Available online at www.sciencedirect.

com

Procedia Environmental Sciences 17 (2013) 285 290

The 3rd International Conference on Sustainable Future for Human Security

SUSTAIN 2012

Fe-treated artificial zeolite as an adsorbent for anionic and

cationic pollutants
Erni Johana,*, Elvis Anup Shuklaa, Naoto Matsuea, Teruo Henmia
a

Laboratory of Applied Chemistry for Environmental Industry, Faculty of Agriculture, Ehime University,
3-5-7 Tarumi, Matsuyama 790-8566, Japan

Abstract
Artificial zeolite (AZ) synthesized from coal fly ash was treated with iron nitrate solution of OH/Fe=2.5 and
OH/Fe=0 in order to make new adsorbent for anionic and cationic pollutants. Decrease in cation exchange capacity
with the iron solution treatment indicated blocking of negative charge on zeolite structure by iron species. Adsorbed
iron was not released by extraction with 1M CH3COONH4, proving that iron is strongly adsorbed on the zeolite. The
AZ treated with the iron solution of OH/Fe=0 had higher capacity for phosphate adsorption. The adsorbed iron seems
to become anion adsorption site newly formed on zeolite structure.

2012 The
The Authors.
Authors. Published
Published by
by Elsevier
Elsevier B.V.
B.V. Open access under CC BY-NC-ND license.
2013
Selection
and/or
peer-review
under
responsibility
of SUSTAIN
conferences
committee
supported
by Kyoto
Selection and
peer-review
under
responsibility
of SUSTAIN
conferences
committee
and and
supported
by Kyoto
University;
University;
(OPIR), (GCOE-ES),
(GCOE-HSE),
(CSEAS),
(RISH), (GCOE-ARS)
(GSS) as co-hosts.
(OPIR), (GCOE-ES),
(GCOE-HSE),
(CSEAS), (RISH),
(GCOE-ARS)
and (GSS) as and
co-hosts.
Keywords: Artificial zeolite; iron; cation exchange capacity; phosphate adsorption

1. Introduction
Development of industry and agriculture is an important factor to support human life. On the other
hand, the development has caused pollutions in environment, such as heavy metals pollution in soil as
well as ground water, eutrophication in lake, and so on. Based on chemical properties, pollutants in soil
and ground water are divided into cationic and anionic species. Heavy metals pollutants are usually
present as cationic species; on the other hand arsenic, phosphorus, and chromium are usually present as
anionic species. Zeolite is tectoaluminosilicates characterized by three-dimensional network structure

* Corresponding author. Tel/fax:+81-89-946-9681.

E-mail address:johan@agr.ehime-u.ac.jp

1878-0296 2013 The Authors. Published by Elsevier B.V. Open access under CC BY-NC-ND license.

Selection and peer-review under responsibility of SUSTAIN conferences committee and supported by Kyoto University; (OPIR),
(GCOE-ES), (GCOE-HSE), (CSEAS), (RISH), (GCOE-ARS) and (GSS) as co-hosts.
doi:10.1016/j.proenv.2013.02.040

