolite China, 5 0.15 [23]

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modified
Clinoptilolite Turkey 5.2-8.1 [170]
Clinoptilolite+
Turkey 88 10 1.39 >85 [29]
mordenite
Clinoptilolite/
Turkey 60-150 20 9.6 94-75 [164]
heulandite + mordenite
Clinoptilolite/
Turkey 60 10 80 [164]
heulandite + mordenite
Fauyasite CFA-derived 144 19.2 [161]
NaA Synthetic 144 50.2 [161]
NaA CFA-derived 144 15.5 [161]
From
NaA 50-300 10 9-35 76-6 [62]
halloysite
NaA Commercial 285 9.6-49.6 5.1-1.4 17-35 [162]
NaA Commercial 3372 26-76 19.5-14.3 19-32 [162]
NaA CFA-derived 285 9.8-47.4 5.0-1.8 17-29 [162]
NaA CFA-derived 3372 23-74 25.4-17.7 17-39 [162]
NaX Commercial 285 12-50 3.0-1.0 13-17 [162]
NaX Commercial 3372 26-74 16.5-19.6 16-43 [162]
NaX CFA-derived 285 9.2-51.2 7.3-2.2 23-40 [162]
NaX CFA-derived 3372 26-79 23.4-18.5 18-43 [162]
NaP1 CFA-derived 285 11.2-51.6 5.3-2.5 20-45 [162]
NaP1 CFA-derived 1600 6-19 [171]
NaX with small amounts of
CFA-derived 43-348 4 7-27.3 66-28 [86]
HS and NaP
NaP CFA-derived 200 10 45 [165]
CFA-derived,
NaP 200 10 60 [165]
acid washed
NaP CFA-derived 3.5 35-47 60-80 [159]
From
NaP 64.4 [158]
Clinoptilolite
NaP and calcium silicate
CFA-derived 130 4 2.5 [166]
hydrate
Blend of NaX, HS, NaA,
CFA-derived 130 4 18.2 [166]
NaP
From
NaY 49.5 [158]
Clinoptilolite
From
NaY 250 10 19.3 [160]
Clinoptilolite
NaY RHA-derived 50 2.5 42.7 71 [207]
Rozic et al. [11] investigated the NH4+ removal from water with natural and modified bentonite clay
and Croatian clinoptilolite. The results showed that natural zeolite had much higher removal
efficiency (61.1 wt% at 100 mg N-NH4+ l-1) when compared with that of the clay (<47 %) at the
same conditions. With the increase of the initial concentration of ammonia, the removal efficiency
rapidly decreased. A contact time of 60 min was found to be sufficient for quantitative removal of
NH4+ by zeolite. Cooney et al. [172] undertook a laboratory study of Australian clinoptilolite, to
remove ammonia from water. They investigated the equilibrium and kinetic characteristics of
ammonia exchange in the zeolite under binary and multi-component conditions. The results
revealed that the highest ammonia removal efficiency was achieved with the sodium form of
zeolite. For a multi-component system there was a competitive effect between ammonia and other
cations such as Ca2+, Mg2+, K+ and the zeolite’s selectivity for ammonium ions was over other
cations typically present in sewage. Malekian et al. [157] studied the ammonia removal from
aqueous solutions with different Na+ concentrations (0.03, 0.1, and 0.3 M) by Iranian clinoptilolite
in millimeter and nanometer particle sizes. The maximum NH4+ exchange capacity by the zeolite at

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equilibrium was obtained for the lowest sodium concentration in the solution - 11.31 and 13.27 mg
NH4+ g-1 for millimeter- and nanometer-sized zeolite, respectively.
Weatherley and Miladinovic [156] compared the ammonia uptake performances of New Zealand
clinoptilolite and mordenite in the concentration range of 0–200 mg NH4+ g−1. The results showed
that the mordenite exhibited higher overall uptake at equilibrium compared with clinoptilolite at
solution concentrations greater than 80 mg l-1. The influence of other cations (K+, Ca2+ and Mg2+)
present in water upon the ammonia uptake was estimated to be relatively small and smaller for
mordenite. In all cases, the ammonium ion showed the highest uptake on to both zeolites, wich is in
a contrast with the majority of other researches reporting that clinoptilolite exhibits higher affinity
for K+ than for NH4+. Other components in the solution such as heavy metal ions and organics also
may affect ammonia exchange due to competitive adsorption [9,24], as indicated the investigation
of Farkas et al. [24] who studied the adsorption of ammonium ions and organic pollutants on
clinoptilolite from leakage waters from waste dumps. Without pre-treatment of leakage water, the
exchange of NH4+ on the zeolite was found to be 4.2 mg NH4+ g-1, while in pure ammonia solution,
the exchange was 17.70 mg NH4+ g-1, suggesting that organic pollutants and K+ and Ca2+ ions in
leakage water prevents the exchange of NH4+ ions.
Englert and Rubio [20] studied ammonia exchange by natural and modified Chilean clinoptilolite.
The ammonia uptake tests were conducted with 0.25 g zeolite, 100 ml of 100 mg NH3-N l-1 solution,
for 2 h and varying the feed solution concentrations. The Langmuir isotherm model provided best
correlation of the equilibrium data reaching saturation values at 0.68 meq NH4+ g-1. Results from
batch experiments at different pH (2-12) of the suspension showed optimal pH=6, while at acidic
and basic conditions the removal was decreased. Optimal pH values in the close to neutral range
(pH=5-8) were obtained in a number of other studies [62,86,107,164,165,167], as well.
Theoretically, according to the equilibrium reaction (NH3+H2O↔NH4OH), ammonia removal
should be greater at lower pH and smaller at higher pH values, as the cation exchange mechanism
occurs only by means of the ammonium ion. The steep reduction of ammonia uptake at alkaline
conditions (pH>9) thus could be partially explained by the presence of significant amount of
electrically neutral NH3 [20] in the solution. Although it could be expected that the volatilization of
NH3 contributes to the elimination of ammonia at alkaline pH values, the data obtained by Zhang et
al. [165] indicated that only about 5% of the ammonia is lost by volatilization for a solution of 25
mg N.l-1 and pH=11.4. Partial dissolution of the zeolite is suggested as another possible reason
contributing to the reduction of ammonia uptake of natural zeolites pH > 8 [167]. The observed
reduction of ammonia removal at acidic conditions (pH<5) is probably a result from the
competition between NH4+ and H+ for the exchangeable sites on zeolite [20,165]. Quite acidic
conditions (pH<2) could cause structural degradation of the zeolite [173], as well.
The sorption kinetics studies of Englert and Rubio [20] showed that the ammonia removal
proceeded very rapidly (rate constant of 0.3 min-1), indicating approach to chemical equilibrium in
approximately 15 min. Similar kinetic results were obtained by Demir et al. [174] with a
clinoptilolite from Turkey, and by Zhao et al. [62] with NaA zeolite. Saltali et al. [164] studied the
removal efficiency of NH4+ ion from aqueous solution using the natural Turkish zeolite, containing
clinoprtoloite, heulandite and mordenit. The experiments were carried out using batch method (60
mg NH4+ and 10 g zeolite per liter) at room temperature and pH=8. The results showed that removal
efficiency of NH4+ ion increased with increasing shaking time and 75% of NH4+ ion removal was
completed within 15 min. It reached up 80% within 30 min and than became very slow. The
kinetics studies have clearly demonstrated that the rate of NH4+ ions removal by zeolite is initially
very high, but thereafter significantly reduces. This change in the adsorption rate could be explained
with the fact that initially all adsorbent sites are vacant, and the solute concentration gradient is

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high, but afterwards the decrease in adsorption sites and concentration gradient lead to rate decrease
in NH4+ uptake rate [62]. The contact time is particularly important for continuous process
operation, because lower resident times are required to reduce footprint installations using compact
units [20]. Sarioglu [29] investigated the ammonia uptake from drinking water by natural zeolite in
column tests performed at different flowrates. It was found that the system saturated within 5 min.
The highest adsorption capacity (1.08 mg NH4+-N g−1) was obtained at a contact time of 40 min (at
pH=4 and 0.5 ml min−1). For influent concentration of NH4+-N 5 mg l−1 100% removal efficiency
was achieved, but it was not possible to reach such high values when initial concentration of 12 mg
l −1 NH4+ were used.
Huang et al. [167] studied ammonia removal from aqueous solutions by using natural zeolitic
material containing 46% heulandite, 24% montmorillonite and 30 % illite. The optimum pH was
found to be 8 and the pH dependence of absorption followed similar trend to that of clinoptilolite.
The effect of other cations on the removal of ammonia followed the order of preference
Na+>K+>Ca2+>Mg2+ at identical mass concentrations, and the effect of the presence of individual
anions followed the order of preference CO32->Cl->SO42->HPO42-. It was observed that NH4+
removal efficiency rose from 67.4% to 81.1% with reduction in the zeolite particle size range from
0.2-0.3 mm to 0.074-0.125 mm, due to the increase of specific surface. Sorption equilibrium was
attained after approximately 180 min of adsorption for all zeolites of different particle size ranges.
Equilibrium isotherm data was fitted better to the Freundlich model. At optimal conditions, NH4+
removal rose from 61.4% to 96% with the increase of zeolite dose from 8 to 64 g l-1.
Wang et al. [160] investigated the equilibrium uptake behaviour of NH4+ in the concentration range
of 50–250 mg l-1onto clynoptilolite and obtained from it zeolite NaY. It was established that due to
its bigger aperture and lower Si/Al molar ratio zeolite NaY had much (almost twice) higher
ammonium exchange capacity than the natural zeolite (see Table 7). Adsorption isotherms of the
two materials were similar and fitted good to Freundlich model. In order to establish the influence
of K, Ca and Mg ions alone upon NH4+ uptake, further equilibration experiments were conducted
with metal cation concentration of 100 mg l-1, which equals to 2.6 meq K.l-1, 5 meq Ca.l-1 and 8.3
meq Mg l-1. The results showed that in both cases the presence of additional cations leads to
significant reduction in the equilibrium uptake of ammonia. For the natural zeolite, the reduction
followed the order of K+>Ca2+>Mg2+ (opposite to the order of equivalent concentrations used),
which is consistent with the results obtained by Farkas [24]. For zeolite NaY the order of preference
was Mg2+>Ca2+>K+, i.e. corresponding to the their equivalent concentrations. This indicates that
zeolite NaY exhibits lower selectivity for these cations than the natural clinoptilolite. The reason for
this is that NaY has much bigger aperture and the ionic strength in the solution turns into the
principal factor in ion exchange. Another study of the same authors [158] on the NH4+ exchange
with natural clinoptilolite and synthetic zeolites NaY and NaP confirmed that although the two
synthetic materials have much higher CEC than the natural one, the latter has the highest selectivity
for NH4+ among the three materials. Calculated thermodynamic parameters indicated that ammonia
adsorption on zeolite at ambient conditions is an exothermic and spontaneous process, which was
confirmed by several other investigation [62,86].
Zhao et al. [62] investigated the adsorption behaviour of ammonium ions from aqueous solution
onto zeolite NaA, synthesized from natural halloysite, as a function of equilibrium time, pH, initial
NH4+ concentration, temperature and competitive cations. A maximum adsorption capacity deduced
from Langmuir isotherm was 44.3 mg NH4+ g−1. The equilibrium adsorption was reached within 15
min. The effect of the presence of competitive cations was studied at 288 K, 0.2 g l-1 adsorbent and
initial NH4+ concentration of 100 mg l-1. It was found that the adsorption capacities of NH4+ on NaA
zeolite were significantly reduced by the presence of competitive cations. When the concentration

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of Na+, K+, Ca2+ and Mg2+ increased from 0 to 0.1 mol l-1, the NH4+ adsorption capacities decreased
from 22.06 to 0.50, 0.51, 0.56 and 7.66 mg g−1, respectively. This indicates that the selectivity order
of ammonia over other cations was Na+>K+>Ca2+>Mg2+, which is consistent with the result
reported for natural zeolite (heulandite + montmorillonite) [167], but does not match the order of
selectivity reported for clinoptilolite (Ca2+>K+>Mg2+) [156] and CFA-derived NaX
(K+>Ca2+>Na+>Mg2+) [86]. These findings suggest that different type of zeolites, and even different
zeolites of the same type [156], may exhibit different cation selectivities. In the case of NaX
obtained from CFA [86], the increase of Ca2+, Mg2+, Na+ and K+ concentrations from 0 to 10 meq.l-1
decreased the removal efficiency of NH4+ from 69.9% to 44.9%, 64.4%, 53.8%, and 41.5%,
respectively. When the initial ammonium ion concentration increased from 2.56 to 25.07 meq l-1
with CO32-, Cl-, and SO42- individually present in the solution, the ammonia removal decreased from
about 68.7% to 26.5%, 28.3%, and 38.4%, respectively, i.e. the order of anion effects on ammonia
uptake was CO32->Cl->SO42-, which is in agreement with the results obtained by other authors
[167].
Otal et al. [162] investigated the application of several synthetic zeolites to the decontamination of
leachate produced in a MSW treatment plant and to liquid waste from a pig farm. The reduction of
organic matter, ammonia and total nitrogen, phosphorus and metals contents was evaluated.
Commercial zeolites (NaA and NaX) and CFA-derived zeolitic materials (containing NaA, NaX
and NaP1) were tested in a stirred tank and in a column experiments. For the different types of
zeolites tested, the maximum elimination percentages ranged from 16.7 to 45.0% in the case of the
landfill leachate and from 32.2 to 43.4% in the case of the pig slurry. In general, the behaviour of
any given zeolite with regard to the elimination of nitrogen was always slightly superior in the case
of the pig slurry samples, which had almost ten times greater concentration of NH4–N. It was found
that the performance of CFA-derived zeolites was similar to those of the commercial zeolites of the
same type (see Table 7). Authors estimated the total manufacturing cost of 1.7 EUR per kg of pure
zeolite NaA, which could be considered competitive to other commercial adsorbents. Zeolite (NaP1
with small amounts of analcime and chabazite), synthesized from CFA, was used a bench-scale
study both as a decantation aid reagent and as an adsorbent of COD and NH4–N [159]. The leachate
was collected directly from a storage unit of the organic fraction of MSW, before it was composted.
The sludge was recirculated to enhance the removal efficiency of nutrients as well as to optimize
flocculant saving and to decrease sludge production. The results showed that it is possible to
remove 43%, 53% and 82% of COD, NH4–N, and suspended solids, respectively.
Yusof et al. [107] performed recently kinetic and equilibrium studies of the removal of ammonium
ions from aqueous solution by RHA-synthesized zeolite NaY and powdered and granulated
mordenite. They showed that NaY presents the superior adsorption capacity, which is 3 times
greater than that of mordenite. The maximum monolayer adsorption capacity, obtained from the
Langmuir plots for NaY, powdered mordenite and granulated mordenite were 42.37, 15.13, 14.56
mg NH4+ g−1, respectively. The initial uptake of ammonia occurred rather fast for NaY and
powdered mordenite and reached equilibrium in less than half and hour, and two hours,
respectively. Inversely, granular mordenite demonstrated slower ammonia uptake and reached
equilibrium in about 24 h. Adsorption kinetics can be best represented by a pseudosecond-order
model with initial sorption rate being highest for adsorption on zeolite Y. Authors concluded that
zeolite Y synthesized from RHA can be utilized as an alternative sorbent to remove ammonia from
water owing to its rapid adsorption rate, high adsorption capacitiy and low production cost.
Since the ammonia-removal efficiency of zeolite decreases after operating for a long duration, due
to the depletion of the free ion exchange sites, the investigation of zeolites regeneration behavior is
of a great practical interest. For this purpose, number of methods for the regeneration of

___________________________________________________________________________________________________________
ammonium-loaded zeolite have been elaborated and tested. They includes heating (at 200–500ºC in
air stream) leading to NH3 evaporation [23], biological regeneration by nitrifying bacteria which
converts NH4 + to NO3– on the surface of zeolite in oxygen-enriched air [155,175], acid washing
leading to the ion exchange of NH4+ with H+ [23,62], treatment with sodium salt to obtain Na-
zeolite [23,29,62,86,155], and electrochemical regeneration (using a Ti/IrO2–Pt anode and Cu/Zn
cathode) in the presence of chloride ions aiming the convertion of ammonia into nitrogen gas [176].
The comparison of the reported results indicated that treatment with NaCl solution (0.5-2.0 mol.l-1)
for a period varying from half an hour to several hours is probably the most effective and feasible
method for regeneration NH4+- loaded zeolite.
Li et al. [23] have tested heating (at 200 °C for 24 h), acid washing (with 1.0 mol.l-1 HCl solution
for 24 h) and NaCl treatment (2.0 mol.l-1 for 24 h) method for the regeneration of natural and
modified Chinese clinoptilolite used for ammonia removal from drinking water. Their experiments
showed that the adsorption capacity of the modified clinoptilolite after three regeneration cycles
was only 4 % lower than that of the fresh material, while the other two methods gave much worse
results. Zhao et al. [62] studied the reusable ability of synthetic zeolite NaA. For this aim the
adsorption experiments were performed using 0.2 g NaA zeolite and 50 ml 100 mg l−1 NH4+ at
288K for 30 min, and desorption of adsorbed NH4+ onto NaA zeolite was studied using 100ml
1mol. l−1 NaCl solution at 288 K for 30 min. Consecutive adsorption–desorption cycles were
repeated six times. The results showed only 2.2 % decrease in adsorption capacity - from 16.72 mg
g−1 for the first cycle to 16.35 mg g −1 for the last cycle. Similar results were obtained when 1M
NaCl solution was used for regeneration of ammonia -saturated CFA-derived NaX [86]. The
mixture (25 ml NaCl solution and 2 g zeolite) was stirred at 180 rpm at 25 °C for 1.25 h, dried and
sieved. The results show that the patterns of ammonia uptake by the regenerated zeolite with
different pH values (3–12) and adsorbent dosages (0.5–20.0 g l-1) were similar to those of original
zeolite. To examine the recyclization of the synthesized zeolite, the regenerative zeolite was further
used to treat wastewater from a sewage treatment plant containing competitive ions (K+, Ca2+, and
Mg2+). The results showed that the regenerated zeolite had almost the same ammonia uptake
capacity as the original zeolite. Malekian et al. [157] investigated the kinetics of the ammonia
release from NH4+- loaded Iranian clinoptilolite in NaCl solutions of different ionic strengths and
established that the process was rapid for the first 60 min and nearly complete within 150–200 min
at all ionic strengths. The amount of NH4+ released in 0.3 MNa+ was almost two-fold greater than
that in 0.03 M Na+, and the NH4+ release of deionized water was negligible. Authors suggested that
the exhausted NH4+- saturated zeolite could be utilized as a controlled-release ammonia fertilizer.
On the base of the reviewed investigations on ammonia removal by zeolites, it could be summarized
that ion exchange of NH4+ by zeolite is feasible, spontaneous and exothermic in nature process.
Increased temperature has unfavorable effect on NH4+ sorption. At ambient conditions, NH4+
adsorption on zeolite surface is a diffusion-controlled process, which rate is limited mainly by
heterogeneous diffusion on the zeolite-solution interface. Decrease in particle size of zeolites and
intensive stirring of the suspension enhance the adsorption of NH4+. Most of batch studies reported
that feasible degree of ammonia uptake from wastewaters is achieved in one hour or less, while the
equilibrium is reached within 2-3 hours. The complete removal of ammonia requires longer
treatment duration (up to several days), and is usually achieved by higher zeolite dosage and lower
initial concentration of NH4+. At higher NH4+ concentration in the solution the ammonia adsorption
capacity of zeolites is higher, but the degree of removal is lower, while with the increase of the
zeolite dosage NH4+ removal efficiency increases at the expense of adsorption capacity. The optimal
zeolite dosage varies from several grams up to several dozens grams per liter ammonia solution and
depends upon the concentration ammonia in the influent, the desired degree of its reduction, and the

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presence of competitive ions. Maximum ammonia uptake is usually achieved at pH of the

suspension in the neutral or close to the neutral area (pH=5-8). With the increase of pH above the
optimal area NH4+ removal quickly decreases, due to the transformation of NH4+ into the neutral
NH3. The decrease of pH below the optimal range leads to a slower decrease in NH4+removal, due
mainly to competitive adsorption of H+. At acidic conditions partial dissolution of the zeolite is also
possible. The presence of competitive alkali metal and alkaline earth metal ions in the solution
affects the removal of ammonia ion. This influence is related to the selectivity of the zeolite used,
which is different for different zeolites. Natural clinoptilolite has higher selectivity for NH4+ ion
than synthetic zeolites. Potassium ion has the strongest negative effect on ammonia uptake, due to
higher affinity of clinoptilolite to K+ than to NH4+. For other types of natural zeolite, ion exchange
with NH4+ is similar to clinoptilolite. Sodium form of both natural and synthetic zeolites is the most
appropriate for ammonia removal. Ammonium-loaded zeolite could be easily and almost entirely
regenerated. The regenerated zeolite could be re-used several times without noticeable affect of its
performance. Тhe spent NH4+-loaded zeolites could be utilized as а fertilizer with controlled
ammonia release. Despite of their lower selectivity to ammonia ion, synthetic zeolites, namely types
A, X and Y, have much higher ammonia exchange capacity than naturally occurring zeolites. Some
synthetic zeolites, obtained from waste materials (e.g. CFA and RHA) performed well in ammonia
removal processes and are considered as a good alternative of the natural zeolites and the other
commercial adsorbents.
3.2.3. Heavy metals removal
Heavy metals are generally considered to be those whose density exceeds 5 g cm-3 [177]. A large
number of elements fall into this category, but the ones of relevance in the environmental context
are Cd, Cr, Cu, Ni, Zn, Pb and Hg [177]. Heavy metals are well known with their toxicity. Some of
them tent to accumulate in living organisms, and may cause serious health effects, including
reduced growth and development, cancer, organ damage, nervous system damage, and even death
[151]. The recommended maximum content of some heavy metals according to the WHO’s
guidelines for drinking-water quality [151] are presented in Table 8 along with the possible negative
effects of heavy metals over-exposure on human health.
Table 8. Maximum heavy metals content and possible negative effects on humah health
Metal Effect on human health Max. content, mg l-1
Carcinogenic, accumulates in the kidney and has a biological half-life in humans of
Cd 0.003
10–35 years
Cr(VI) Genotoxic and carcinogenic 0.05
Cu Affects gastrointestinal tract 2
0.006
Hg Damages the kidney and causes haemorrhagic gastritis and colitis
for inorganic Hg
Mn Neurological 0.4
Mo Not reported 0.07
Ni Carcinogenic 0.07
General toxicant that accumulates in the skeleton and interferes with calcium
Pb 0.01
metabolism, both directly and by interfering with vitamin D metabolism
Sb Genotoxic 0.02
U Carcinogenic 0.015
Treatment processes for the removal of heavy metals from wastewater include coagulation, carbon
adsorption, ion exchange, precipitation, reverse osmosis, etc. The new trends in removing heavy
metals from industrial wastewater were reviewed by Barakat [177]. Zeolites have beed widely
explored for heavy metals immobilization form natural or industrial water. The applicability of
many natural and synthetic zeolites for the uptake of different heavy metal ions from variety

___________________________________________________________________________________________________________
synthetic and real wastewater compositions was extremely extensively researched in the last few
decades. The number of the scientific articles devoted on this problem in the past ten years exceeds
one hundred. Some of those concerning the application of natural zeolites for heavy metals removal
have been reviewed in [9]. It is known that the immobilization of heavy metal ions from aqueous
solutions by zeolites is quite a complicated process, consisting of ion exchange and adsorption and
is likely to be accompanied by precipitation of metal hydroxide complexes on active sites of the
particle surface. Similarly to the sorption of ammonia, the heavy metal cations removal efficiency
depends upon the type, dose and grain size of zeolite used, contact time, pH, temperature, initial
metal concentration and to a significant extent to the presence of competitive ions. Experimental
data for the sorption of heavy metal cations by natural and synthetic zeolites are presented in Table
9. Table 10 summarizes data for cation exchange selectivity of heavy metal ions on natural and
synthetic zeolites.
Table 9. Heavy metals adsorption on some natural and synthetic zeolites
Metal Zeolite Metal Metal
Metal Refe-
Zeolite Zeolite origin conc. dosage, sorption, removal,
ion rence*
mg l-1 g l-1 mg g-1 %
Ag+ Clinoptilolite Bulgaria 500 5 32.2 43 [19]
Ag+ Na-clinoptilolite Bulgaria 500 5 82.1 84 [19]
Ag+ Beneficiated clinoptil. USA 1072 4 84 [178]
Ag+ Beneficiated erionites USA 1072 4 94-96 [178]
Ag+ Beneficiated chabazites USA 1072 4 88-90 [178]
Ag+ Beneficiated mordenites USA 1072 4 38-75 [178]
Cd2+ Natural scolecite Brazil 50 17 2.5-8.9 84-59 [179]
Cd 2+ Na-scolecite Brazil 15 5 0.18 [180]
Cd2+ Na-clinoptilolite Croatia 1124 10 23.6 [181]
Cd2+ Clinoptilolite Croatia 1124 10 13.5 [181]
Cd2+ Clinoptilolite Greece 100 10 4.1 [182]
Cd2+ Beneficiated clinoptil. USA 1124 4 41-46 [178]
Cd2+ Beneficiated erionites USA 1124 4 61-85 [178]
Cd2+ Beneficiated chabazites USA 1124 4 53-65 [178]
Cd2+ Beneficiated mordenites USA 1124 4 29-32 [178]
Cd2+ Mordenite New Zealand 0.025 10 45 [183]
Cd2+ NaP Synthetic 0.025 10 100 [183]
Cd2+ NaP1 From CFA 100 10 50.8 [182]
Cd2+ NaP1 From CFA 11 0.1 85 [184]
Cd2+ NaP1 From OSA 100 1 95.6 [93]
Cd2+ NaA Commercial 25-100 25 98-73 [185]
Cd2+ NaA From kaolin 20 8 >99 [54]
Cd2+ NaA+ tobermorite From MSWIA 3.5 2 >99 [186]
Cd2+ Blend of NaA and KA From CFA 100 200 100 [82]
Cd2+ 13X Commercial 25-100 25 97-71 [185]
Cd2+ NaX From kaolin 20 8 >99 [54]
Cd2+ NaX + activated carbon From CFA 500 2 129.3 [187]
2+
Co Na-scolecite Brazil 15 5 0.23 [180]
Co2+ Clinoptilolite Turkey 50 20 2.0 78 [188]
Co2+ NaA From CFA 50-100 1 16.8-5.5 [80]
Cr3+ Natural scolecite Brazil 50-250 17 3.0-14.5 100-96 [179]
Cr3+ Clinoptilolite Greece 100 10 4.1 [182]
Cr3+ Natural mordenite 500 5 3.5 [53]
Cr3+ Blend of NaX and NaA From kaolin 500 5 71.1 [53]
Cr3+ Blend of NaY and NaP From mordenite 500 5 83.2 [53]
Cr3+ NaP From mordenite 500 5 52.0 [53]
Cr3+ NaP1 From CFA 100 10 43.6 [182]

___________________________________________________________________________________________________________
Cr3+ Hydroxysodalite From kaolin 500 5 34.7 [53]

Cr3+ 13X Commercial 500 5 60.7 [53]
Cr3+ NaY Commercial 500 5 36.4 [53]
Cr3+ NaA Commercial 500 5 53.7 [53]
Cr3+ NaA From CFA 50-100 1 38.7-56.4 [80]
Cr3+ NaA+ tobermorite From MSWIA 11 2 >99 [186]
Cr3+ Blend of NaA and K-A From CFA 100 200 100 [82]
Cu2+ Clinoptilolite Bulgaria 50 10 2.9 57 [189]
2+ NaOH-modified [189]
Cu Bulgaria 50 10 4.8 95
clinoptilolite
CH3COONa - modified [189]
Cu2+ Bulgaria 50 10 4.7 93
clinoptilolite
Cu2+ Na-clinoptilolite Bulgaria 50 10 4.8 95 [189]
Cu2+ Na-clinoptilolite Ecuador 635 19.2 [190]
Cu2+ Clinoptilolite Ecuador 635 0.8 [190]
Cu2+ Clinoptilolite Egypt 10-100 5 91-50 [191]
Cu2+ Clinoptilolite Greece 100 10 5.3 [182]
Cu2+ Heulandite Ecuador 635 3.9 [190]
Cu2+ Stilbite Brazil 635 2.1 [190]
Cu2+ Beneficiated clinoptilolite USA 635 4 30-35 [178]
Cu2+ Beneficiated erionites USA 635 4 63-82 [178]
Cu2+ Beneficiated chabazites USA 635 4 43-59 [178]
Cu2+ Beneficiated mordenites USA 635 4 8-18 [178]
Cu2+ Mordenite New Zealand 0.25 10 53 [183]
Cu2+ NaP Synthetic 0.25 10 98 [183]
Cu2+ NaP1 From CFA 100 10 50.5 [182]
Cu2+ NaP1 From CFA 6.4 0.1 89 [184]
Cu2+ Zeolite type 13A Synthetic 63.5-635 4 99-78 [178]
Cu2+ Zeolite type 3A Synthetic 63.5-635 4 61 [178]
Cu2+ Zeolite type 5A Synthetic 63.5 4 56 [178]
Cu2+ Zeolite type 4A Synthetic 63.5 4 64 [178]
Cu2+ NaA From kaolin 20 8 >99 [54]
Cu2+ NaA From CFA 200 5 38.0 [81]
Cu2+ NaA From CFA 50-100 1 39.8-72.0 [80]
Cu2+ Blend of NaA and K-A From CFA 100 200 100 [82]
Cu2+ Chabazite From CFA 25-54 10 87-97 [192]
Cu2+ NaX From kaolin 20 8 >99 [54]
Cu2+ NaX From CFA 200 5 28.9 [81]
Cu2+ NaX + activated carbon From CFA 500 2 101.7 [187]
Fe3+ Natural phillipsite Jordan 400 20 14.6 73 [193]
Fe3+ Clinoptilolite Turkey 400 37-150 6.4-2.6 59-97 [13]
Fe3+ Chabazite From CFA 24-49 10 99-61 [192]
Fe3+ NaP1 From CFA 5.6 0.1 29 [184]
Hg2+ Beneficiated clinoptil. USA 2006 4 5-6 [178]
Hg2+ Beneficiated erionites USA 2006 4 7-9 [178]
Hg2+ Beneficiated chabazites USA 2006 4 3-6 [178]
Hg2+ Beneficiated mordenites USA 2006 4 1-2 [178]
From filtrate from
Blend of Faujasite,
Hg2+ CFA and AMD 0.00047 20 64 [194]
Sodalite and zeolite A
co-disposal
Mn2+ Natural scolecite Brazil 50 17 2.3-9.4 75-63 [179]
Mn2+ Clinoptilolite Turkey 50 20 0.5 20 [188]
Mn2+ Clinoptilolite Turkey 20 37-150 0.52-0.13 95-99 [13]
Mn2+ Clinoptilolite Greece 4-100 10 up to 7.69 65-30 [195]
Mn2+ Fe-clinoptilolite Greece 4-100 10 up to 27.1 100-93 [195]
Mn2+ Na-clinoptilolite Serbia 50-400 10 5.0-8.0 [196]

___________________________________________________________________________________________________________
NaOH-modified
Mn2+ Chile 100 2.5 20.3 [197]
(clinoptilolite + mordenite)
Na-(clinoptilolite +
Mn2+ Chile 100 2.5 13.0 [197]
mordenite)
Na-(clinoptilolite +
Mn2+ Chile 100 25 12.4 [198]
mordenite)
Mn2+ MnO2-(clinoptilolite + Chile 100 1-6 15.1-11.8 42-99 [198]
mordenite)
Mn2+ MnO2-(clinoptilolite + Chile 100 25 30.2 [198]
mordenite)
Ni2+ Natural scolecite Brazil 50 17 2.9-6.0 96-40 [179]
Ni2+ Na-scolecite Brazil 30 5 0.9 [180]
Ni2+ Na-Clinoptilolite Serbia 100-600 10 6.0-10.6 [199]
Ni2+ Beneficiated clinoptilolite USA 587 4 20-23 [178]
Ni2+ Beneficiated erionites USA 587 4 15-17 [178]
Ni2+ Beneficiated chabazites USA 587 4 20-25 [178]
Ni2+ Beneficiated mordenites USA 587 4 8-10 [178]
Ni2+ Clinoptilolite Greece 100 10 2.0 [182]
Ni2+ NaP1 From CFA 100 10 20.1 [182]
Ni2+ NaX From kaolin 20 8 >99 [54]
Ni2+ NaX + activated carbon From CFA 500 2 132.1 [187]
Ni2+ NaA From kaolin 20 8 >99 [54]
Ni2+ NaA From CFA 50-100 1 11.5-6.1 [80]
Ni2+ Blend of NaA and K-A From CFA 100 200 100 [82]
2+
Pb Na-scolecite Brazil 30 5 5.8 97 [180]
Pb2+ Clinoptilolite Greece 1036 20 33.7 65 [200]
Pb2+ Clinoptilolite Croatia 2072 10 78.7 [181]
Pb2+ Clinoptilolite Ecuador 2072 40.4 [190]
Pb2+ Na-clinoptilolite Croatia 2072 10 91.2 [181]
Pb2+ Na-clinoptilolite Ecuador 2072 73.4 [190]
Pb2+ Heulandite Ecuador 2072 20.4 [190]
Pb2+ Stilbite Brazil 2072 8.8 [190]
Pb2+ Beneficiated clinoptil. USA 2072 4 42-69 [178]
Pb2+ Beneficiated erionites USA 2072 4 92-94 [178]
Pb2+ Beneficiated chabazites USA 2072 4 92-96 [178]
Pb2+ Beneficiated mordenites USA 2072 4 10-17 [178]
Pb2+ Mordenite New Zealand 0.05 10 89 [183]
Pb2+ NaP Synthetic 0.05 10 100 [183]
Pb2+ NaP1 From CFA 21 0.1 98 [184]
Pb2+ NaP1 From CFA 200 2.4 >95 [201]
Pb2+ NaP1 From OSA 100 1 70.6 [93]
Pb2+ NaX From kaolin 20 8 >99 [54]
Pb2+ NaX + activated carbon From CFA 100 2 228 [187]
Pb2+ NaA From kaolin 20 8 >99 [54]
Pb2+ NaA+ tobermorite From MSWIA 22 2 >99 [186]
Pb2+ Blend of NaA and K-A From CFA 100 200 100 [82]
From filtrate from
Blend of Fauja site,
Pb2+ CFA and AMD 0.00323 20 95 [194]
Sodalite and zeolite A
co-disposal
Pb2+ Hydroxysodalite From CFA 200 2.4 >95 [201]
Pb2+ Hydroxysodalite From CFA 21 0.1 65 [184]
Pb2+ Analcime From CFA 21 0.1 65 [184]
Pb2+ Cancrinite From CFA 21 0.1 45 [184]
Pb2+ Chabazite From CFA 25-49 10 99-100 [192]
Pb2+ Faujasite From CFA 0.00323 20 88 [194]
Pb2+ Faujasite From CFA 21 0.1 90 [184]

___________________________________________________________________________________________________________
Zn2+ Beneficiated mordenites USA 654 4 22-23 [178]

Zn2+ Clinoptilolite Greece 100 10 3.1 [182]
Zn2+ Mordenite New Zealand 0.5 10 42 [183]
Zn2+ NaP1 From CFA 100 10 32.6 [182]
Zn2+ NaP1 From CFA 6.5 0.1 65 [184]
Zn2+ NaP Synthetic 0.5 10 97 [183]
Zn2+ 13X Commercial 25-100 25 95-79 [185]
Zn2+ NaX From kaolin 20 8 >99 [54]
Zn2+ NaX From CFA 200 5 22.4 [81]
Zn2+ NaA Commercial 25-100 25 97-87 [185]
Zn2+ NaA From kaolin 20 8 >99 [54]
Zn2+ NaA From CFA 200 5 29.7 [81]
Zn2+ NaA From CFA 50-100 1 40.4-19.6 [80]
Zn2+ Blend of NaA and K-A From CFA 100 200 100 [82]
Zn2+ Chabazite From CFA 25-43 10 97-33 [192]
Bektas and Kara [210] studied the removal of Pb2+ from aqueous solution using natural
clinoptilolite. The effects of initial metal concentration (10–100 mg l-1), pH (2–7), agitation speed
(100–225 rpm), particle size (315–1600 µm) and temperature (25 – 50◦C) on the uptake process
were investigated. The sorption isotherms were described well by the Langmuir model with the
maximum sorption capacity of 166 mg g-1 of lead on clinoptilolite. At the maximum temperature,
and equilibrium lead concentration of about 1000 mg l-1 a sorption capacity of approximately 180
mg g-1 was reached. The sorption kinetics study indicated that the Pb2+ uptake process followed the
pseudo-second order rate expression, which is consistent with the results obtained for Mn and Zn
sorption on cliniptilolites [197,199]. Stylianou et al. [202] performed fixed bed experiments for the
removal of Pb, Cu and Zn from aqueous solutions by clinoptilolite from Greece. Experiments were
performed at volumetric flow rates of 5, 7 and 10 bed volume h-1, under a total normality of 0.01N,
at initial pH = 4 and ambient temperature. It was found that the removal efficiency increased when
decreasing the flow rate. The obtained selectivity order was Pb>Zn≥Cu, which is in agreement with
some of the results reported for clinoptilolites [203,204,206,211] but does not match the order of
selectivity (Pb>Cu>Zn) obtained for other clinoptilolites [188,205,207], and other natural zeolites
like chabasite [206,207] and mordenite [183]. These discrepancies could be explained with the
specific composition of natural zeolites from different deposits and with the differences in the
experimental methods used. Conductivity measurements showed that Pb removal follows mainly
ion exchange mechanism, while Cu and Zn removal involves sorption mechanism as well [202].
Erdem et al. [188] investigated adsorption behaviour of clinoptilolite from Western Anatolia with
respect to Co2+, Cu2+, Zn2+, and Mn2+ removal from aqueous solutions. Batch method was
employed, using metal concentrations in solution ranging from 100 to 400 mg l-1. It was found that
the adsorption phenomena depend on charge density and hydrated ion diameter. According to the
equilibrium studies, the selectivity sequence can be given as Co>Cu>Zn>Mn. The maximum
adsorption capacities for Co, Cu, Zn and Mn, according to the Langmuir equation were 244, 141,
134 and 77 mmol kg -1 in the same order.
Motsi et al. [13] studied the adsorption behaviour of clinoptilolite in order to determine its
applicability in treating acid mine drainage (AMD) containing 400, 120, 20, 20 and mg l−1 of Fe3+,
Zn2+, Cu2+, and Mn2+ respectively. Tests to determine both the rate of adsorption and the uptake at
equilibrium were performed under batch conditions from single and multi-component solutions.
The optimum conditions for the treatment process were investigated by observing the influence of
pH levels, the presence of competing ions zeolite dosage and thermal modification of the natural
zeolite. The adsorption studies showed rapid uptake for the first 40 min, corresponding to about
80% total removal. Approximately 80%, 95%, 90% and 99% of Fe3+, Mn2+, Zn2+ and Cu2