286

Erni Johan et al. / Procedia Environmental Sciences 17 (2013) 285 290

composed mainly of Si and Al tetrahedra [1]. The Al tetrahedron is formed when Si atom is replaced by
Al atom by isomorphous substitution resulting in negative charge in zeolite structure and the amount is
commonly called as cation exchange capacity (CEC). Due to this negative charge, zeolite is known as a
good adsorbent for heavy metals, such as lead, cadmium, copper, zinc and nickel [2, 3, 4]. Zeolites can be
found in nature (natural zeolite) and can be synthesized from pure chemical reagents (synthetic zeolites),
as well as from industrial by-products (artificial zeolites). In the recent decades, many studies have been
pointed out on recycling of by-products. For example, hydroxy sodalite and zeolite P (Na-P1) have been
synthesized from coal fly ash by heating treatment under alkaline conditions [5, 6, 7]. In the same manner,
zeolite can be synthesized from paper sludge ash [8, 9]. The products are called artificial zeolites. The
artificial zeolites have much greater CEC than natural zeolites do. Unfortunately, zeolites have no
positive charge in their structure; so, it is difficult to adsorb anionic pollutants, such as phosphate or
arsenate on them.
In this study, artificial zeolite synthesized from coal fly ash was treated with iron nitrate solution
(Fe(NO3)3), then physical and chemical properties were characterized by using powder X-ray diffraction
(XRD) and thermal gravimetry-differential thermal analysis (TG-DTA) techniques, CEC determination,
exchangeable iron and phosphate adsorption. The objective of this study was to produce useful adsorbent
from artificial zeolite, which has adsorption capacities for both cationic and anionic pollutants.
2. Materials and methods
Artificial zeolite (AZ) from coal fly ash, produced by Maeda Corporation, Japan, with calcium
saturation was used. Fe(NO3)3 was purchased from Nacalay Tesque. Two kinds of 0.01M Fe(NO3)3
solutions were prepared, one with NaOH/Fe molar ratio of 2.5 and another with NaOH/Fe of 0. To make
0.01M Fe(NO3)3 with NaOH/Fe of 2.5, 0.05M-Fe(NO3)3 solution was titrated slowly with NaOH solution,
so as to give final Fe(NO3)3 concentration of 0.01M with NaOH/Fe molar ratio of 2.5. Another solution
was made by simple dilution of 0.1M Fe(NO3) solution by distilled water.
Five grams of AZ was mixed with 200 mL of 0.01M Fe(NO 3)3 solution of NaOH/Fe=2.5, then was
shaken reciprocally for one hour and followed by centrifugation at 3000 g for 10 minutes. Supernatant
was decanted, another 200mL of the same solution was added again and the same procedure was repeated.
Addition of the Fe(NO3)3 solution was carried out totally three times. The sample was, then, washed with
distilled water for three times and followed by drying at 40 C for 24 h. The sample was abbreviated as
Fe-A. Similar saturation procedure was done with the Fe(NO) 3 solution of NaOH/Fe=0, with the solid
solution ratio of 10g/200mL; the product was abbreviated as AZ-B. Original AZ sample was washed with
distilled water for three times and was used as a reference sample.
The three samples (AZ, Fe-A, Fe-B) were subjected to physical characterizations by XRD (Rigaku
Ultima IV X-ray diffractometer) and TG-DTA (Rigaku Thermoplus TG 8100) techniques. Exchangeable
Fe was determined by extraction of the sample with 1M CH 3COONH4, followed by Fe analysis of the
extract using atomic absorption spectrophotometer (Hitachi Z-5000). Another extraction with 1M HCl
was done to determine total iron content of the samples.
The values of CEC were measured by a modified Schofield method: saturation with 0.5 M CaCl2
solution, followed by removal of excess CaCl2 by washing with 80% ethanol and extraction of Ca retained
on the samples by washing with 1M NH4Cl solution. Anion exchange capacity (AEC) was determined by
amounts of Cl- retained at pH 4. The analysis of Cl- was done by mercury (II) thiocyanate method; using
spectrophotometry [10] Phosphate, adsorption experiment was carried out by mixing each 50 mg of the
sample with NaH2PO4 solution of 0 to 2 mM, with total volume of 100 mL. The mixtures were shaken
reciprocally for 24 hours, and then were centrifuged at 9000 g for 15 minutes. Separated supernatants
were subjected for phosphate analysis by spectrophotometry method using ascorbic acid blue method [11].