___________________________________________________________________________________________________________
respectively, were adsorbed from single component solutions. Only Fe3+ adsorption of was
unaffected by the presence of competing ions, which was explained with the precipitation
mechanism of Fe3+ removal. The adsorption of the other 3 cations from multi-component solutions
of concentration 40 mg l−1 decreased with 30-40%. Promising results were obtained from the
preliminary tests using real AMD, as well. The process of continuous elimination of Pb2+, Cu2+,
Zn2+ from AMD wastewater by natural stilbite, heulandite, and clinoptilolite was investigated by
Calvo et al. [190]. The general order of effective CEC obtained from breakthrough curves of these
zeolitic tuffs, was the following: clinoptilolite > heulandite > stilbite. The raw clinoptilolite sample
showed very good exchange capacity for Pb2+ (40.4 mg g-1), and also a high exchange capacity for
Cu2+ (19.2 mg g-1) and Zn2+ (7.8 mg g-1) when conditioned with 2M NaCl. The sorption of Pb2+ on
the Na-clinoptilolite reached 73.4 mg g-1, witch value is comparable only with that obtained for the
unmodified Croatian clinoptilolite [181].
Table 10. Cation exchange selectivity of heavy metal ions on natural and synthetic zeolites
Zeolite Zeolite origin Selectivity order Reference
Clinoptilolite Greece Pb2+ > Zn2+ ≥ Cu2+ [202]
Clinoptilolite Greece Pb2+ > Cr3+ > Fe3+ ≥ Cu2+ [203]
Clinoptilolite Greece Cu2+ > Cr3+ > Zn2+ > Cd2+ > Ni2+ [182]
Clinoptilolite Turkey Co2+ > Cu2+ > Zn2+ > Mn2+ [188]
Clinoptilolite Turkey Fe3+ > Zn2+ > Cu2+ > Mn2+ [13]
Clinoptilolite Turkey Pb2+ > Zn2+ > Cu2+ > Ni2+ [204]
Clinoptilolite Croatia Pb2+ > Cd2+ [181]
Clinoptilolite Italy Pb2+ > Cu2+ > Cd2+ ≈ Zn2+ [205]
Clinoptilolite Italy Pb2+ > Cd2+ > Zn2+ ≈ Cu2+ [206]
Clinoptilolite Commercial Cs+ > Cu2+ > Sr2+ > Zn2+ > Co2+ [207]
Natural chabazite Commercial Cs+ > Sr2+ > Cu2+ > Zn2+ ≈ Co2+ [207]
Natural chabazite Italy Pb2+ > Cd2+ > Zn2+ > Co2+ [206]
Natural chabazite Italy Pb2+ > Cd2+ > Cu2+ > Zn2+ > Co2+ [206]
Natural scolecite Brazil Ni 2+ > Cr3+ > Cd2+ > Mn2+ [179]
Natural scolecite Brazil Cu2+ > Zn2+ > Pb2+ > Ni2+ > Co2+ > Cd2+ [180]
Natural mordenite New Zealand Pb2+ > Cu2+ > Zn2+ ≈ Cd2+ [183]
NaP1 From CFA Cr3+ > Cu2+ > Zn2+ > Cd2+ > Ni2+ [182]
NaP1 From CFA Ba2+ > Cu2+ > Cd2+ ≈ Zn2+ > Co2+ >Ni2+ [78]
NaP1 From CFA Pb2+ > Cu2+ > Cd2+ > Zn2+ [184]
NaA Commercial Cu2+ > Cr3+ >Zn2+ > Co2+ >Ni2+ [80]
NaA From CFA Cu2+ > Cr3+ >Zn2+ > Co2+ >Ni2+ [80]
NaA From kaolin Pb2+ > Cd2+ > Cu2+ > Zn2+ > Ni2+ [54]
NaX From kaolin Pb2+ > Cd2+ > Cu2+ > Zn2+ > Ni2 [54]
NaY Commercial Pb2+ > Cd2+ > Cu2+ > Ni2+ [208]
NaY From CFA Pb2+ > Cu2+ > Cd2+ > Ni2+ [187]
Faujasite From CFA Fe3+ > As2+ > Pb2+ > Zn2+ > Cu2+ > Ni2+ > Cr3+ [209]
Cancrinite From CFA Pb2+ > Cu2+ > Ni2+ > Co2+ > Zn2+ [6]
Coruh [212] investigated Zn2+ removal from aqueous solutions by raw and NaCl conditioned (10 ml
2M NaCl solution per gram zeolite) clinoptilolite. The pre-treatment was performed by three
different methods: at room temperature, at 70°C and with a preliminary treatment with 0.1 M HCl
to wash out carbonates and clays. The results prove that the conditioning improved both the
exchange capacity and the removal efficiency [212,181]. It was found that the increase of
temperature from 10 to 90°C resulted in a rise of removal efficiency from 90.7 to 99.7%. The
maximum sorption capacity, calculated from the Langmuir equation for the sample conditioned at
increased temperature was 22.2 mg g-1, while for the raw zeolites it was 17.9 mg g-1. The change of
pH from 4 to 8 had a negligible effect on the performance of the conditioned sample, while the
effect for the raw one was significant.

___________________________________________________________________________________________________________
Panayotova examined the kinetics and thermodynamics of Ni2+[213], Cu2+ [189] and Cd2+ [214]
removal from wastewater by use of raw and modified Bulgarian clinoptilolite [189]. It was found
that the modification of zeolite with NaOH, NaCl, and CH3COONa increased significantly metal
ions uptake, whereas the HCl treatment has negative effect on the process. The uptake equilibriums
of Ni2+ and Cu2+were best described by the Langmuir adsorption isotherm, while the uptake of Cd2+
fitted better to Freundlich isotherm. The uptake of Cu2+ by zeolite from neutral wastewater has
proved to be as effective as precipitation of copper hydroxide. The simultaneous presence of Ca2+
and Mg2+ did not significantly influence the uptake of Cu2+, however the uptake of Cd2+ was
considerably decreased in the presence these ions. Desorption experiments showed that Cu2+ ions
were strongly immobilized by zeolites modified with NaOH, NaCl and CH3COONa, while the
immobilization by natural sample was weaker. Loaded natural and modified cliniptilolites were
easily regenerated by 2M NaCl solution [189]. Panayotova and Velikov [215] further studied the
kinetics of the uptake of Cd, Pb, Cu, Ni and Zn from single ion solutions and from their mixture. It
was found that Pb2+ were strongly immobilised by the zeolite, in single ion and mixed solutions, as
well as in soft and in hard water. It was also reported that pre-treatment of zeolite with NaCl
increased the rate of heavy metal ions’ uptake and the distribution coefficients, but does not change
zeolite selectivity sequence for the ions in multi-component solutions [216].
Bosso and Enzweiler [180] investigated the potential of natural Brazilian scolecite as a new material
for heavy metal removal (Pb2+, Cu2+, Zn2+, Ni2+, Co2+ and Cd2+) from aqueous. Samples were pre-
treated with 2M NaCl solution. The experiments were carried out under constant agitation for 24 h,
at ambient temperature. The quantity of cations retained per mass of scolecite was evaluated as a
function of initial concentration (5–60 mg l-1), pH (4–6), liquid/solid ratio and particle size. The
results indicated a great affinity of scolecite for Cu2+ with a retention value of 0.13 meq g-1 at pH=
6, initial Cu2+ concentration mg l-1 and liquid/solid ratio of 200. In the same conditions, the
maximum retention measured for the other ions was 0.064 meq g-1 (Zn2+), 0.056 meq g-1 (Pb2+),
0.031 meq g-1 (Ni2+), 0.00.8 meq g-1 (Co2+) and 0.0032 meq g-1 (Cd2+). The selectivity sequence
calculated in milliequivalents per gram of zeolite is therefore Cu>>Zn>Pb>Ni>>Co>Cd. The
maximum uptake was for all the ions studied was obtained at pH=6. Dal Bosco et al. [179] further
studied the cation exchange capacity of the same material for the sorption of Cr3+, Ni2+, Cd2+, and
Mn2+ in single-metal synthetic solutions. The results demonstrated that removal of metals from
specific metal solutions is best described by a Freundlich isotherm. The sorption capacity of
scolecite for metals at 298 K followed the series Cr>Mn>Cd>Ni. This order could be related to
such properties as the radius of hydration and the hydration enthalpy of the cations. There was a
significant enhancement in the sorption of metals at high temperature values for the metals tested,
except for Ni. Thermodynamic data indicated the spontaneity of the endothermic cation exchange
process and suggested the following selectivity series at 298 K: Ni>Cr>Cd>Mn.
The adsorption of Mn2+ onto natural and activated Chilean zeolites was investigated by Taffarel and
Rubio [197]. Zeolite activation was carried out by treatment of 5g zeolite with 1l 1M solutions of
NaCl, NH4Cl, Na2CO3 or NaOH for 24 h at room temperature. It was found that zeolite
modification by treating with all the above listed chemicals increased the Mn2+ uptake capacity
from 0.26 meq g-1 (raw zeolite) to 0.67-0.77 meq g-1. Solution alkalinity influenced significantly the
Mn2+ adsorption rate and capacity and the best results were obtained at pH=6–6.8. The adsorption
onto the activated zeolite followed the pseudo-second-order kinetic model. Activation with NaOH
resulted in the highest reaction rate. The same authors [198] further investigated the removal of
Mn2+ from aqueous solution by Chilean natural zeolite coated with MnO2. The results showed that
the coated zeolite has almost 2.5 higher Mn2+ adsorption capacity than the Na-form and that it is
able to remove up to 99% of Mn2+ from solution with initial concentration of 3.64 meq.l-1. Kinetic

___________________________________________________________________________________________________________
and thermodynamic data obtained, indicated that Mn2+ capturing onto zeolite is the result of a
combination of several interfacial reactions namely, ion exchange, chemisorption, and adsorption.
The maximum Mn2+ adsorption capacity was 1.12 meq g-1.
Rajic et al. tested NaCl-modified Serbian clinoptilolite as adsorbent for Ni2+ [199] and Mn2+ [196]
ions from aqueous solutions. It was found that Ni2+ sorption at 298 K varies from 1.9 mg g-1 to 3.8
mg g-1 at initial Ni2+ concentrations in the range of 100-600 mg l -1. At 338 K roughly three-fold
increased sorption capacities - up to 6 mg g-1 (for 100 mg l -1 Ni2+) and 10.6 mg g-1 (for 600 mg l -1
Ni2+) were observed. For Mn2+ the increase of temperature also led to significant increase in
sorption rate and capacity. The sorption isotherm for both elements on clinoptilolite was best
represented by the Sips model, and the kinetics followed the pseudo-second-order model. It was
found that the sorption involved film diffusion, intra-particle diffusion, and chemical cation
exchange processes [199]. The sorption of both metals was found to be an endothermic and
spontaneous in the temperature range studied. Maximum Mn2+ adsorption was achieved at pH=6.
Dimirkou and Doula [195,217,218] tested natural and Fe(III)-overexchanged clinoptilolite in Zn2+
and Mn2+ removal from drinking water samples. The Fe-overexchanged clinoptilolite was prepared
by mixing 20 g of clinoptilolite, 100 ml 1M Fe(NO3)3x9H2O solution, and 180 ml of 5M KOH
solution, suspension delution to 2l and subsequent thermal treatment 70ºC for 60 h. Batch
adsorption experiments were carried out to determine the effectiveness both adsorbents in the
removal of Zn and Mn from drinking water. The maximum adsorbed Mn amount for raw
clinoptilolite was 7.69 mg g-1, whereas that for the Fe-clinoptilolite system it was much higher -
27.1 mg g-1. The respective values for the adsorption of Zn were 71.3 mg g-1 and 94.8 mg g-1. The
maximum adsorption efficiency of the raw zeolite is observed at initial metal concentration of 4-5
ppm for both cations, while the Fe-modified samples showed > 90% removal efficiency in a broad
range of concentrations – from 4 to 100 ppm for Mn and from 5 to 200 ppm for Zn. The tests for
simultaneous removal of Cu, Mn and Zn from drinking water showed that both substrates reduced
Mn adsorption in the presence of Cu and Zn.
Katsou et al. [219] recently investigated the potential regeneration of natural zeolite, which had
been contaminated with Pb, and Zn contained in aqueous solutions, treated secondary effluent and
primary treated wastewater. The adsorption experiments were conducted in batch reactors at initial
heavy metals concentration of 320 mg l-1 and zeolite dosage 10 g l-1. Several desorbing solutions
were examined for the removal of Pb and Zn and KCl (at 3M and 1M concentration, respectively)
was found to be the most effective exhibiting very high desorption efficiencies (>98.5%) for both
metals. Successive regeneration cycles resulted in the reduction of desorption efficiency by more
than 50% after 9 and 4 cycles for lead and zinc, respectively. Kinetics examination showed that
desorption was slower than adsorption. Adsorption was characterized by a three-stage diffusion
process, while desorption followed a two-stage diffusion process.
Although the above-reviewed investigations demonstrated that under appropriate conditions natural
zeolites, could be very effective in the uptake of some heavy metals from (waste)waters, several
comparative studies [182,183] clearly indicated that generally synthetic zeolites have much better
removal performance than natural ones. Alvarez-Ayuso et al. [182] studied the sorption behaviour
of natural zeolite (predominantly clinoptilolite) and zeolite NaP1, obtained from CFA, with respect
to Cr3+, Ni2+, Zn2+, Cu2+ and Cd2+ in order to consider their applicability for purification of metal
electroplating wastewaters. The batch method was employed using metal concentrations in solution
ranged from 10 to 200 mg l-1 and zeolite ratios dose from 2.5 to 10 g l-1. It was found that synthetic
zeolite exhibited about 10 times greater sorption capacities than natural zeolite, and that while the
metal sorption on natural zeolite increased with time, the sorption on NaP1 zeolite appeared to be
practically instantaneous. The metal amounts, sorbed by NaP1 in the first half an hour,

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corresponded to 100% of equilibrium amounts. Metal sorption affinity was found to follow the
sequence: Cr>Cu>Zn>Cd>Ni for NaP1 and Cu>Cr>Zn>Cd>Ni for the natural zeolite. The main
factors responsible for the retention sequences were recognized to be CEC of zeolites and the
strength of the hydration shells of cations. Zeolite NaP1 showed the same high sorption capacity
values when used in the purification of real metal electroplating wastewaters. Pitcher et al. [183]
conducted batch experiments with natural mordenite and synthetic NaP zeolite to test their ability to
remove dissolved heavy metals (Zn, Cu, Pb, Cd) from simulated and spiked motorway stormwater.
Synthetic NaP zeolite showed almost complete removal (>91%) of the studied heavy metals from
both solutions and did not appear to be affected by the calcium present in the motorway stormwater,
while mordenite was less effective at reducing the levels of heavy metals (42–89% in synthetic
solution, 6-44% in motorway stormwater).
Purna Chandra Rao et al. [185] compared the sorption of Cd2+ and Zn2+ by bentonite and
commercial zeolites 13X, 4A in a batch tests at different equilibrium time, pH (2-8) and sorbent
dose (5-30 g l-1). They reported the metals sorption by zeolite 4A was higher than that by zeolite
13X and bentonite. The sorption peak values for all the sorbents were obtained at pH 6.0 and 6.5 for
Cd2+ and Zn2+respectively and the sorption followed the Freundlich model. More than 70% sorption
occurred within 20 min and equilibrium was attained at around 90 min for the three sorbents. The
experimental data revealed that with an initial concentration of 25 ppm, the removal of Cd at pH 6
was 0.088 mmol/g with zeolite 4A, 0.086 mmol/g with zeolite 13X and 0.084 mmol/g with
bentonite. With an initial concentration of 25 ppm, the removal of Zn at pH 6.5 was 0.148 mmol/g
with zeolite 4A, 0.145 mmol/g with zeolite 13X and 0.141 mmol/g with bentonite. The maximum
percentage desorption was obtained using 10% NaCl solution and was 76% for Cd and 80% for Zn.
The presence of competitive cations (Ca2+, Mg2+ and Fe2+) in the solution reduced the efficiency of
Cd2+ and Zn2+ uptake wit about 10% for all studied sorbents.
Covarrubias et al. [53] investigated Cr(III) exchange on zeolites obtained by HT synthesis from
kaolin (hydroxisodalie, and a blend of zeolites X and A) and from natural mordenite (a blend of
zeolites Y and P2, and pure zeolite P). Batch experiments were carried at initial Cr3+ concentration
of 500 mg l-1, adsorbent dosage of 5 g l-1, room temperature, continuous agitation and 24 h
treatment time. It was found out that the Cr3+ exchange of synthesis products was determined by
zeolite type and the fraction of amorphous phase in the solid product. The highest Cr3+ exchange
capacity was obtained for the products containing FAU-type zeolites (X and Y), which could be
explained with the larger pore opening, which facilitates the diffusion of large hydrated chromium
ions into the internal cation exchange sites. The synthesized zeolites products presented higher
Cr(III) exchange capacity (4.1 and 4.8 meq g-1 for zeolites X and Y respectively) than commercial
zeolites types 13X, 4A and NaY (2.1, 3.1, and 3.5 meq g-1 ).
In addition to the type of zeolite, its cation form was found to play an importat role in the heavy
metals exchange process. Keane [220] investigated the removal of Cu2+ and Ni2+ from aqueous
solution using Li-, Na-, K-, Rb-, and Cs-exchanged Y zeolites under competitive and non-
competitive conditions. The results indicated that the extent of transition metal removal is
dependent strongly on the nature of the out-going alkali metal cation with the overall preference of
the zeolite for exchange with both metals decreasing in the order LiY>NaY>KY>RbY>CsY,
corresponding to the order of increase of the size of the bare alkali metal cation. As this size
increases, the charge density decreases, the solid phase ions are present in a less hydrated state,
interacting more strongly with the zeolite lattice and, consequently, are more resistant to exchange
with external cations. The heavy metal removal was found to be is independent of the nature of the
anion, coming from heavy metal salt used [208], however it is dependent of the heavy metal
hydrated ion diameter [184,221]. Jamil et al. [54] performed series of experiments in order to