Erni Johan et al. / Procedia Environmental Sciences 17 (2013) 285 290

3. Results and discussion

Visual observation showed that colour of artificial zeolites changed from grey (AZ) to reddish (Fe-A
and Fe-B). These indicated that iron was present in the Fe-A and Fe-B. Figure 1 shows XRD patterns of
the three samples: AZ, Fe-A and Fe-B. Original AZ sample showed mainly peaks of Na-P1
[Na6(Si10Al6O32).12H2O], quartz (SiO2), mullite and calcite (CaCO3). This indicated that the AZ contains
mainly Na-P1 type of zeolite. Quartz and mullite were still remained on the AZ, because those
compounds were hardly dissolved during zeolitization process. Furthermore, calcite was formed during
saturation process with calcium solution, where calcium reacted with CO3- ion. Similar patterns were
observed for Fe-A sample; but, in case of Fe-B sample, calcite peak was disappeared, and intensities of
all peaks were lower as compared to AZ and Fe-A. This is due to the dissolution of calcite with the
treatment by Fe(NO3)3 of NaOH/Fe=0, but not with that by Fe(NO3)3 of NaOH/Fe=2.5. Furthermore, the
decrease of the XRD peaks of Fe-B might be due to partial dissolution of zeolite even though, Na-P1
peaks were still observed clearly for both Fe-treated zeolite samples.

Fig. 1. Powder XRD patterns of the samples; (a). original AZ , (b). Fe-A, and (c): Fe-B

Figure 2 presents DTA curve of the samples. The original AZ sample showed three endothermic peaks
at 81 C, 125 C, and 160 C. These endothermic peaks appeared due to loss of water adsorbed on AZ
sample. The appearance of the three endothermic peaks indicated that there were three sites of water
adsorption with different bonding energy. First was water adsorbed on the surface, second was water
adsorbed between zeolite particles and third was water adsorbed by cations adsorbed on zeolite. Broad
exothermic peak around 650 C was due to combustion of carbon contained in the artificial zeolite.
Furthermore, a sharp exothermic peak at 876 C might be due to formation of mullite or -Al2O3. Iron
treated zeolite (Fe-A and Fe-B) showed broad endothermic peak at 82 C and a sharp endothermic peak
177 C, higher than that of the original sample. This means that water was absorbed more strongly in FeA and Fe-B; probably, it was adsorbed on Fe retained on zeolite. Furthermore, the exothermic peak due to

287

288

Erni Johan et al. / Procedia Environmental Sciences 17 (2013) 285 290

formation of mullite or -Al2O3 was not observed

iron.

l
l

it might be due to the protection of Al by adsorbed

Fig. 2. DTA (differential thermal analysis) patterns of the samples

Table 1 shows chemical properties of the samples. Total Fe was considerably high for Fe-A (355.6
cmol kg-1), even greater than CEC value of the original sample (324.8 cmol kg -1). Amounts of total iron
of Fe-B (144.9 cmol kg-1) was lower as compared to that of Fe-A. Furthermore, total amounts of iron and
CEC of iron treated samples were greater than that of original AZ samples, due to adsorption of iron on
zeolite in polymeric forms. However, the amounts of exchangeable iron were very low for all samples,
indicating that Fe was bonded strongly on zeolite structure. This means that these materials were stable
and possible to be applied in the environmental fields.

Table 1. Chemical properties of the samples.

Samples
AZ
Fe-A
Fe-B

Exchangeable Fe
(cmol kg-1)
UD*
0.1
UD*

Total Fe
(cmol kg-1)
5.6
355.6
144.9

CEC (cmol kg-1)

324.8
179.3
221.3

AEC (cmol kg-1)

UD*
1.5
4.5

*UD: undetectable

Furthermore, CEC decreased from 324.8 cmol kg-1 to 179.3 cmol kg-1 and 221.3 cmol kg-1 for Fe-A
and Fe-B, respectively indicating that the negative charge sites of the structure of zeolite were blocked
by adsorbed iron. Even though, the remained CEC value was high enough to provide adsorption sites for
cationic pollutants, such as heavy metals, cesium (including radioactive 137Cs) or strontium. As a
comparison, vermiculite (a clay mineral with the highest CEC in soil) has CEC about 100 cmol kg-1. AEC
values were relatively low for all Fe treated samples. It seemed that Fe adsorbed on zeolite did not create
so much newly positive charges.
Figure 3 shows phosphate absorption isotherm of Fe-B sample, with abscissa was equilibrium
phosphate concentration (C) and ordinate was the amounts of P adsorbed. At low phosphate concentration,

289

Erni Johan et al. / Procedia Environmental Sciences 17 (2013) 285 290

amounts of P adsorption increased steeply with increasing phosphate concentration, then became plateau
and increased again, steeply. The adsorption isotherm was plotted according to Langmuir equation, up to
equilibrium concentration of 0.62 mmol L-1. Langmuir adsorption equation is described as,
(1)
where X is amount of P adsorption, Xm is maximum P adsorption, C is equilibrium phosphate
concentration and K is a constant related to binding energy. That equation can be re-arranged as follow.
(2)
By plotting C/X against C, regression equation could be obtained; then, Xm and K could be calculated.
Plot of Langmuir equation is presented in Fig. 4. Maximum phosphate adsorption was calculated as 567
mmol kg-1. This amount was similar with phosphate adsorption on natural allophone [12]. Binding energy
was calculated as 3.4 (mM)-1. Allophane (natural clay found in volcanic ash soil), is known to have high
capacity for anionic pollutants, such as phosphate [12] and arsenate [13]. However, it is rarely found in
nature and it is difficult to synthesize in a large scale. By using artificial zeolite treated with Fe, we
produced cheap adsorbents for anionic and cationic pollutants.
1000

2
1.8

y = 1.7624x + 0.5185
R2 = 0.9684

1.6
1.4

C/X (g/L)

P Adsorbed (mmol/kg )

800

600

400

1.2
1
0.8
0.6

200

0.4
0.2

0
0.0

0.5

C (mmol/L)

1.0

1.5

Fig. 3. Phosphate adsorption isotherm of Fe-B sample

0
0.0

0.2

0.4
0.6
C (mmol/L)

0.8

1.0

Fig. 4. Plot of Langmuir equation of Fe-B sample

Equilibrium pH was around 6, and no increase pH was observed. The iron species retained on the
artificial zeolite may contain much Fe-OH groups, which is responsible for phosphate adsorption.
Phosphate represents anion; so, it is expected that the sample has the ability to adsorb other anionic
pollutants, such as arsenic or chromium. Study of adsorption of arsenic by this iron treated zeolite was
done elsewhere. Furthermore, only small amount of P adsorption was observed on Fe-A sample. This
means that iron treated procedure by using 0.01M Fe(NO 3)3 solution without addition of NaOH solution
gives better results for the adsorption of anions.
4. Conclusions
1.

Iron treatment on AZ changed physical and chemical properties of AZ, and created new anion
adsorption sites that are not existed in AZ.

2.

Iron treated artificial zeolite has high capacity for phosphate adsorption.

290

Erni Johan et al. / Procedia Environmental Sciences 17 (2013) 285 290

References
[1]
[2]
[3]
[4]

Hara N, Takashi H. Zeolite, basic and application. Kodansha, Tokyo; 1975, p. 330. In Japanese.
Ibrahim HS, Jamil TS, Hegazy EZ. Journal of Hazardous Materials 2010;182:842-847.
Miyaji F, Masuda S, Suyama Y. Journal of the Ceramic Society of Japan 2010;118:1062-1066.
Saito M, Ando T, Sugiyama O, Hiyoshi K, Satomic K, Henmi T. Journal of the Ceramic Society of Japan, supplement
2004;112(5):S79-S83.
[5] Henmi T. .Soil Sci. Plant Nutr. 1987; 33:517-521.
[6] Henmi T. New Ceramic. 1997;7:54-62. In Japanese.
[7] Molina A, Ploole C. Minerals Engineering. 2004;17:167-173.
[8] Ando T, Saito M, Muramatsu S, Hiyoshi K, Haruna J, Matsue N, Henmi T. Nendo Kagaku. 2003; 3: 158-166. In Japanese, with
English abstract.
[9] Fukugaichi S, Matsue N, Henmi T. Nendo Kagaku. 2007; 45 (4):233-237. In Japanese, with English abstract.
[10] Huang WD, Johns WD. Anal. Chim. Acta. 1966;37:508-515.
[11] Murphy J, Riley JP. Anal. Chim. Acta. 1962;27:31-36.
[12] Johan E, Matsue N, Henmi T. Clay Science 1997;10:259-270.
[13] Elvis AS, Matsue N, Henmi T, Johan E. Environmental Research Engineering and Management 2011;4(58):5-9.