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determine the optimum conditions for removal of Cd2+, Cu2+, Pb2+, Zn2+ and Ni2+ using zeolites A
and X prepared from kaolin. Metal removal was investigated using synthetic solutions at initial
concentrations of 20 mg l-1 of individual metals and mixture of metals with concentration of 20 mg
l-1 for each, at 25°C and pH = 7.5. It was found that the optimum contact time for removal of Cd,
Cu, Pb and Zn was 30 min and for Ni was 60 min for both zeolite types. At the optimum time the
efficiencies of zeolite A and X were almost equal and above 99% for all the cations studied. In the
second part of the investigation [221] authors reported that according to the equilibrium studies, the
selectivity sequence of both zeolites can be given as Pb>Cd>Cu>Zn>Ni, which is in conformity
with the orders obtained for commercial and CFA-derived zeolite A [80], and zeolite Y [208,220],
but does not match those reported for zeolite NaP1 [78,182,184], which was found to be less
selective to the Cd2+ ion.
The intensive research on the applicability of the zeolitized CFA as ion exchangers for water
decontamination has shown that CFA-derived zeolites are also very effective in the removal heavy
metals from industrial wastewaters and that, although initial CFA usually contain heavy metals, the
synthesized zeolites are environmentally safe, due to the immobilization of heavy metals by
sorption in the zeolite framework or by precipitation of insoluble hydroxides [78].
Hui et al. [80] performed a comparative study on the uptake Cu2+, Cr3+, Zn2+, Co2+ and Ni2+ from
mixed metal ions solution by commercial zeolite 4A (Valfor 100) and CFA-based pure zeolite 4A.
Batch method was employed to study the influential parameters such as initial metal ions
concentration, adsorbent dose, contact time and initial pH of the solution on the adsorption process.
The experimental data were well fitted by the pseudo-second-order kinetics model (for Co2+, Cr3+,
Cu2+ and Zn2+ ions) and the pseudo-first-order kinetics model (for Ni2+ ions). The equilibrium data
for both NaA zeolites were well fitted by the Langmuir model and showed the same affinity order:
Cu>Cr>Zn>Co>Ni. It was found out that the increase of the initial concentration from 50 to 300 mg
g-1 of the mixed metal ions led to significant decrease in the sorption of Zn2+, Co2+ and Ni2+ ions,
which could be attributed to the higher selectivity of the zeolite to Cu2+ and Cr3+ ions. The
adsorption process was found to be pH and concentration dependent. It was demonstrated that the
sorption rate and capacity of metal ions could be significantly improved by increasing pH value.
Commercial grade zeolite 4A and the CFA-4A showed very similar heavy metals uptake behaviour,
despite its lower crystallinity and specific surface. For CFA-prepared zeolite, the equilibrium
sorption capacities obtained were 50.45 mg g−1 for Cu2+, 41.61 mg g−1 for Cr3+, 30.80 mg g−1 for
Zn2+, 13.72 mg g−1 for Co2+, and 8.96 mg g−1for Ni2+. For commercial zeolite 4A, they were 53.45
mg g−1 (Cu2+), 45.29 mg g−1 (Cr3+), 31.58 mg g−1 (Zn2+), 11.52 mg g−1 (Co2+), and 7.9 mg g−1 (Ni2+).
Wang et al. [81] synthesized two pure-form zeolites (A and X) from CFA by a two-stage method
and tested their potential as adsorbents for Zn2+ and Cu2+ uptake from wastewater. The results from
comparative studies showed that zeolite A was more effective in removing both ions, Cu2+ and
Zn2+, compared to zeolite X. The influential parameters were studied for the removal performance
of metal ions on three adsorbents: CFA-derived pure zeolite A, hydroxisodalite, obtained from raw
CFA, and commercial zeolite A. All the adsorbents showed effective adsorption with higher
capacity for Cu2+ than for Zn2+. The greatest removal efficiency, obtained for the three zeolites were
respectively 99.7%, 89.6% and 99.1% for Cu2+, and 93.2%, 81.5%, and 96.1% for Zn2+.
Jha et al. [187] prepared composite materials of activated carbon and zeolite X have by fusion of
CFA with NaOH at 750ºC in N2 followed by HT treatment. The samples were subjected to Ni2+,
Cu2+, Cd2+ and Pb2+ uptake experiments by a batch method at room temperature, solid/solution ratio
0.1 g 50 ml-1, initial metal ion concentrations 20-500 ppm of Ni2+, Cu2+, Cd2+ and 100–2000 ppm of
Pb2+, and treatment time of 24 h. The kinetic experiments were performed at 500 ppm for Ni2+,
Cu2+, Cd2+ and 1000 ppm for Pb2+ for times of 0.5–6 h. The relative selectivity of the sorbent for the

___________________________________________________________________________________________________________
various ions was found to be Pb>Cu>Cd>Ni, with equilibrium uptake capacities of 2.65, 1.72, 1.44
and 1.20 mmol.g-1, respectively. The sorption isotherm fitted to the Langmuir isotherm. The overall
sorption is pseudo-second order with an initial rapid and quantitatively predominant sorption
followed by a second slower and quantitatively insignificant sorption. Although the uptake amounts
of metal ions in multi-component systems were decreased by competitive reactions, the total uptake
was increased. The adsorption isotherms [222] of the obtained NaX based on the characteristics
required to remove Pb2+, Cu2+, Cd2+ and Ni2+ were examined in multi-metal systems. Thus obtained
experimental data suggested that the Langmuir and Freundlich models are more accurate compared
to the Dubinin–Kaganer–Radushkevich model. Further, in going from a single- to multi-metal
system, the degree of fitting for the Freundlich model compared with the Langmuir model was
favored due to its basic assumption of a heterogeneity factor.
Lee et al. [184] investigated Pb2+ sorption from aqueous solutions using five different zeolites
(NaP1, faujasite, hydroxy sodalite, analcime, and cancrinite) obtained by HT treatment of CFA
under different conditions. It was found that all the zeolites synthesized have greater adsorption
capabilities for heavy metals than the original CFA and natural zeolites. NaPl exhibited the highest
adsorption capacity with a maximum value of about 1.29 mmol Pb g-1 and had a strong affinity for
Pb 2+ ion. They also studied the sorption of Cu2+, Cd2+ and Zn2+ by NaP1 and found that the metal
ion selectivity of NaP1 decreases in the order: Pb>Cu>Cd>Zn, which is consistent with the
decreasing order of the radius of hydrated metal ion. The experiments of Woolard et al. [201] also
proved that CFA-derived zeolite NaP1 is more effective at removing Pb2+ than hydroxysodalite.
The maximum Pb2+ sorption capacities calculated, using Langmuir’s model were 0.985 mmol.g-1 for
NaP1 and 0.628 mmol.g-1 for hydroxisodalite, while for the untreated CFA it was 0.217 mmol.g-1.
Zeolite NaP1 demonstrated high removal efficiency (>95%) in abroad range of pH (3-8.5), while
for hydrixisodalite the maximum efficiency was reached at pH above 5.5, and could be attributed to
the precipitation of PbO. Steenbruggen and Gollman [78] tested the ability of zeolitized CFA
containing 45% zeolite NaP1 to remove heavy metals and ammonia from aqueous solutions in batch
and column tests. Batch sorption experiments indicated that the selectivity series for NaP1 is
Ba>Cu>Cd≈Zn>Co>Ni. Column experiments results indicated that, besides cation exchange
reactions, precipitation of hydroxides also played a role in the immobilization of heavy metals.
Column leaching tests showed that compared to the original CFA, the zeolitized CFA is of a better
environmental quality.
Rios et al. [209] compared the performance of CFA, natural clinker and synthetic zeolites in heavy
metals removal from AMD generated at the Parys Mountain Cu–Pb–Zn deposit, North Wales.
Zeolites were prepared by two methods: by classic HT synthesis using natural clinker (producing
Na-phillipsite), and by alkaline fusion prior to HT treatment using both CFA and natural clinker
(producing faujasite type zeolites). Faujasite showed higher heavy metal removal efficiency than
Na-phillipsite. The results indicated that pH play an important role in the process. The higher
adsorbent dose promoted an increase in pH, which led to a reduction in metal concentration. This
result is inconsistent with the results reported by Endres et al. [192], whose investigations on the
removal of Fe2+, Cu2+, Pb2+, Zn2+ from wastewaters using CFA-derived chabazites clearly indicated
that heavy metals removal is enhanced at the lower pH. Qiu and Zheng [6] studied the removal of
Pb2+, Cu2+, Ni2+, Co2+, and Zn2+ from water by a cancrinite-type zeolite synthesized from CFA.
Adsorption equilibriums of the metals on the zeolite were studied in synthetic solutions and were
well represented by Langmuir isotherms. The increase of pH levels during the adsorption process
suggests that the uptake of heavy metals on ZFA inolves ion exchange. It was found that the
maximum exchange level followed the order: Pb>Cu>Ni>Co >Zn. Comparison with previous
studies shows that the sorption capacity of CFA-derived cancrinite is higher than the commonly

___________________________________________________________________________________________________________
used natural zeolites; and it is also comparable to (or higher than) several synthetic zeolites (NaP1,
NaY, NaA), and ion exchange resins (IRN 77, SKN 1, Ca-alginate-resin). Koukouzas et al. [82]
tested four zeolitic materials (containing zeolites NaA, KA, erionite, ZSM-18 and Linde L) obtained
form Polish bituminous and South African CFA for removal of Cd2+, Cu2+, Pb2+, Zn2+, Ni2+ and
Cr3+ from aqueous solutions. The results showed that at initial cation concentration of 100 mg l-1
and adsorbent dose of 200 mg l-1, all the materials synthesized were able to remove completely
(99.8-100%) the studied heavy metals in two hours of contact time.
Somerset et al. [194] studied the removal of Hg2+ and Pb2+ ions from wastewater by zeolites
obtained from CFA and from the filtrate of co-disposal of CFA and AMD. The results showed that
the second material was more effective. At 20 g l-1 adsorbent dosage this zeolite material reduced
Pb2+ concentration from 3.23 to 0.17 µg kg-1 and Hg2+ from 0.47 to 0.17 µg kg-1.
Pena et al. [186] examined the retention of Cs+, Cd2+, Pb2+ and Cr3+ by zeolitic materials formed as
a result of the HT treatment of the bottom ash from fluidized-bed incineration of MSW. The amount
of Cs+ retained was considerably lower than those for Cd2+, Pb2+, and Cr3+, independently of the
type of compounds, formed by the different bottom ash treatments. The higher percentage of Cs+
retained (31%), occurred after treatment of the bottom ash in NaOH at 200°C, where zeolite NaA
was the major compound, together with aluminum tobermorite. In the case of Cd2+, Pb2+ and Cr3+,
the removal efficincy was about 99% under all of the conditions studied.
Shawabkeh [93] tested zeolite NaP1, obtained from OSA, as ion exchanger for Pb2+ and Cd2+
cations from aqueous solutions. The adsorption capacities were estimated to be 70.58 mg g-1 Pb2+
and 95.6 mg g-1 for Cd2+ when the initial concentration for both ions was 100 mg l-1. For Cd the best
fit was obtained with the Sips model while, for Pb the Sips models fits the experimental data
adequately. Based on the results obtained, it was concluded that the treated OSA possessed strong
potentials for zeolite production used in wastewater treatment.
On the base of the reviewed investigations, it could be summarized, that heavy metals uptake
capacity and selectivity depend mainly upon the zeolite type, its cation form, and the hydrated
radius of the heavy metal ion. Good performance in the treatment of waters contaminated with
heavy metals was demonstrated by Brazilian scolecite and some modified clinoptilotites. However,
yet again, synthetic zeolites (types P1, A, X, and Y), including zeolites and zeolitic materials,
obtained from wastes such as CFA and MSWIA have higher heavy metal uptake capacity than
naturally occurring zeolites. For practical purposes the sodium form of both natural and synthetic
zeolites is the most appropriate for heavy metals removal. Most of zeolites have high sorption
capacity and selectivity for Pb2+, Cd2+, Cu2+, Zn2+, and Cr3+, whereas their affinity to sorb Mn2+,
Ni2+, Co2+, especially from multi-component solutions, is smaller. Several mechanisms, including
ion exchange, chemisorption, adsorption and precipitation, could be involved in the heavy metals
uptake from aqueous solutions by zeolites, but even so, generally, the sorption of heavy metals on
zeolites is a feasible, spontaneous and endothermic in nature process, which is enhanced by
temperature increase. The sorption of heavy metals onto zeolite surface is a diffusion-controlled
process, therefore the decrease in particle size of zeolites and intensive stirring have positive affect
the process positively. The optimal zeolite dosage varies from several grams up to several dozens
grams per liter wastewater and depends upon the concentration of heavy metal in the influent, the
desired degree of its reduction, and the presence of competitive ions. Most of batch studies reported
that acceptable degree of heavy metals uptake from wastewaters is achieved in less than one hour,
while the equilibrium is reached within a few hours. The complete removal of heavy metals requires
longer treatment duration and higher zeolite dosage. Maximum metal uptake is usually achieved at
initial pH of the suspension in the neutral range (pH=6-8). In batch condition, longer time of contact

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between zeolite and heavy metal solution leads to an increase in the alkalinity, which in turn
facilitates heavy metal removal via precipitation of insoluble metal hydroxides onto zeolite surface.
Heavy metals-loaded zeolite could be partially regenerated and recycled.
3.2.4. Radioactive species removal
Various processes used in the nuclear fuel cycle and in the application of radionuclides in industry,
medicine, and research generate low or intermediate level liquid wastes, containing radioactive
isotopes (e.g. 137Cs, 90Sr, 60Co, 45Ca, 51Cr, 111mCd, 110mAg). Such effluents usually require treatment
to remove radioactive contaminants or to reduce them to levels, which allow safe discharge. One of
the first publications on the utilization of zeolites for the sorption of radioactive species was
probably the patent of Ames [14] who proposed a method for removal of cesium from aqueous
solutions by sorption with clinoptilolite. Table 11 summarizes some of the more recently reported
results for radioactive metals uptake by zeolites.
Table 11. Radioactive elements adsorption on some natural and synthetic zeolites
Metal Zeolite Metal Metal Uptake
Metal Zeolite Refe-
Zeolite conc. dosage, sorption, removal, distr. coef.
ion origin rence*
mg l-1 g l-1 mg g-1 % ml g-1
U6+ HEU - type Greece 20000 10 8.7 0.43 0.4 [223]
U6+ HEU - type Greece 1000 10 4.7 4.7 5.0 [223]
U6+ HEU - type Greece 250 10 3.5 13.9 16.1 [223]
U6+ HEU - type Greece 100 10 1.6 16.0 19.1 [223]
U6+ HEU - type Greece 50 10 1.0 19.6 24.5 [223]
Greece, Na- 10 [223]
Th4+ HEU - type 20000 11.0 0.55 0.6
exchanged
Greece, Na- 10 [223]
Th4+ HEU - type 1000 12.4 12.4 14.2
exchanged
Greece, Na-
Th4+ HEU - type 250 10 12.1 48.2 93.4 [223]
exchanged
Greece, Na-
Th4+ HEU - type 100 10 6.6 65.6 192.9 [223]
exchanged
Greece, Na-
Th4+ HEU - type 50 10 1.6 31.4 46.2 [223]
exchanged
I+ 74-152 [224]
Clinoptilolite Iran 635 40
x103
I+ Mesolite Iran 635 40 165 x103 [224]
I+ Analsite Iran 635 40 119 x103 [224]
199-230 [224]
Mo2+ Clinoptilolite Iran 480 40
x103
Mo2+ Mesolite Iran 480 40 313 x103 [224]
Mo2+ Analsite Iran 480 40 206 x103 [224]
Mo2+ NaA ZM Synthetic 96 99.8 [225]
3+
La Clinoptilolite Iran 695 40 TA** [224]
La3+ Mesolite Iran 695 40 506 x103 [224]
La3+ Analsite Iran 695 40 TA [224]
Nd3+ Clinoptilolite Iran 721 40 400 x103-TA [224]
Nd3+ Mesolite Iran 721 40 545 x103 [224]
Nd3+ Analsite Iran 721 40 TA [224]
926-5470
Sm3+ Clinoptilolite Iran 752 40 [224]
x103
3+
Sm Mesolite Iran 752 40 1760x103 [224]
Sm3+ Analsite Iran 752 40 3070 x103 [224]

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Cs+ NaA ZM Synthetic 133 99.4 [225]

Cs+ Clinoptilolite USA 1329 220.6 [14]
Blend CFA-derived
Cs+ 133 1 37.8 76 390 [83]
NaA-X Si and Al
Blend NaA + MSWIA-
Cs+ 26 2 31 222 [186]
tobermorite derived
+
Cs Clinoptilolite Turkey Total 10 186.1-252.5 [16]
Co2+ Clinoptilolite Turkey activity 10 26.5-32.4 3.75-4.45 [16]
Ag+ Clinoptilolite Turkey 8.45x105 10 107.8-151.0 x103 [16]
Sr2+ Clinoptilolite Turkey Bq.l-1 10 74.5-96.4 [16]
Sr2+ NaA ZM Synthetic 88 99.8 [225]
2+
Co Erionite Mexico 1.5 10 32.4 [226]
Co2+ NaA Synthetic 1.5 10 58.9 [226]
Co2+ NaX Synthetic 1.5 10 73.7 [226]
Co2+ NaY Synthetic 1.5 10 38.3 [226]
Co2+ ZSM-5 Synthetic 1.5 10 26.5 [226]
Cd2+ NaA Synthetic 2.8 10 157.4 [226]
Cd2+ NaX Synthetic 2.8 10 207.9 [226]
Cd2+ NaY Synthetic 2.8 10 140.5 [226]
Cd2+ ZSM-5 Synthetic 2.8 10 84.3 [226]
* Some values are recalculated and/or rounded; **TA- total adsorption.
Misaelides et al. [223] studied the uptake of thorium and uranium from their aqueous solutions by
untreated and NaCl-pre-treated HEU type zeolite-bearing rock from Greece using batch method.
The preliminary experiments had indicated NaCl pretreatment of the materials improved the
thorium but not the uranium uptake. Therefore, the raw zeolite was used for the U and NaCl-
pretreated form was used for Th uptake experiments. Eight solutions of different concentrations
ranging between 20 000 mg l-1 and 50 mg l-1 were used. The absolute Th uptake was between 1.57
and 12.41 mg g-1, while for U it was between 0.98 and 8.70 mg g-1. Kd values obtained showed that
the relative Th4+ and U6+ uptake was higher for initial concentrations below 250 mg l-1. The zeolitic
materials showed high resistance to the initial low pH (2.16 for Th and 2.78 for U) of the solutions,
which was significantly increased during the experiments, due to the simultaneous adsorption of H+.
The authors discussed in details the aqueous chemistry of the elements and concluded that thorium
and uranium uptake is quite a complicated phenomenon, because the various metal species
(depending on the concentration and the pH of the solutions) are bound through different uptake
processes, such as ion exchange, adsorption and surface precipitation. Nevertheless, the ability of
the materials to remove U and Th is mainly due to the microporous ingredients (zeolites, clay
minerals and micas).
Nilchi and collaborators [224] studied natural Iranian zeolites from five different deposits in Iran as
ion exchangers for radioactive waste management. Kd measurements were used to investigate the
uptake of 131I, 99Mo, 153Sm, 140La and 147Nd onto zeolites under circumstances appropriate to the
nuclear industry. They found that all the zeolites, except mesolite from Arababad Tabas, had
extremely high absorption value towards 140La, while just some of them showed good sorption of
the other elements. For instance, clinoptolite from Mianeh and analsite from Ghalehkhargoshi
showed good absorption for 147Nd, while clinoptolite from Semnan and from Firozkoh showed high
absorption for 153Sm. Authors stated that the natural zeolites used, showed a similar pattern to those
of synthetic ion exchangers and in some cases have an extremely high selectivity towards certain
radioactive elements. Osmanlioglu [16] studied clinoptilolites from five zeolite formations in
Turkey for the removal of 137Cs, 60Co, 90Sr and 110mAg from liquid radioactive waste in a combined
process, including chemical precipitation and adsorption. Clinoptilolite were shown to have a high
selectivity for radioactive Cs+ and Ag+. All zeolites showed highest ion exchange capacities for Sr2+

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and lowest for Co2+. Gordes clinoptilolite was the most suitable natural sorbent for all radionuclides
studied. At the end of the liquid waste treatment, decontamination factor achived with 0.5 mm
clinoptilolite, at 30◦C and pH=10 was 430.
Garcia-Sosa and Solache-Ríos [226] determined CEC of synthetic zeolites A, X, Y, ZSM-5 and
natural Mexican erionite and compared the results obtained with the results for the retention of Cd2+
and Co2+ on these zeolites. It was found that the retention of Co and Cd decreases as follows:
X>A>Y>erionite>ZSM-5. This behavior is similar to that observed for the determined CEC, except
that zeolite X retains more cobalt than zeolite A, which could be due to several parameters such as
window size and selectivity. Dyer and Abou-Jamous [227] examined synthetic zeolites X and Y for
their abilities to uptake 60Co, 63Ni and 65Zn radioisotopes from aqueus solution. Distribution
coefficients (Kd) were determined, with and without competing cations, at various pH values. The
effects of sea and ground waters were checked using synthetic solutions. Elution studies on
radioisotopes-loaded zeolites considered the effect of acid and alkaline conditions, calcination and
cement encapsulation. Results showed slight differences between zeolites X and Y reflected the
higher Si/Al ratio in zeoliteY and the order of uptake Zn>Ni>Co mirrored that of increasing cation
size. The general conclusion was that both were suitable for decontamination of aqueous wastes
containing Co, Ni and Zn. Zeolite/cement composites were stable and yielded low leach rates, but
no advantage accured from pre-calcination.
El-Naggar et al. [36] synthesized zeolite NaAX blend from silica extracts obtained from CFA by
alkaline leaching and investigated the sorption potential of the synthesized zeolite for the removal
of Cs from aqueous solutions. The influence of pH (pH=2-9), contact time (up to 90 min) and
temperature (T=298-333K) was investigated. It was found that the acidic medium had an inhibitory
effect on the sorption process, due to the competition behaviour between H+ and studied ions for
sorption onto the synthesized powder. The uptake was continuously increased from 18.6% to 62.6%
with the increase in pH value. The maximum uptake of 64.1% was observed at pH range from 6.0
to 8.0. The obtained time-dependence of the Cs+ uptake showed that a higher initial rate of removal
within the first 30 min was followed by a slower subsequent removal rate till reaching equilibrium.
The metal ions fraction sorbed and the calculated corresponding Kd values increased with
increasing temperature indicating the endothermic nature of Cs+ sorption process. Both of pseudo
second-order and homogeneous particle diffusion models were found to correlate well with the
experimental sorption kinetics data. Some of the parameters obtained indicate that the sorption
process is diffusion-controlled and that the sorption reaction of the Cs+ is an associative mechanism.
The possibility of using zeolitic membranes (ZM) to remove ions from aqueous solutions by reverse
osmosis (RO) has been considered an alternative to polymeric membranes for desalination of
complex wastewaters which contain organic solvents and heavy metals or radioactive elements, or
when high temperature operation is desired [228]. Malekpour et al. [225] studied NaA ZM,
prepared by hydrothermal synthesis on a porous α-alumina support, for the desalination of
simulated radioactive wastes through pervaporation process. The influence of several operating
parameters such as synthesis time, number of zeolite layers and seeding procedure was investigated.
Results showed that membranes, which were prepared in a four-stage process, yield the best
separation. For all the ionic solutions including 0.001 M of Cs+, Sr2+ and MoO42– very high
rejection factors (>99%) were obtained. With increasing the time, the water flux was decreased, due
to the partial fouling of membranes. The lowest amount of flux was obtained for molybdate
solutions although their rejection factor was high. This fact could be explained with the bigger
kinetic radius of MoO42- compared with Cs+ and Sr2+. Authors concluded that NaA ZM could be
used for treatment of low-level radioactive wastes as well as for desalination and volume reduction
of these solutions, especially through the pervaporation process.

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Several practical examples for successful use of zeolites for radioactive species immobilization
have to be mentioned, as well. A mixture of synthetic zeolite A and natural chabazite was used to
take up 90Sr and 137Cs, respectively, from contaminated waters after the nuclear accident at Three
Mile Island (U.S.A.) and about 0.5 million curies of radiation was removed [229]. About 500 000
tons natural zeolite from the Trans-Carpathia area was used after the Chernobyl accident in for
decontamination of rivers polluted with 137Cs and 90Sr [230,231]. Clinoptilolite, currently, is used in
the Sellafield Ion Exchange Effluent Plant to remove 137Cs and 90Sr from low-level effluents
generated in a nuclear power plant before they are released to the Irish Sea in U.K. [232]. Both
clinoptilolite and chabazite have been used in the removal of radioactive 137Cs and 90Sr from high
level radioactive processing wastes at the Henford Atomic Energy Project in the USA [229].
Some of the main advantages of using zeolites for nuclear wastewater are their resistance to
degradation in the presence of ionizing radiation, their low solubility and that they can be used for
long term storage of long-lived radioisotopes after drying the radionuclide-exchanged zeolite at
200ºC, and sealing in a stainless steel containers [7]. The ‘‘saturated’’ zeolite can be also
transformed into concrete, glass, or ceramic bodies, and stored indefinitely [2].
3.2.5. Removal of inorganic anions
Nitrates, phosphates, arsenates, chromates and fluorides are among the most common anionic water
contaminants. As it has been mentioned, raw zeolites are negatively charged, and thus have no
affinity for sorption of anionic species. However, some cation-modified zeolites, having positive net
charge, are able to adsorb anions by means of electrostatic interaction. Summarized data for the
performance of some natural and modified zeolites for anionic contaminant removal from water are
presented in Table 12.
Table 12. Anionic species adsorption on some natural and synthetic zeolites
Anion Zeolite Anion Anion
Refe-
Anion Zeolite conc. dosage, sorption, removal,
rence*
mg l-1 g l-1 mg g -1
%
As (III) Natural zeolites from Mexico 0.1–4.0 0.003-0.017 [233,234]
As (III) Natural zeolite from Hungary 0.1–4.0 0.002 [233,234]
As (III) Fe-modified clinoptilolite 8-10 20 >0.95 [235]
As (III) Fe-modified clinoptilolite 0.36 0.012 99 [236]
As (V) Natural zeolites from Mexico 0.1–4.0 0.025-0.1 [233,234]
As (V) Natural zeolite from Hungary 0.1–4.0 0.006 [233,234]
As (V) Fe-modified clinoptilolite 8-10 20 >0.40 [235]
As (V) Fe-modified clinoptilolite 0.23 0.006 [236]
As (V) Iron oxide modified clinoptilolite 100 0.5-10 21-9 11-96 [237]
As (V) H-Beta 5 100 >95 [238]
As (V) NH4-ZSM-5 5 100 <5 [238]
As (V) NH4-Ferrierite 5 100 <30 [238]
As (V) H-Y (Si/Al=40) 5 100 <40 [238]
As (V) H-Y (Si/Al=6) 5 100 >99 [238]
As (V) NH4-Y (Si/Al=6) 5 100 >99 [238]
As (V) NH4-Y (Si/Al=6) 5 100 >99 [238]
As (V) H-MFI-24 10-150 20 75-70 [239]
As (V) H-MFI-90 10-150 20 79-73 [239]
As (V) NH4-Y (Si/Al = 4) 0.74 10 85 [128]
As (V) Al-modified W (Si/Al = 3.5) 0.74 10 99 [128]
As (V) Zeoite 5A 2.3 0.2-5 4.1 [130]
As (V) NaY 2.3 0.2-5 1.4 [130]
As (V) CFA-derived cancrinite 2.3 0.2-5 5.1 [130]
As (V) Al-modified CFA-derived cancrinite 2.3 0.2-5 34.5 [130]

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As (V) Ce-P, obtained from RHA 500 7.5 23.4 [129]

As (V) Ce-P, obtained from RHA 33.2 0.15-0.6 87-99 [129]
Cr(VI) CPB - modified Iranian clinoptilolite 16.7 15 0.20 [25]
Cr(VI) HDTMA-modified synthetic clinoptilolite 16.7 15 0.16 [25]
Cr(VI) HDTMA-modified ZSM-5 16.7 15 0.07 [25]
Cr(VI) CPB-modified ZSM-5 16.7 15 0.09 [25]
Cr(VI) APTES-modified Y/Maghemite composite 52-78 1 26 [240]
Cr(VI) HDTMA-modified clinoptilolite from New
2.9-4.0 250 0.42 [241]
Mexico, fraction < 0.4 mm
Cr(VI) HDTMA-modified clinoptilolite from New
2.9-4.0 250 0.08 [241]
Mexico, fraction 3.6-4.8 mm
Cr(VI) HDTMA-modified nanozeolite A 1 2 0.25 51 [242]
Cr(VI) HDTMA-modified nanozeolite A 100 5 8.6 43 [242]
Cr(VI) HDTMA-modified nanozeolite A >300 10-11 [242]
F- Unmodified natural zeolite from China 70 5-100 0.7-0.07 5-10 [243]
F- Ca-modified natural zeolite from China 70 5-100 1.8-0.7 13-94 [243]
F- Ca-modified natural zeolite from China 100 50 1.8 90 [243]
F- Fe(III)- modified stilbite 10 10 ≥90 [244]
NO3- Chinese clinoptilolite 50 0.19 [243]
NO3- HDTMA-modified Chinese clinoptilolite 50 1.48 [243]
NO3- HDTMA-modified Australian clinoptilolite 50 1.49 [243]
NO3- HDTMA-modified USA clinoptilolite 50 3.47 [243]
NO3- HDTMA-modified Croatian clinoptilolite 50 2.79 [243]
NO3- HDTMA-modified clinoptilolite 50 2-30 6.2-1.7 25-100 [246]
NO3- HDTMA-modified Clinoptilolite 100 36 >90 [247]
NO3- CPB - modified Clinoptilolite 88.6 2-24 7.1-3.0 16-82 [248]
P La- modified synthetic zeolite from natural 0.5 0.8 99.5 [249]
P NaP1 from CFA, pretreated by 0.9M H2SO4 up to10 10 >98 [165]
P NaP1 from CFA, pretreated by 0.1M H2SO4 100 10 >90 [135]
P Na-zeolite obtained from CFA 50 7.5 2.9 (9.9) [135]
P Ca-zeolite obtained from CFA 50 7.5 19.1 (15.5) [135]
P Mg-zeolite obtained from CFA 50 7.5 2.9 (7.2) [135]
P Al-zeolite obtained from CFA 50 7.5 13.7 (17.1) [135]
P Fe-zeolite obtained from CFA 50 7.5 11.8 (16.5) [135]
P Zeolite from CFA with high Ca content 1000 18.8 >98 [136]
P Zeolite from CFA with medium Ca content 1000 18.8 >98 [136]
P Zeolite from CFA with low Ca content 1000 18.8 >90 [136]
Sb(OH)6- HDTMA-modified Clinoptilolite 20 50 42 [250]
* Some values are recalculated and/or rounded. **Arsenate and arsenite anions are marked as Ar(V) and Ar(III),
respectively, since the prevailing ion form of As in the solution (i.e. AsO43- , HAsO42- or H2AsO4- for As(V)) depends on
the pH. The same is valid for phosphate and chromate ions, which are therefore marked as P and Cr(VI), respectively.
Arsenic is widely distributed throughout the Earth’s crust, most often as arsenic sulfide or as metal
arsenates and arsenides. Arsenicals are used commercially and industrially, primarily as alloying
agents in the manufacture of transistors, lasers and semiconductors. Arsenic is introduced into
drinking-water sources primarily through the dissolution of naturally occurring minerals and ores.
There are a number of regions where arsenic may be present in drinking-water sources, particularly
groundwater, at elevated concentrations [151]. Arsenic is considered to be a high-priority substance
for screening in drinking-water sources, as is a recognized carcinogen for human and other living
organisms [151]. The inorganic arsenic is more toxic than organic arsenic [239]. The inorganic
arsenate (AsO43-) and arsenite (AsO33-), referred to a As(V) and As(III), are most common in
natural waters [239]. Maximum contaminant level standard for arsenic in drinking water,
recommended by the WHO is 0.01 mg l-1. Conventional precipitation methods for arsenic removals
using iron and aluminum salts have not been successful to meet drinking and effluent standards for
As due to limitation of solubility of the resultant product [129]. As an alternative, adsorption was
found to be one of the promising methods for removal of arsenic from water [129]. A

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comprehensive review on arsenic removal from (waste)water using adsorbents, including some
zeolites [233,234,251-253] was published by Mohan and Pittman [254].
Elizalde-Gonzalez et al. [233,234] investigated arsenic sorption on natural zeolites (from Mexico
and Hungary), containing mainly clinoptilolite. The results showed that in the concentration range
of 0.1- 4 mg l-1 all studied zeolites removed more effectively AsO43- than AsO33- at equivalent As
concentrations, which is in agreement with the results obtained for natural chabasite [251]. The
sorption capacities of clinoptilolite, calculated using Langmure model, varied in the ranges 0.002-
0.017 mg g-1 for AsO33- and 0.006-0.1 mg g-1 for AsO43-. It was demonstrated that both the arsenite
and the arsenate content could be lowered from 200 to 10 g l−1 using Mexican zeolite [255]. The
Hungarian zeolite removed up to 75% of the As(V).
Li et al. [235] studied the removal of arsenic from water using Fe3+-exchanged clinoptilolite. It was
demonstrated that arsenic sorption on the Fe-exchanged zeolite could reach up to 0.1 mg g-1.
Columns packed with this zeolite were tested for arsenic removal from water collected from AMD
and Chia-Nan Plain groundwater. With an initial concentration of 147 g l-1 in the AMD water, a
complete As removal was achieved up to 40 pore volumes. However, the Fe-modified clinoptilolite
was not effective to remove As from the groundwater due to its high initial As concentration (511 g
l-1), high amounts of natural organic matter, as well as its low oxidation–reduction potential, under
which the As was in reduced As(III) form. Habuda-Stanic et al. [256] studied arsenic adsorption on
Fe3+ saturated clinoptilolite from solutions prepared from processed groundwater. Results showed
that the zeolite had arsenic sorption capacity of 0.055 mg g-1 for As(III) and 0.036 mg g-1 for As(V).
Similar values were reported by Macedo-Miranda and Olguin [257] who investigated As(V)
sorption on Mexican clinoptilolite-heulandite natural zeolite modified with iron, lanthanum, and
HDTMA. According to Langmuir isotherms obtained, La-modified zeolite possessed highest
arsenate sorption capacity of 0.075 mg g−1 at pH=3, followed by Fe-modified with 0.054 mg g−1 at
pH=6. For HDTMA-modified zeolite as low arsenic sorption capacity as 0.004 mg g−1 was obtained.
Dousova et al. [258] studied the sorption of As (V) from aqueous solution on untreated and Fe2+-
modified metakaoline, clinoptilolite, and synthetic zeolite. The results showed that arsenate sorption
capacity of Fe2+- treated sorbents was increased significantly from about 0.5 to above 20 mg g-1.
Vaclavikova et al. [237] prepared magnetic zeolite by co-precipitation of Fe(II) and Fe(III) in the
presence of NaOH and clinoptilolite. The new material combined the good sorption affinity for
oxyanions of iron oxides with the high CEC, typical, for zeolites. It was testes under batch
conditions for the removal of As(V) from model solutions and demonstrated high sorption capacity-
up to 28 mg g−1. The kinetics study showed fast initial removal in the first 60 min and slower
subsequent removal up to equilibrium, which was achieved after 7 hours.
The test of Xu et al. [252] on the adsorption of AsO43- from drinking water by an Al-loaded natural
zeolite indicated a slight pH dependency of the process in a wide range of initial pH (3–10).
Competiting arsenite, chloride, nitrate, sulfate, chromate, and acetate ions had little affect but
phosphate greatly interfered with the adsorption. The authors supposed a ligand-exchange
mechanism between AsO43- and surface OH- groups on Al-zeolite. Shevade et al. [238] investigated
the performance of 6 synthetic zeolites: ammonium forms of Y (Si/Al = 6), ZSM-5 and Ferierrite,
and hydrogen forms of Y (two samples having Si/Al = 40 and Si/Al = 6) and zeolite Beta, for the
removal of arsenate from aqueous solutionsat initial concentration of 5 ppm. It was found that
zeolites Beta and Y (Si/Al = 6), were very effective for As(V) removal. The reaction was completed
within 15 min for these zeolites. The different arsenic removal capacities obtained for different
zeolites Y indicated that the structure, including Si/Al ratio, played an important role in the arsenic
removal process. The results showed that Si/Al ratio affects aresenate uptake capacity and CEC in
similar way, i.e. high alumina zeolites had higher arsenate sorption capacity, which could be

___________________________________________________________________________________________________________
explained with the higher concentration of terminal Al-OH species, which leaded to a greater
capacity for a ligand exchange reaction [238]. At initial arsenic concentrations of 1 and 0.5 ppm the
treatment with zeolite NH4-Y (Si/Al = 6) decreased the concentration below 0.002 ppm within 15
min. Mexican CFA-derived zeolites, particularly high aluminium zeolite Y (Si/Al=4) in ammonium
form, zeolite W in ammonium form, and aluminum sulfate-modified zeolite W (Si/Al=3.5) were
tested for the removal of arsenate from aqueous solution containing 740 ppb As (V) [128]. NaY
zeolite demonstrated poor As(V) removal under the studied conditions, while the modification of
NaY zeolite with NH4Cl by ion exchange increased the arsenate removal. In contrast, NH4-W
zeolite obtained by the same procedure demonstrated no significant changes in its sorption
behaviour upon ion exchange, due to the increase in pH during the adsorption process, which
indicated that surface sites are being hydrolyzed and zeolite particles were becoming negatively
charged, which reduced arsenic adsorption rates [128]. The best performance was demonstrated by
the Al-modified zeolite W, which reached arsenic removal efficincy of 99%.
Qiu et al. [130] synthesized cancrinite type zeolitic material from CFA by molten-salt method. The
product was further modified by loading it with various amounts of alumina via a wet-impregnation
method (mass of Al impregnated /mass of zeolite = 10, 30, 50 and 80). The arsenate adsorption
capacities of the products were studied and compared with those of activated carbon, silica gel,
commercial zeolites 5A, and NaY. Activated alumina was also used as a reference adsorbent. It was
found that adsorption capacity decreased in the order CFA-derived cancrinite>5A>activated
carbon>NaY>silica gel. However, the adsorption capacities of zeolites were generally lower than
that of activated alumina (16.6 mg g−1), which was ascribed to the small pores in zeolite
frameworks. The modification with Al significantly improved the As(V) sorption. The modified
cancrinite with the optimum alumina loading (mass of Al impregnated/mass of zeolite = 50)
showed an adsorption capacity 2.1 times higher than activated alumina. The adsorption kinetics
study showed that the adsorption for 10 mg l−1 arsenate solution was completed within 1 h at
ambient condition using 1.0 g l−1 of the Al-modified zeolite. Leachability tests proved that both Al-
modified and unmodified spent zeolites were safe to dispose.
Haron et al. [129] prepared Ce(III)-exchanged zeolite P from RHA-derived NaP, and tested it for
As(V) removal from aqueous solutions. Maximum sorption of As(V) by Ce-P occurred at pH range
3-10. In addition, the sorption capacity increased with increasing initial As(V) concentrations. The
sorption followed Langmuir model with maximum sorption capacity of 8.72 mg g−1 at 25◦C and
23.42 mg g−1 at 90 ◦C, indicating an endothermic process. The mechanism of the sorption was thus
likely to be the formation of surface complex via interaction between negative arsenate ion and
positively charge Ce(III) metal ion on the zeolite. The arsenic sorption by Ce-P was not affected by
the present of nitrate, chloride, sulphate, carbonate and bromide but was reduced significantly in the
presence of phosphate. This result was in compliance with the results obtained by Xu et al. [252] for
AsO43- removal Al-loaded natural zeolite. The Ce-P was found to be effective in removal of arsenic
ion from sample of real wastewater samples from wood treatment industry.
Chutia et al. [239] investigated the adsorption of arsenic from aqueous solution on synthetic zeolites
H-MFI-24 and H-MFI-90 at room temperature applying batch equilibrium techniques. It was found
that the adsorption of arsenic followed the first-order kinetics and equilibrium time was about 100
min for both the adsorbents. Adsorption performance of H-MFI-90 was higher compared to H-MFI-
24 due to its highly mesoporous nature, which in turn accelerated the diffusion. As(V) sorption
capacity derived from Langmuir isotherm for H-MFI-24 and H-MFI-90 were 35.8 and 34.8 mg g−1,
respectively. The regeneration experiments performed in acidic (0.1N HCl) and alkaline medium
(0.1N NaOH) showed that under acidic conditions arsenic removal capacity of the regenerate
material was almost same with the fresh material, but the degree of arsenic recovery were low,

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while in base regeneration tests As recovery increased significantly at the cost of decrease of
arsenic removal capacity.
Antimony is suspected to be carcinogenic and similarly toxic as arsenic, thus WHO recommends
for potable water as low limit as 0.02 mg l-1 [151]. Concentrations of Sb in groundwater and surface
water normally range from 0.1 to 0.2 µg l-1, however higher concentrations of Sb in drinking water
could appear as a result of dissolution from metal plumbing and fittings [151]. Wingenfelder et al.
[250] investigated the sorption of antimonate from aqueous solutions by HDTMA-modified zeolite
in sodium form. The results showed that Sb(OH)6- binding was most effective when the zeolite was
treated with HDTMA solutions exceeding the zeolites external CEC. SMZ suspension (50 g l-1)
sorbed up to 42% of antimonate from solutions containing from 0.09 to 2.15 mmol.l -1Sb.
Industrial wastewater from textile, leather tanning and dyes often contain carcinogenic hexavalent
chromium in form of chromate (CrO42-) and dichromate (Cr2O72-) oxyanions, which are soluble in
aqueous systems and are readily transported in ground water. The limit for chromium in drinking
water recommended by WHO is very low (0.05 mg. l-1 total Cr) [151], thus the development of
methods for effective removal of chromates from aqueous solution is of permanent interest. Several
studies on application of surfuctant-modified zeolites for cromate removal were recently published.
Synthetic zeolite ZSM-5 and clinoptilolite, modified by HDTMA bromide and CPD bromide were
tested for the removal of chromate from aqueous solution [25]. The highest chromate adsorption
capacity of about 15 mmol.kg-1 was obtained for CPD modified clinoptilolite, and, generally,
zeolites modified by CPD showed higher adsorption capacities than those modified by HDTMABr.
For ZSM-5 zeolites with different SiO2/Al2O3 ratios, it was found that the higher the SiO2/Al2O3
ratio, the greater the chromate adsorption capacity was achieved. Good results were obtained for
cromate sorption from aqueous solutions by HDTMABr-modified nanozeolite A in batch tests
performed at room temperature [242]. Adsorption isotherms were studied under different conditions
(pH, adsorbent dose, Cr(VI) concentration and interaction time). At room temperature and pH=3.0
the Langmuir monolayer Cr(VI) adsorption capacity was 14.16 mg g-1. Chromate adsorption on
surface modified nanozeolite A was found to be inversely proportional to the pH. The presence of
competitive sulfate ions in concentrations up to 1000 mg l-1 did not affect chromate adsorption.
Results of examinations on a polluted natural sample showed that HDTMA-nanozeolite A could
reduce Cr (VI) concentration to acceptable level. Li et al. [241] performed column tests to study the
effect of particle size on the chromate adsorption by natural and HDTMABr modified clinoptilolite.
At an input concentration of 11-15 mg l-1, unmodified zeolite did not retard chromate transport for
all three particle size ranges studied, while for the modified zeolite, smaller particle size resulted in
a higher amount of surfactant, and respectively in a higher retardation factor for chromate transport.
Desorption of bromide accompanying chromate sorption confirmed that anion exchange is the
mechanism for chromate retention by SMZ.
Barquist et al. [240] prepared zeolite Y/maghemite (γ-Fe2O3) composites, which were subsequently
functionalized with 3-aminopropyltriethoxysilane to form bifunctional zeolite composites. The
adsorption capacity determined from the fit to the Langmuir isotherm was 0.849 mmol g-1.
Chromate adsorption on the composite material was attributed to external surface adsorption
through an electrostatic interaction between the positively charged amine groups and the negatively
charged chromate anions.
Fluoride in the environment occurs through its natural presence in the earth's crust and some
industrial activities, such as electroplating, aluminum, glass, steel, and fertilizer production.
According to the recommendation of the WHO the fluoride content in drinking water should no
exceed 1.5 mg l-1. Two recently published studies reported effective water defluorination by

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modified natural zeolites [244,259]. Zhang et al. [259] used Ca-modified natural zeolite for removal
of F- from aqueous solution. Batch adsorption experiments were conducted to examine the influence
adsorbent dosage, contact time, pH, presence of co-ions, and initial fluoride concentration. The
fluoride removal efficiency increased from 13.3% to 94.3% with increase in adsorbent dose from 5
to 100 g l-1, while it was only 5.2% to 9.6% for unmodified zeolite. Maximum fluoride adsorption
capacity of CaCl2 modified-zeolite was 1.766 mg g−1 at an initial fluoride concentration of 100 mg
l−1. High fluoride removal efficiency was achieved in a wide range of pH (5-7). The decline of
above 30% in the F- removal at pH>8 was explained with the competition of F− with OH− ions.
Kinetic study reveals that the fluoride adsorption by Ca-modified zeolite follows both pseudo-
second order kinetic and intra-particle diffusion models. Thermodynamic values suggest that the
fluoride adsorption process is spontaneous and endothermic. It was observed that Cl− and SO42- ions
at all the concentrations studied did not affect the fluoride removal efficiency of zeolite, while the
presence of CO32- ion caused significant drop in the fluoride removal efficiency. Similar
observarions for the effect of HCO3- were reported by Karthikeyan et al. [260]. The fluoride
removal efficiency of zeolite in aluminum industry wastewater treatment was found to be slightly
lower than that in synthetic water probably, due to the presence of competing ions.
Sun et al. [244] tested Fe(III)-modified natural stilbite for fluoride removal from synthetic water.
The adsorption of F- was studied as a function of contact time, adsorbent dose, initial concentration,
pH and coexisting ions. It was demonstrated that fluoride concentration could be reduced down to
level below 1 mg l-1 under the optimum condition (adsorbent dosage 10 g l−1 and the contact time of
2 h and pH 6.94) when initial fluoride concentration of 10 mg l−1 is employed. The fluoride
adsorption on Fe(III)-stilbite was well described by the Langmuir model, according to which the
maximum F− adsorption capacity is 2.31 mg g−1. The percentage of fluoride removal was almost
unchanged when the coexisting ion concentration was below 300 mg l−1, and decreased
dramatically in the presence of over 500 mg l−1 competitive anions.
Nitrate and nitrite are naturally occurring ions that are part of the nitrogen cycle. The nitrate
concentration in groundwater and surface water is normally low but agricultural and industrial
wastewaters are often characterized by excessive nitrate concentrations, which could cause human
health problems and eutrophication. Nitrate content in drinking water should not exceed 50 mg l-1
according to the WHO’s guidelines [151]. The process of nitrate uptake by SMZ has been
investigated is a few studies [245-248].
Masukume et al. [246] tested HDTMABr-modified clinoptilolite for the uptake of nitrate
contaminated synthetic water. They tested the effect of modifier loading in SMZ, adsorbent mass
(from 2 to 30 g l-1), and temperature (20ºC, 45ºC and 60ºC). The results clearly demonstrated that
unmodified zeolite had quite low efficiency in NO3- removal (<10%), while at the same conditions
SMZ replaced up to 92 % of the nitrate ions. The best results were obtained when clinoptilolite
were modified using a solution of 3 g l-1 HDTMABr (at solid:liquid ratio 1:100). Total nitrate
removal was achieved at the maximum zeolite dosage (30 g l-1). Experimental data showed that
adsorption of nitrate onto SMZ was exothermic process and thus, the adsorption is enhanced at
lower temperatures. pH was found to have a negligible effect on nitrate adsorption onto zeolite.
Column study and breakthrough analysis were carried out to evaluate the effects of inlet flow rate,
adsorbent mass, initial concentration and column diameter on the adsorption of nitrates onto
surfactant modified natural clinoptilolite in a fixed bed column. As it was expected, the decrease in
zeolite mass and flow velocity and the increase in initial nitrate concentration resulted in a reduction
of breakthrough time. Column diameter had negligible effect on the adsorption of nitrates on SMZ
in a fixed bed column. Schick et al. [247] also performed fixed-bed column experiments for nitrate
removal by HDTMA-modified clinoptilolite. The influence of the initial nitrate concentration

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(0.32–2.42 mmol.l-1), the flow rate or flux (1.6–47.2 cm.min-1) and the presence of competing
anions Cl-, SO42- and HCO3- (with concentrations of 1.61 meq.l-1), was examined. At the beginning
of each experiment, removal rates were very high (>95%), and then decreased progressively. With
an initial nitrate concentration of 100 g l-1, the nitrate removal was kept equal or above 50% up to a
filtered volume corresponding to 1.1 l filtered on 40 g of SMZ, allowing thus to meet the European
standard for potable water, even with the very short residence time of about 1 min. The longer
residence time of 36 min improved the performance and removal reached values above 90% for the
same filtered volume. For higher initial nitrate ion concentration of 150 g l-1 and residence time of
3.5 min, nitrate removal value was >66% when up to a volume of approximately 0.4 l. The full
breakthrough occurred when about 60% of the available adsorption sites had been exchanged. In the
presence of competing anions, the nitrate uptake performances were variously affected, being
significantly reduced by SO42- and slightly reduced in case of HCO3-. Cl- had practically no
influence on the nitrate removal. It was demonstrated the nitrate-loaded SMZ could be complete
regenerated by treatment with 1M NaBr solution.
Guan et al. [245] examined the nitrate sorbtion by HDTMABr-modified natural zeolites (mainly
clinoptilolite) from selected locations in the USA, Croatia, China, and Australia. It was found that
nitrate sorption capacity decreased in the following order: SMZ-USA (56 mmol.kg-1) > SMZ-
Croatia (45 mmol.kg-1) > SMZ-Australia = SMZ-China (24 mmol.kg-1) > raw Chinese clinoptilolite
(3 mmol.kg-1). The different SMZ nitrate removal performance was explained by the varying
amounts of the bi-layer surfactant loadins. It was demonstrated that thermo-gravimetric analyses
(TGA) could be used to distinguish between a HDTMA bi-layer and a HDTMA mono-layer on the
SMZ surface, which had not been previously reported in the literature.
Zhan et al. [248] investigated the removal of nitrate from aqueous solution using CPD bromide -
modified natural zeolite. It was found that SMZ with monolayer CPD coverage (<150 mmol.kg-1
zeolite) had negligible affinity for nitrate, while samples with patchy bilayer or bilayer CPD
coverage were much more efficient. The amount of adsorbed nitrate increased quickly (from 3.8 to
6.1 mg g-1) in the first 10 min and reached the equilibrium value of 6.55 mg g-1 after 1.5 h. The
process was well described by the pseudo-second order kinetic model. The amount of adsorbed
nitrate increased from about 5.5 to 8.5 mg g-1 with the increase of the nitrate concentration from 20
to 100 mg l-1, and decreased with the increase of temperature, indicating an exothermal nature of the
process. The removal efficiency of nitrate increased from 16% to 82% with the increase of the
adsorbent dosage from 2 to 24 g l-1. The presence of competing anions Cl-, SO42- and HCO3- slightly
reduced the nitrate adsorption. Anionic exchange and electrostatic interaction were proven to be the
main mechanisms that govern the adsorption of nitrate on SMZ.
Phosphates, along with ammonia, are the primary nutrients responsible for the eutrophication of
aqueous systems, leading to short and long term environmental problems. The two most common
methods for phosphate removal from wastewater are chemical precipitation and biological
treatment, however complete removal of phosphates is still unattainable by these methods, due to
thermodynamic and kinetic limitations [249]. In phosphate removal by zeolites good results have
been obtained with the use CFA-derived zeolites.
Chen et al. [136] subjected to HT zeolitization fifteen Chinese CFA and obtained zeolites having
from 1.2 to 7.6 times higher phosphate immobilization capacity than initialmaterials. The results
indicated that Ca and Fe components were mainly involved in phosphate immobilization. Since
their there was no significant change of Ca and Fe content following the conversion of CFA to
zeolite, it was supposed that the enhanced phosphate uptake resulted from the increase in
dissociated Fe2O3 and specific surface area of zeolites compared with corresponding CFA. The
greatest removal of phosphate occurred within the pH range of 3.5-9 for zeolite synthesized from

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high calcium CFA, and in the range of 3.5-5.5 for zeolites, synthesized from medium and low
calcium fly ash. This behaviour was explained by the reaction of phosphate with calcium and iron
components. Authors concluded that the mechanism of phosphate removal by CFA-derived zeolite
was the formation of calcium phosphate precipitate and the sorption through ligand exchange with
Fe-related component. Guan et al. [135] examined the influence of seawater electrolytes on removal
of phosphate by zeolite (type P1) synthesized from CFA. A low-calcium zeolite was initially
saturated with Na+, Mg2+, Ca2+, Al3+, and Fe3+. Al- and Fe-zeolites showed nearly complete removal
of phosphate regardless of the major seawater electrolytes, pH, and salinity. This result was
explained primarily on the basis of the adsorption mechanism through the formation of inner-sphere
complexes. The remaining zeolites showed lower phosphate removal (mostly by precipitation), in
general with the order of Ca-zeolite>Mg-zeolite>Na-zeolite. The individual presence of major
seawater electrolytes all facilitated the retention of phosphate, with CaCl2 being the most effective.
In Table 12, the phosphate sorption values obtained for simulated seawater are given in brakes.
Zhang et al. [165] investigated the simultaneous removal of ammonia and phosphate by acid-
pretreated zeolite NaP1, obtained from CFA. At low initial concentrations of phosphate, zeolite
treated with 0.9M and 1.8M H2SO4 showed the greatest affinity for phosphate. This was explained
by the fact that the adsorption mechanism of phosphate was primarily associated with Fe and Al
through ligand exchange at acidic pH levels. However, the removal efficiency quickly declined as
the initial phosphate concentration increased due to the limited immobilization capacity. At all
initial phosphate concentrations, zeolite treated with 0.01M and 0.1M H2SO4 showed notably higher
removal efficiency than the untreated one, which was explained by the fact that acid treatment
caused transformation of CaCO3 into more soluble calcium sulphates, thus favoring the dissolution
of Ca2+ and precipitation of calcium phosphate.
Ning et al. [249] synthesized a novel La(III)-modified zeolite adsorbent for selective removal of
phosphate in the presence of competitive anions like sulfates, bicarbonates, and chlorides. Batch
tests showed that this adsorbent was quite effective for removal phosphates in low concentrations.
At phosphate concentration of 1.5 mg l−1, a complete removal was achieved at zeolite dosage of 1.2
g l−1. It was proved that the La-modified zeolite had high selectivity to phosphates. The adsorption
superiority order of anions followed the order: PO43−>CO32−>SO42−>Cl− and the presence of
competing anions in the effluent from sewage treatment plant did not affect the phosphate
adsorption. Regeneration tests were also performed. In the seven regeneration experiments,
adsorption capacity of regenerated zeolite was never lower than 90% of that of the fresh one.
3.2.6. Organic compounds removal
Organic contaminants are important pollutants in water and their removal in an economic way
remains a significant problem, although various methods have been developed [9]. Owing to their
native negative surface charge, zeolites are able to capture organic cations by ion exchange.
However, both natural and synthetic zeolites exhibit little adsorption of organics in aqueous solution
due to their surface hydrophilics. The modification of zeolite by suitable surfactant can change the
surface functionality by adding hydrophobic groups and thus to enhance the adsorption of various
organics, including non-polar species. In the last decade SMZ was extensively researched as
sorbents of benzene, toluene, ethylbenzene, xylenes, phenols, pesticides, herbicides, dyes, humic
acids, etc. from aqueous solutions. The application of natural SMZ for organic matter removal from
wastewaters was recently reviewed by Apreutesei et al. [123] and by Wang and Peng [9].
3.2.6.1. Dyes removal
Dyes in wastewater originate mainly from textile, printing, food and leather industries. In aqueous
ecosystems dyes reduce sunlight penetration and thus affect photosynthesis. Some dyes, in addition,

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are toxic or carcinogenic [261]. The most important types of water-soluble dyes are acid, basic
(cationic), direct (anionic), and reactive dyes. The application of different adsorbents for dye
removal from wastewaters was reviewed by Gupta and Suhas [262]. The adsorption dyes by natural
and modified clinoptilolites was recently reviewed in [9]. Table 13 presents selected data for the
performance of some natural and modified zeolites for the removal of various dyes.
Table 13. Dyes adsorption on some natural and synthetic zeolites
Zeolite Dye
Dye Refe-
Dye Zeolite dosage, Dye sorption removal,
concentration rence*
g l-1 %
Zeolite products, obtained
Thionine 5.10-6 mol.l-1 10 3.5-3.7x10-6 mol.g-1 [263]
from CFA
Safranine T Zeolite products, obtained
5.10-6 mol.l-1 10 1.3-2.37x10-6 mol.g-1 [263]
from CFA
Rhodamine B Clinoptilolite + mordenite
10-6-10-5 mol.l-1 0.25 2.58 x10-5 mol.g-1 [18]
from Australia
Methylene Clinoptilolite + mordenite
10-6-10-5 mol.l-1 0.25 6.3 x10-5 mol.g-1 [18]
blue from Australia
2.7x10-5 mol.l-1 0.1 5 x10-5 mol.g-1 [264]
blue from Australia
Methylene
CMC-22 2.7x10-5 mol.l-1 0.1 1.7x10-4 mol.g-1 [264]
blue
100 mg l-1 27.0 mg g-1 [47]
blue from Chile
Methylene Zeolite A, obtained from
50 mg l-1 1 37.8 mg g-1 80 [265]
blue CFA
Methylene Zeolite X, obtained from
50 mg l-1 1 43.0 mg g-1 90 [265]
blue CFA
Methylene Hydroxisodalite obtained
0.5 mmol.l-1 10 0.28 mmol.g-1 [266]
blue from CFA
Methylene Ti-modified zeolite A,
blue obtained from RHA, as a 10 mg l-1 0.7 92 [267]
photodegradation catalyst
Derma blue Cu–NaY as a catalyst for
IDB oxidation with H2O2 (175 50 mg l-1 0.3 100 [268]
mmol.l-1)
Reactive Fe-modified zeolite ZSM-5
Brilliant Blue as a catalyst for oxidation 250 mg l-1 4 >95 [269]
KN-R with H2O2 (50mmol.l-1)
Acid red1 Fe-modified zeolite Y as a
catalyst for oxidation with 50 mg l-1 2.5 >99 [270]
H2O2 (16 mmol.l-1)
Blend of 6 5 g l-1
H-ZSM-5 (Si/Al=40) 10 59 [271]
printing inks TOC-1052 mg l-1
Blend of 6 5 g l-1
H-ZSM-5 (Si/Al=25) 10 60 [271]
Blend of 6 5 g l-1
NH4-ZSM-5 10 62 [271]
Blend of 6 5 g l-1
NH4-beta 10 67 [271]
Blend of 6 5 g l-1
NH4-mordenite 10 46 [271]
Blend of 6 5 g l-1
H-Y 10 55 [271]
Blend of 6 5 g l-1
NaY 10 29 [271]

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Blend of 6 5 g l-1
13X 10 12 [271]
* Some values are recalculated and/or rounded. **TOC-total organic carbon.
Basic (cationic) dyes are used for coloring of paper, polyacrylonitrile, silk, wool, cotton, modified
nylons, modified polyesters, cation dyeable polyethylene terephthalate, etc. [262]. In aqueous
solutions basic dyes yield coloured cations, which could be captured on zeolites by cation ion
exchange [263-265,272,273], if the geometry of zeolite pores allows their sorption.
Australian natural zeolite, composed of clinoptilolite and mordenite was tested for basic dyes
adsorption in aqueous solution [18]. The results showed that the natural zeolite presents higher
adsorption capacity for methylene blue (MB) than for rhodamine B. The maximal adsorption
capacities were 2.8x10-5 and 7.9x10-5 mol.g-1 at 50 ◦C, respectively. Thermodynamic and kinetic
calculations indicated that the adsorption was endothermic reaction with two-step diffusion process.
The adsorption kinetics could be described by the pseudo second-order model. Both Langmuir and
Freundlich models fitted well the adsorption isotherm. Wang et al. [264] compared MB adsorption
by the same natural zeolite and by synthetic zeolite MCM-22. Two methods, Fenton oxidation and
high temperature combustion, have been tested for regeneration of used materials. It was found that
MCM-22 exhibits much higher dye adsorption than the natural zeolite. Increase of solution pH from
3 to 9 increased the adsorption capacity twice. Physical regeneration by high temperature (540ºC)
calcination recovered more than 88% of MCM-22 adsorption capacity, while chemical regeneration
by Fenton oxidation - only 60%. For the natural zeolite, the regeneration tests showed that both
techniques were able to restore only 60% of the adsorption capacity on the fresht adsorbent. Tsai et
al. [274] studied synthetic zeolite type P2 as an adsorbent for removal of MB and bisphenol-A (4,4-
isopropylidenediphenol), which had similar molecular sizes, but quite different chemical properties.
The results indicated that the zeolite P2 exhibited significantly higher adsorption capacity for MB
than that for bisphenol-A, due to the difference in molecular properties. The adsorption kinetics of
MB onto the zeolite was well described by pseudo-second-order model. Wang et al. [265]
performed kinetic and equilibrium studies on the adsorption of MB from wastewater by zeolites A
and X, synthesized from CFA. Batch method was used to study influence of initial pH value of the
solution (3-11), temperature (20-50°C), and adsorbents dosage (0.1-0.3mg.), on the adsorption
process. Generally, the removal efficiency of MB increased with a rise of these three factors. The
experimental data well fitted to Ho’pseudo-second-order model and liquid film diffusion model.
The Langmuir model was found to describe accurately the sorption isoterms. In all the experiments,
the adsorption capacity of zeolite X was higher than that of zeolite A. The greatest adsorption
capacity value obtained for zeolite X and A, were respectively 31.9 mg g-1 and 23.2 mg g-1 at 20°C,
and 51.2 mg g-1 and 43.8 mg g-1 at 40°C. Woolard et al. [266] investigated the sorption of MB and
alizarin sulfonate (anionic dye) by CFA-derived hydroxysodalite. The CEC of the modified ash was
significantly increased over that of the raw CFA (188 vs 2 mg g-1). Adsorption experiments showed
that hydroxysodalite adsorbed the cationic dye to a much greater extent than the anionic one. Since
the adsorption capacity of MB on the zeolitized CFA was much lower than the CEC, the adsorption
of MB was ascribed to be a surface effect rather than involving incorporation into the channels of
the hydroxysodalite structure. Atun et al. [263] investigated the adsorption characteristics of two
basic dyes, thionine and safranine T, onto CFA, and three zeolitized products prepared from CFA at
different HT treatment conditions. Typical two-step isotherms were observed for thionine
adsorption onto four adsorbents, whereas the isotherms of the larger safranine T molecules were S-
shaped. The adsorption capacities of the zeolitized fly ash estimated from the first plateau region of
the thionine isotherms was nearly twice the CFA capacity. The capacities increased by up to five
times in the second plateau region. The safranine T adsorption capacities of CFA and zeolites were
lower than those found for thionine. The equilibrium results were well described by the Freundlich

___________________________________________________________________________________________________________
isotherm model. Petkowicz et al. [267] investigated the photodegradation of MB by in-situ

generated titania supported on a NaA zeolite, which were obtained by using alternative silicon
sources, namely rice husk and chrysotile. The highest catalyst activity was reached with samples
having 10 wt.% Ti. Catalyst activity was shown to be comparable to that exhibited by commercial
P-25 after 1 h of UV light exposition. Experiments, carried out in natural sunlight reached 92% MB
decomposition.
Acid dyes (used for nylon, wool, silk, modified acrylics, paper, leather, ink-jet printing, food, and
cosmetics), direct dyes (used for cotton and rayon, paper, leather, and nylon) and reactive dyes
(used for cotton and other celluloses, wool and nylon) [262] are among the most widely used types
of water-soluble anionic dyes. Several researchers have investigated the process of oxidation of acid,
direct, and reactive dyes using zeolite-based catalysts [268-270].
Copper(II) complex of NN’–ethylene bis(salicylidene-aminato) encapsulated in zeolite Y was tested
as a catalysts for wet hydrogen peroxide oxidation of an anionic dye (Derma blue IDB, Clariant)
[268]. The effects of various parameters such as pH, catalyst and hydrogen peroxide concentration
onthe oxidation of dye were studied. Complete removal of color was obtained after treatmnt for less
than 1 h at 60 ºC, 0.175M H2O2, and 0.3 g l-1 catalyst. Dye removal from commercial tannery dye
effluent was also experimented in order to assess the efficiency of the catalyst to oxidize the dye in
the presence of other chemicals used in leather processing. Above 95% dye removal efficiency for
the commercial effluent was attained. COD removal of 85% was observed after the treatment. The
catalyst was reused more than 10 times without any significant change in the catalytic property.
Chen et al. [269] examined the decolorization of an anthraquinone dye (Reactive Brilliant Blue KN-
R) by H2O2 using Fe-containing Y and ZSM-5 zeolites as heterogeneous catalysts. Catalysts were
prepared by ion exchange and co-precipitation methods, and calcined at different temperatures. The
influence of dye concentration, catalyst dosage, and solution pH was evaluated. The results showed
that both zeolites exhibited similar or better catalytic efficiency compared to homogeneous Fenton
reagent, with Fe-containing ZSM-5 being more efficient. Fe-containing ZSM-5, which was
prepared by coprecipitation and calcination at 450◦C, displayed the greatest decolorization capacity.
Under the conditions of initial pH 2.5, 30 mmol.l-1 H2O2 and 4.0 g l-1 catalyst, 250 mg l-1 KN-R was
decolorized over 90% within 20 min. A resent investigation on the oxidative decolorization of Acid
Red 1 solutions by Fe–loaded zeolite Y catalyst [270] showed that at the optimal reacting
conditions (initial pH 2.5, 16 mmol.l-1 H2O2 and 2.5 g l-1 catalyst, 50 mg l-1 dye, at 30 °C) 99%
decolorization efficiency could be achieved within 60 min of reaction time. Karadag et al. [276]
studied raw and SMZ for adsorption of Basic Red 46 and Reactive yellow 176 dyes from aqueous
solutions. They compared the effect of different surfactants, CTAB and HTDMA, on dye adsorption
and established that the increase in ionic strength caused a decrease in adsorption of basic and an
increase in adsorption of the reactive dye. Adsorption of the cationic dye on natural zeolite was
more favourable than Reactive Yellow 176 on the CTAB and HTDMA modified zeolites. Another
study on the removal of reactive dyes by CTAB-modified natural zeolite [277] demonstrated that
the adsorption capacity for Reactive Red 239 was almost twice higher than that of Reactive Blue 5,
due to the hydrophilicity of the dye molecules. Benkli et al. [278] also investigated HDTMA-Br
modified clinoptilolite for removal of reactive dyes, (Reactive Black 5, Reactive Red 239 and
Reactive Yellow 176), in a fixed bed column. The results indicated the order of dye removal by
SMZ was the following: Black >Yellow>Red. However, the results obtained by Armagan et al.
[279] for the sorption of the same dyes by HTDMA-modified zeolite showed that maximum
adsorption capacities of decreased in the order Red (111 mg g-1)>Yellow (89 mg g-1) > Black (61
mg g-1).
Ozdemir et al. [280] investigated the ability of SMZ to remove color from real textile dyeing

___________________________________________________________________________________________________________
wastewater, containing blend of reactive dyes and auxiliary chemicals. Tests were performed in a
fixed-bed column reactor and the surface of natural zeolite was modified with HDTMA-Br. Effects
of wastewater color intensity, flow rates and bed heights were also studied. Wastewater was diluted
several times in the ratios of 25%, 50% and 75% in order to assess the influence of wastewater
strength. The breakthrough curves of the original and diluted wastewaters were dispersed due to the
fact that breakthrough color intensities and saturation of the bed appeared faster at higher color
intensities. The column had a 3-cm diameter and four bed heights from 12.5 to 50 cm, which treated
from 5.25, to 51 l original textile wastewater, respectively, at the breakthrough time at a flow rate of
0.025 l min−1. The various design parameters obtained from fixed-bed experimental studies showed
good correlation with corresponding theoretical values, under different bed heights.
Metes et al. [271] investigated the unselective adsorption of residual organic pollutants from
flocculated printing ink wastewater onto eight synthetic zeolites as a finishing method for additional
reduction of total organic content (TOC) in this effluent. Simulated wastewater was obtained by
combining six single wastewaters of a specific printing ink, each at a concentration of 5.0 g l-1. The
initial TOC of wastewater at pH 7.5-7.8 was 1052 mg l-1. The amount of adsorbed organics was
largest for ZSM-5 and NH4-Beta while the other zeolites studied showed lower efficiency,
suggesting that adsorption was independent of pore structure. All the zeolites tested, except NaY
and 13X were found to have a higher organic capacity in comparison to that obtained with
powdered activated carbon. The adsorption rates of organic pollutants were fast as well. The 88%
reduction of TOC obtained with a single flocculation treatment was improved with the combination
of flocculation and adsorption with ZSM-5, which resulted in the overall TOC efficiency of 95%. It
was concluded that flocculation followed by adsorption with zeolites is an effective treatment
method for this kind of wastewater.
3.2.6.2. Humic substances removal
Humic substances (including humic acid, fulvic acid, and humin) make up about 80% of soil
organic matters in dark soils [9]. Their presence in surface and ground water may produce toxic
chemicals during disinfection processes and thus should be reduced. Some important studies on
humic substances adsorption by natural zeolites were summarized by Wang and Peng [9].
Capasso et al. [281] investigated the adsorption of humic acid on raw Neapolitan yellow natural
zeolitic tuff (containing phillipsite and chabazite), and Li+, Na+, K+, NH4+, Ca2+ or Ba2+ - enriched
samples. The raw zeolite showed humic acid sorption capacity of about 8.5 mg g-1. It was
demonstrated that the enrichment of tuff by monovalent cations slightly reduced the adsorption
(down to 6.5-7.0 mg g-1), whereas the enrichment by divalent cations significantly enhanced humic
acid sorption. Ca and Mg - enriched samples, yielded the best results - 21.5 and 22 mg g-1,
respectively. Compared to the Neapolitan tuff, natural clinoptilolite, even in Ca-exchanged form,
was found to be much more ineffective [282] with humic acid adsorption capacity of 2.6 mg g-1.
Remarkably, high humic acid adsorption of 68 mg g-1 was achieved for Australian natural zeolite
tuff [283] at 30ºC and pH=5.
HDTMA-modified natural and synthetic zeolites have been also investigated for humic substances
removal. Li et al. [286] recently reported an investigation on the performance of HDTMA-modified
zeolites, obtained from CFA, for adsorption of humic acid from water. Two zeolite samples were
synthesized from high-Ca and low-Ca CFA and then modified with HDTMA as described in [287].
The performance of modified and unmodified samples was examined in a batch tests. The
experiments were performed with adsorbent dosage of 5 g l-1, humic acid initial concentrations
ranging from 50 to 900 mg l-1, at room temperature, and 24 h treatment time. The results showed
that, although CFA-derived zeolites had little affinity for humic acid, the adsorption by SMZ was

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high. The maximum adsorption capacities calculated from the Langmuir model for low-Ca and
high-Ca SMZ was respectively 31.6 mg g-1 and 126.6 mg g-1, which values were comparable or
higher than those for activated carbons and clays previously reported. It was observed that the
uptake of humic acid on SMZ was substantially increased under acidic pH conditions and that the
removal efficiency of low-Ca SMZ was more pH sensitive than that of high-Ca sample. For high-Ca
SMZ removal efficiency of nearly 100% was reached at pH<9, while for low-Ca SMZ the same
results were achieved at pH ≤ 5. The uptake of humic acid was improved in the presence of
electrolyte (NaCl).
3.2.6.3. Removal of other organics
Phenols are toxic compound coming from a variety of industrial sources, such as pesticides, dyes,
and paper industries, coke and resin manufacturing, textile, plastic, rubber, pharmaceutical, and
petroleum production. Wu et al. [286] examined the adsorption of bisphenol A by two zeolite
samples, synthesized from CFA, and modified with HDTMA. The SMZ showed greatly enhanced
adsorption capacity than the parent zeolite. Bisphenol A uptake increased at alkaline pH conditions,
which enabled the formation of bisphenolate anion [286]. The SMZ having higher BET surface area
and higher amount of loaded HDTMA showed greater retention for bisphenol A. The uptake of
bisphenol A was improved slightly in the presence of NaCl, and was enhanced at a low temperature.
The authors proposed that the anions interact strongly with the positively charged heads of
HDTMA, with the two hydrophobic benzene rings of bisphenol A pointing to the inside of
HDTMA bilayers, while the adsorption of uncharged bisphenol A probably involved hydrophobic
partitioning into HDTMA bilayers and the coordination of the oxygen atoms of bisphenol A with
positively charged heads of HDTMA. Tsai et al. [287] obtained very good results for the sorption of
bisphenol-A by zeolite Y (up to 120 mg g-1) and negligible sorption (<0.5 mg g-1) for zeolite type
P2 [274], although the specific surface area of the zeolites were similar - 500 m2 g-1 and 400 m2 g-1,
respectively. These results were explained with the repulsive interaction between the hydrophilic
surface of the zeolite P2 (having low Si/Al ratio) and, conversely, the attracting interaction between
the bisphenol-A and hydrophobic surface of high-silica zeolite [274]. Kuleyin [288] investigated the
adsorption of phenol and 4-chlorophenol on HDTMA- and BDTDA-modified natural zeolite. At
initial concentration of 50 mg l-1 the phenol removal efficiencies reached up to 71% and 73% for
HDTMA-zeolite and BDTDA-zeolite, and the 4-chlorophenol removal efficiencies reached up to
81% and 89% for HDTMA-zeolite and BDTDA-zeolite. The maximum capacities of surfactant-
modified zeolite for phenol and 4-chlorophenol have been calculated in the range of 0.7647–1.2977
mg g-1and 6.4102–12.7065 mg g-1, respectively. Lopez [289] studied the adsorption of
paranitrophenol in a packed bed adsorption reactor filled with dealuminated Y (Si/Al=20) zeolite
and granulated active carbon. The maximum amount of paranitrophenol adsorption on the zeolite
was found to be as high as 330 mg g-1.
Benzene, toluene, ethylbenzene, and xylene (abbreviated as BTEX) are volatile aromatic
compounds, typically found in petroleum products, such as gasoline and diesel fuel. BTEX are
carcinogenic and have harmful effects on the central nervous system. BTEX are notorious due to
the contamination of groundwater and soil that typically occurs near petroleum and natural gas
production sites, and petrol stations and other areas with storage tanks containing gasoline or other
petroleum-related products. Ranck et al. [290] investigated the effectiveness of HDTMA-modified
zeolite in BTEX removal along with changes in sorption properties with long-term use. The results
showed 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. The
most soluble compound, benzene, began to elute first - at 8 pore volumes (PV), while the least
soluble compounds, ethylbenzene and xylenes, began to elute at 50 PV, which was in agreement

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with the BTEX behaviour previously reported by Bowman [122]. The field-scale system was also
tested at a natural gas produced-water treatment facility. In the field column, initial benzene
breakthrough occurred at 10 PV and toluene breakthrough began at 15 PV and no breakthrough of
ethylbenzene or xylenes occurred throughout the 80 PV experiment. Altare et al. [291] performed
column tests to estimate applicability of HDTMA-modified clinoptilolite for the removal of BTEX
from produced water generated as a byproduct of oil and gas recovery. The results showed that
BTEX removal was controlled by the total number of PV that passed through the SMZ bed, and to a
minor degree by flow rate, 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. Only a small loss in sorption affinity after 50 cycles was detected.
Ghiaci et al. [292] investigated the adsorption of benzene, toluene and phenol by CPD- and
HDTMA- modified ZSM-5-31, ZSM-5-88, and clinoptilolite besides as-synthesized MCM-41
molecular sieve. They found that the increase in contaminant concentration or initial concentrations
of surfactants resulted in an increase in the adsorption. At equal concentration, CPD modified
zeolite showed higher adsorption than that of the corresponding HDTMA-modified zeolite.
Sorption capacity of the organics onto the as-synthesized MCM-41 and modified zeolites were in
the order of MCM-41> SMZclinoptilolite >ZMZ ZSM-5-88> SMZ ZSM-5-31. Benzene and
toluene showed almost similar sorption capacity, whereas phenol showed the lowest sorption
capacity among them.
Ersoy and Celik [293] examined the adsorption of aniline and nitrobenzene on raw and HDTMA-
modified natural zeolite. In batch tests the adsorption capacity of aniline and nitrobenzene onto
natural zeolite surface was negligible, while that onto SMZ was significant. In the column tests,
adsorption capacity of two compounds on SMZ from the breakthrough curves was determined as
2.36 and 3.25 mg g-1 for aniline and nitrobenzene, respectively.
Atrazine is a widely used herbicide, which use is controversial, due to widespread contamination in
drinking water and its associations with birth defects, and other health problems. Although it has
been banned in the EU, it is still one of the most widely used herbicides in the world. Grcic et al.
[294] studied the application of different types of synthetic zeolites (CuZSM-5, FeZSM-5, HZSM-
5, NH4ZSM-5 and HY) as adsorbents for atrazine removal from wastewater. After two hours of
treatment the highest removal efficiency was demonstrated by CuZSM-5 (54.3%), while the
protonated form of ZSM succeeded to remove only 5.1% of the initial pollutant. The application of
a combination of advanced oxidation technologies and adsorption resulted in complete removal of
atrazine from model wastewater and significant decrease in TOC value. Lemic et al. [295]
performed systematic adsorption tests in order to determine the efficiency of SDBAC-modified
zeolite for removal of pesticides, atrazine, lindane and diazinone from water. The effects of
adsorbent particle size and dosage, and the initial organic compaound concentration in the solutions
were investigated. The adsorption capacities, calculated by Langmuir–Freundlich equation, were
2.0 µmol.g-1 (atrazine), 4.4 µmol.g-1 (diazinone), and 3.4 µmol.g-1 (lindan).
Bai et al. [296] investigated the removal of pyridine and quinoline from synthetic and coking
wastewater by bio-zeolite composed of mixed degrading bacteria and modified clinoptilolite. The
modified zeolite was made of clinoptilolite, white cement, natural zeolite gizzard, amylum, and coal
powder with the proportion of 24:6:30:5:3 (v/v). After the addition of 7% carboxylic methyl
cellulose solution, the mixture was extruded and then burned at 650 ◦C for 2 h. The experimental
results indicated that the mixed bacteria could degrade pyridine and quinoline simultaneously, while
zeolite could remove the NH4+-N transformed from pyridine and quinoline.

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Some results for the performance of natural and synthetic SMZ for organic species removal are
presented in Table 14.
Table 14. Performance of some SMZ for separation of different organic contaminants
Organic compound Zeolite Removal
Organic Organics Refe-
Zeolite concentration, dosage, efficiency,
compound sorption rence*
mg l-1 g l-1 %
Bisphenol-A NaY (Si/Al=100) 30 0.5 120 mg g-1 [287]
Bisphenol-A NaP2 (Si/Al=5) 20 0.5 <0.5 mg g-1 [274]
Bisphenol-A NaP1 L 100 0.5 42 mg g-1 [286]
Bisphenol-A Hydroxisodalite and NaP1 100 0.5 100 mg g-1 [286]
Naphthalene HTDMA-clinoptilolite 20 6-120 2 µmol C. g-1 [124]
Phenol HTDMA-clinoptilolite 50 71 [288]
Phenol BDTDA-clinoptilolite 50 81 [288]
4-chlorophenol HTDMA-clinoptilolite 50 73 [288]
4-chlorophenol BDTDA-clinoptilolite 50 89 [288]
O-xylene HTDMA-clinoptilolite 30 6-120 3 µmol C. g-1 [124]
Atrazine H-ZSM-5 1 0.5 5 [294]
Atrazine NH4-ZSM-5 1 0.5 39 [294]
Atrazine Cu-ZSM-5 1 0.5 54 [294]
Atrazine Fe-ZSM-5 1 0.5 46 [294]
Atrazine H-Y 1 0.5 45 [294]
Atrazine SDBAC-natural zeolite 1.8 0.5 0.45 µmol g-1 [295]
Diazinone SDBAC natural zeolite 3.9 0.5 1.8 µmol.g-1 [295]
Another perspective application of zeolites exploiting their absorption and molecular sieving
properties is for the productions of supported polycrystalline zeolite membranes (ZM). ZM can be
prepared by different methods: in-situ HT synthesis, chemical vapor phase method, spray seed
coating [228] on the supporting material (e.g. sintered alumina), but regardless to the method of
preparation, ZM have several important advantages when compared to conventional polymeric
membranes, namely chemical, mechanical, and thermal resistance that allow ZM to be used at
strong solvent environments, and at high temperatures and pressures [178]. ZM have been
extensively researched for separation of organic contaminants from (waste)water, since most of
organic pollutants damage the polymeric membranes [228]. Selected results from zeolitic
membrane separation of different organic contaminants are presented in Table 15.
Table 15. Zeolitic membrane separation of different organic contaminants
Organic
Organic Conc. of Zeolite Membrane Refe-
Water flux rejection,
compound solution, % membrane thickness rence*
%
Isopropanol 90 NaA on α-Al2O3 10 µm 1.2 kg.m−2 h−1 >98 [225]
Pentanoic acid 0.01 MFI on α-Al2O3 1.2 µm 0.03 kg.m−2 h−1 96.5 [297]
Toluene 0.1 MFI on α 1.2 µm 0.33 kg.m−2 h−1 99.5 [297]
Etanol 0.1 MFI on α 1.2 µm 0.31 kg.m−2 h−1 17.0 [297]
Oil 0.1 NaA on α-Al2O3 60 l.m−2 h−1 98.8 [298]
Oil contaminated water is commonly discharged by large steel mills and related industries and is a
major pollution problem because of the difficulty in treating oily wastewater. Cui et al. [298]
investigated the application of zeolite/ceramic microfiltration membranes for treatment of oil-
contaminated water. NaA ZM with different average inter-particle pore sizes of 1.2 µm and 0.4 µm
were prepared on α-Al2O3 tube by in situ HT method. The filtration decreased the oil content in the
emulsions from 100–500 mg. l-1 down to < 3 mg. l-1 at moderate to high flux. Consistent membrane

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performance was maintained by a regeneration regime consisting of frequent backwash with hot
water and alkali solution.
MFI silicate ZM was synthesized on the inner surface of tubular α-alumina substrates [297]. The
obtained membrane was tested for separation of pentanoic acid, toluene and ethanol from aqueous
solutions. The results indicate that ZM have great potential for separation of dissolved organics
from wastewater. At initial concentrations of 100 ppm ZM rejected 96.0% of pentanoic acid and
99.5% of toluene in the solutions. It was observed that organic rejection and water flux were
affected by the organic concentration. As pentanoic acid concentration increased from 100 ppm to
500 ppm, both organic rejection and water flux decreased slightly.
3.2.6.4. Micro-organisms capturing
The large surface area of the zeolites is accessible for adhering microorganisms. This makes
zeolites a suitable material for biofilter for removal of pathogen microorganisms [125], or for
cultivation of bacteria, employed in active sludge at wastewater treatment plants [8]. The main
advantage of zeolites in comparison with clay adsorbents is that zeolite has better hydraulic
properties [122]. The main drawback of the use of zeolites is the slow rate of bacteria uptake from
wastewater (when zeolite is used for bacteria removal) or the slow rate of formation of the bacteria
layer on the zeolite surface (when zeolite is used as bacteria carrier) [8].
Garcia et al. [300] conducted a research on removal of bacteria indicators of pollution (total
coliforms, faecal coliforms and faecal streptococci) and organic matter (evaluated as COD and
BOD) from wastewater from the water treatment plant at Santa Cruz de Tenerife city (Canary
Islands) using natural phillipsite. The tests were performed in a percolation reactor at a constant
solution flow rate. Faecal coliform and faecal streptococci were totally removed at the 10th and 17th
day, respectively. 75% COD retention at the 25th day and 100% BOD in the 90th day were achieved.
Escherichia Coli, poliovirus, coxsackie virus and bacterophages from drinking water was
effectively removed from drinking water using Al2(SO4)3 coagulant and clinoptilolite [230]. The
microorganisms were captured by the formation of microorganism-clinoptilolite-coagulant
complexes. Research on the potential of clinoptilolite for removal of coliform bacteria, total
bacteria, phyto-and zooplankton from drinking water showed that the physiochemical and
mechanical properties of the zeolite were kept unaltered after 3 years of usage and gave a stable
decrease in the content of microorganisms [230].
The modification of zeolites by cation active polyelectrolytes accelerates the interaction between
the bacteria and the zeolite surface, thus increases the sludge activity [243]. The SMZ show better
ability to bind pathogen microrganisms, as well [122,301,302]. The investigation of Nikashina and
Myasoedov [302] demonstrated that Escherichia coli could be totally removed from drinking water
by treatment with clinotsid, an organozeolite, prepared by modifying natural clinoptilolite with
amine groups-polyhexamethylene guanidine chloride linked with epichlorohydrine. Bowman [122]
studied HDTMA-modifyed clinoptilolite from St. Cloud, New Mexico, as adsorbent for removal of
Escherichia coli and bacteriophage MS2 from sewage-contaminated water. Results indicated the
complete removal of Escherichia coli by the SMZ. Based on laboratory and field results, SMZ
performed very well in removing viruses from groundwater. The only concern is the non-selectivity
of SMZ, e.g. the removal of both viruses and negatively charged ions such as bromide, which may
limit the applicability of SMZ in high-salinity waters and in long-term applications. Most of the
virus removal by SMZ was attributed to sorption. It was observed that a minor amount of the
surfactant coating dissolved into the water and thus probably removed a significant percentage of
the viruses in the field test. Escherichia coli was completely removed by SMZ during the field tests.
Author commented that although HDTMA was bactericidal in aqueous solution, the adsorbed

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Escherichia Coli might remain viable for a period of time, because the toxicity of HDTMA to the
organisms is greatly reduced when surfactant was bound to zeolite. Finally, laboratory experiments
showed that toluene-degrading organisms could be effectively cultured on SMZ.
3.2.7. Permeable reactive barriers (PRB)
The leakage of municipal, industrial, and radioactive waste disposal sites may cause distribution of
contaminants in the surrounding environment. PRB have been developed and successfully used for
in-situ treatment of contaminated ground water [124,303]. The barriers are filled with reactive
material, which captures or modifies the contaminants, thus improving the ground water quality.
The high sorption capacity, plasticity, chemical stability, mechanical strength, and thermal
conductivity make the raw and modified zeolitic materials, along with the clays, suitable for
utilization as liners prohibiting the spreading of the contaminants [8]. The use of SMZ as a PRB
sorbent offers several advantages when dealing with mixed contaminant plumes [122]. Bowman
[122] evaluated HDTMA-modified natural clinoptilolite in a permeable reactive barrier for the
removal of contaminants from sub-surface water. A 15-week pilot test showed barrier retardation
factors of 44 and 39 for chromate and PCE, respectively, similar to the values predicted from
laboratory experiments. SMZ was also tested for removal of organics from oilfield wastewaters.
The results showed that the higher solubility species benzene and toluene appeared first in the
effluent and reach influent concentrations relatively rapidly, followed by the more hydrophobic,
more strongly retained ethylbenzene and xylenes. At influent concentration of 13-15 mg l-1 the total
mass of BTEX retained by the SMZ-filled column is 65.3 mg for benzene, 148 mg for toluene, 628
mg for methylbenzene, 698 mg for m-, p-xylene, and 657mg for o-xylene, respectively. Total
removal of bacteria and viruses from sewage effluent, was also reported (see 3.2.7). Northcott et al.
[124] synthesized hydrophobic zeolite and characterized its suitability as a PRB material for
treatment of hydrocarbons in groundwater. Batch sorption tests were performed along with a
number of standard characterization techniques. High and low ionic strength and pH tests were also
conducted to determine their impact on hydrocarbon uptake. Further ion exchange tests were carried
out to evaluate the potential of zeolite to act as both a hydrocarbon capture material and nutrient a
delivery system for bioremediation. The natural zeolite was coated with octadecyltrichlorosilane to
change its surface properties. The results of the surface characterization tests showed that the
underlying zeolite structure was largely unaffected by the coating. TGA measurements showed a
reactive carbon content of 1–2%. O-xylene and naphthalene sorption isotherms results compared
well with the behaviour of similar materials investigated by other researchers. Ionic strength and pH
had little effect on hydrocarbon sorption and the treated zeolite had an ion exchange capacity of 0.3
meq g-1, indicating it could be utilized as a nutrient source in PRB. Recycle tests indicated that the
zeolite could be re-used at least three times without significant reduction in treatment effectiveness.
Hornig et al. [304] tested several sorbent materials (MYCELX coated sand, granular activated
carbon and HDTMA-modified clinoptilolite) for treatment of hydrocarbon-contaminated ground
water in cold regions. Batch sorption tests at 20 °C and 4 °C were performed with using toluene, o-
xylene and naphthalene. The results of the surface characterization tests showed that the quality of
the MYCELX coating on the sand was highly variable, thus leading to unreliable adsorption results.
Activated carbon proved to be the best sorbent material at high and low temperatures on a mass
basis, while on a surface area basis, SMZ performed better. High ionic strength and high and low
pH had little effect for hydrocarbon sorption. Both materials exhibited reduced adsorption
efficiency at 4 °C compared to 20 °C. For SMZ the decrease of temperature caused about 40% the
reduction of the distribution coefficient for all hydrocarbons. A study [305] on the application of
clinoptilolite in PRB for the treatment of heavy metal contaminated waters in Antarctic also
indicated that the performance of the zeolite was significantly reduced at low temperatures.

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3.2.8. Sea water desalination

A number of seawater desalination technologies were developed during the last several decades to
augment the supply of water in arid regions of the world. Two of the most commercially important
technologies are based on the multi-stage flash distillation and reverse osmosis (RO) processes
[306]. In the RO process, the osmotic pressure is overcome by applying external pressure. Thus,
water flows in the reverse direction to the natural flow across the membrane, leaving the dissolved
salts behind [306]. The reverse osmosis membrane materials for desalination have been recently
reviewed by Lee at al. [307]. A molecular dynamic simulation has shown that some ZM are
theoretically suitable for ion removal from aqueous solutions by RO [228]. For instance, MFI ZM
was expected to reject 100% Na+ through size exclusion of hydrated ions, which have kinetic sizes
larger than the aperture of zeolite. The sizes of some hydrated ions are presented in Table 16 [309].
Table 16. Size of hydrated ions
Ion Hydrated diameter, nm
H2O 0.26
Li+ 0.76
Na+ 0.72
K+ 0.66
Mg2+ 0.86
Ca2+ 0.82
OH- 0.60
Cl- 0.66
NO3- 0.68
According to this mechanism, MFI zeolite, which has an effective intracrystal nanopore diameter of
0.51 nm, is supposed to be suitable for separating the small water molecules (0.26 nm) from larger
ions like Na+ and Cl− having hydrated sizes of 0.72 and 0.66 nm, respectively [309]. However, the
first experimental attempt for RO of a NaCl solution using a MFI silicalite-1 ZM showed only 77%
salt rejection and a water flux as low as 0.003m3m−2 day−1 at 21 bar [310]. It was also reported that
rejection of bivalent cations was higher than for monovalent ions, in a test using a feed containing
mixed ion species. These results showed that the filtration mechanism was not only dependent on
size exclusion, but also on Donnan exclusion, due to the charged double layer induced by adsorbed
ions on the pore or the intercrystalline walls. Although the first RO test with a ZM was
unsuccessful, subsequent work was conducted to improve both salt rejection and water flux by
modifying the zeolite structure. The Si/Al ratio, which dominates the wettability and membrane
surface charge, was optimised to give improved flux. Duce et al. [311] developed silicalite and
ZSM-5 ZM and tested desalination using the thermally based pervaporation, and RO operation
modes. ZM were synthesized by template-free secondary growth technique with varying Si/Al
ratios. In pervaporation with 3.8 wt% sea salts feed, zeolites containing alumina actively rejected
ions, displaying equivalent rejections exceeding 99%. Flux typically decreased after introduction of
seawater, but the membrane with Si/Al ratio of 100 (ZSM100) uniquely showed a 30% increase in
flux, which could only be explained by an ion exchange/interaction mechanism, which opened the
zeolite structure to permeation. Optimal temperature for pervaporation was found to be 80°C, where
high rejections persisted, and flux increased to 0.72 kg.m-2.h-1. In RO at the consistent conditions of
room temperature operation and 0.5 wt% sea salts fed at 700 kPa, strikingly different results for
both flux and rejection for the different membranes were observed. In terms of flux, ZSM100
showed 3-fold greater flux than silicate and ZSM020 (Si/Al ratio of 20). Li et al. [312] investigated
RO of 0.1M solutions of alkali metal chlorides, including LiCl, NaCl, KCl, RbCl, and CsCl on
MFI-type ZM synthesized from an aluminum-free precursor. The MFI zeolite membrane exhibited
high rejection rates (>95%) for all alkali metal ions at an applied pressure of 2.75 MPa. The

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rejection rates of Li+ and Na+ declined slightly, while the ion flux increased more dramatically than
did the water flux with moderately raising the temperature. Increasing the hydraulic pressure
difference across the membrane resulted in significant enhancements in both the water flux and the
ion rejection rates but with much less influence on the ion flux. The ion flux increased
monotonically with the crystallographic ion size from Li+ to Cs+ while the dependence of the water
flux on ion size exhibited a maximum for the 0.1M KCl solution.
Kazemimoghadam [309] synthesized hydrothermally hydroxysodalite ZM (pore diameter 0.4 nm)
and tested its performance using an experimental pervaporation setup. Effects of temperature, rate
and pressure on the membrane structure and performance were investigated for hydroxysodalite ZM
grown onto seeded mullite supports. Increasing pressure, feed rate and temperature increases the
flux linearly. Water flux of about 4 kg.m-2.h-1 was achieved at 3 bar, 3 l.min-1 and 60°C. Khajavi et
al. [313] synthesized hydroxysodalite ZM and tested it pervaporative desalination of North Sea
water and aqueous salt solutions for more than 100 h over a temperature range of 303–473 at 2.2
MPa. In all cases the membrane showed salt rejection better than 99.99%, the collected permeate
was ultra pure water with a resistance of 0.1 µS/cm at 25 ◦C. Flux through the membrane in
seawater desalination showed a steep increase with feed temperature, exceeding the flux values
obtained for pure water. Increasing the salt concentration of NaCl in the feed led to an increase in
the water flux, whereas the opposite trend was observed for NaNO3 solutions. It was speculated that
under the applied HT conditions, hydroxide groups in the sodalite cages were exchanged with
chloride anions of the solution, resulting in higher water mobility. The bulkier nitrate could not do
so, and a decrease in water flux was attributed to the decrease in water activity in combination with
a blocking effect by the nitrate anion.
Cho et al. [314] investigated the pervaporative seawater desalination characteristics of the NaA ZM
having upper limit of the non-zeolitic pore diameter 0.8 nm. ZM showed excellent (> 99.9%) salt
rejections for all of the ions in the seawater (Na+, K+, Mg2+, Ca2+, Sr2+, SO42-, PO43-, NO3-, F-, Cl-,
Br-), and up to 79.2% rejection for boron. The high rejections were attributed to a joint size
exclusion/charge exclusion/surface evaporation mechanism. High water flux in the seawater (1.9
kg.m-2.h-1at 69◦C) also was manifested, and was much higher than that in pure water at
temperatures below 100°C. Moreover, the apparent activation energy of the water permeation in
seawater was always lower than that in pure water. The higher water flux and low activation energy
were explained by the reduced electrostatic interaction between the positive surface charge and the
polar water. The positive surface charge was induced by the charge reversal that was incurred by
the adsorption of metal species on the zeolite surface. The water flux in the NaOH, NaCl, NaNO3
and Na2SO4 solutions also was investigated, and could be understood as a function of the surface
charge. The excellent salts rejection and water flux data indicated that the pervaporation process
incorporating the NaA ZM was a promising candidate for seawater desalination applications.
In addition to ZM, zeolite nano-particles was used to prepare polymer-zeolite nanocomposite
membranes, which were expected to combine the advantages of both materials. Jeong et al. [315]
prepared zeolite NaA/polymer membrane. For this aim, NaA type nanopartices in the size range of
50–150 nm with a Si/Al ratio of 1.5 were first synthesized and then dissolved into a cross-linking
agent solution before the interfacial polycondensation reaction. A homogeneous dispersion of
zeolite particles was achieved using ultrasonication. RO membranes with various zeolite loadings
were prepared. The membrane with increased zeolite loading was found to be smoother, more
hydrophilic and more negatively charged. The membrane exhibited 90% of flux and a slight
improvement in salt rejection relative to the polymer membrane without zeolite nano-particles.
Fathizadeh et al. [316] studied the effect of added NaX nano-zeolite into polyamide as a top thin
layer of membrane on water flux and salt rejection in a RO process. The thin film nanocomposite of

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polyamide and nano-NaX (40–150 nm) membranes was coated via interfacial polymerization of
trimesoyl chloride and m-phenylenediamine monomers over porous polyethersulfone ultrafiltartion
support. Different types of nanocomposite films were synthesized using two levels of monomer
concentrations and nanozeolite loading into the polyamide film. The prepared nanocomposite
membranes had higher thermal stability and more water permeability than the pure polyamide
membranes. The results showed that addition of nano-NaX to the polyamide membrane led to
improvement of surface properties such as RMS roughness, contact angle and solid–liquid
interfacial free energy, a decrease in film thickness and an increase in pore size and water flux.
Excellent membrane performance was observed for the nanocomposite membrane containing about
0.2% nano-NaX zeolite, 0.1% trimesoyl chloride and 2% m-phenylenediamine.
4. CONCLUSION
On the base of the reviewed publications, it could be concluded that, due to their unique properties,
zeolites have a great potential as effective sorbent materials for a large number of water treatment
applications, such as water softening (for boilers and drinking), ammonia removal (from municipal
sewage, animal farms, fertilizer factory wastewaters, fish breeding ponds, swimming pools),
removal of heavy metals (from natural waters, acid mine drainages, industrial wastewater),
phosphates removal, removal of dissolved organic compounds and dyes, oil spillages treatment,
separation of solid impurities, radioactive wastewater purification, seawater desalination, PRB, and
many others.
Synthetic zeolites obtained by reprocessing of industrial, municipal or agricultural waste materials,
especially CFA and RHA, have huge potential as a cost-effective, environmental-friendly solution
that can improve the efficiency of (waste)water treatment. The low price and the additional
ecological benefit (reduced raw materials mining and solid wastes disposal) of the production of
zeolites from wastes increase their popularity and inspire growing interest among zeolite
researchers and manufacturers worldwide.
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Zeolites for water and wastewater treatment: An overview

Rostislaw Kaischew Institute of Physical Chemistry, Bulgarian Academy of Sciences, Bulgaria

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Zeolites are crystalline microporous aluminosilicates, built up of a 3-dimentional framework of

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some cost-effective, environmental-friendly zeolites or zeolitic materials, obtained on the base of

3. RESULTS AND DISCUSSION

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Table 2. CEC of clinoptilolite from different deposits

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traces of NaP and NaA

3.1.2.2.2. Zeolites from municipal solid waste incineration ash (MSWIA)

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Table 5. CEC of some RHA-derived zeolites

3.1.2.2.5. Zeolites from other wastes

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3.2. (WASTE)WATER TREATMENT APPLICATIONS OF ZEOLITES

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presence of competitive ions. Maximum ammonia uptake is usually achieved at pH of the

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Cr3+ Hydroxysodalite From kaolin 500 5 34.7 [53]

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Zn2+ Beneficiated mordenites USA 654 4 22-23 [178]

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Cs+ NaA ZM Synthetic 133 99.4 [225]

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As (V) Ce-P, obtained from RHA 500 7.5 23.4 [129]

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