Available online at www.sciencedirect.

com

Procedia Environmental Sciences 17 (2013) 279 284

The 3rd International Conference on Sustainable Future for Human Security

SUSTAIN 2012

Arsenate adsorption on iron modified artificial zeolite made

from coal fly ash
Elvis Anup Shuklaa*, Erni johana , Teruo Henmia and Naoto Matsuea
a

Faculty of Agriculture, Ehime University,3-5-7 Tarumi, Matsuyama 790-8566, Japan.

Abstract
Arsenic in its organic and inorganic forms has threatened the human life since ages. Many researchers and scientists
had made efforts in all the directions to find and remove poisonous arsenic from human surroundings. In the present
study an attempt was made to see the adsorption behavior of arsenate on the chemically modified artificial zeolite,
synthesized from coal fly ash. In the modification process the iron was rearranged and loaded on the surface of the fly
ash by dissolution and precipitation processes. Artificial zeolite synthesized from coal fly ash was treated with iron
nitrate solution. The decrease in the CEC indicates the reduction of negative charge on the zeolite structure by iron.
The iron modified artificial zeolite has comparatively high capacity for arsenate adsorption which was described by
the Langmuir isotherm model.
2013 The Authors.
2012
Authors. Published
Publishedby
byElsevier
ElsevierB.V.
B.V.
peer-review
under
responsibility
of SUSTAIN
conferences
committee
and and
supported
by Kyoto
University;
Selection and
and/or
peer-review
under
responsibility
of SUSTAIN
conferences
committee
supported
by Kyoto
(OPIR), (GCOE-ES),
(GCOE-HSE),
(CSEAS), (RISH),
(GCOE-ARS)
and (GSS) as and
co-hosts.
University;
(OPIR), (GCOE-ES),
(GCOE-HSE),
(CSEAS),
(RISH), (GCOE-ARS)
(GSS) as co-hosts.
Keywords: Arsenate; artificial zeolite; iron modification; fly ash, and Langmuir.

1. Introduction
Arsenic had always affected the mankind since ages, sometimes in a positive way as wood
preservatives, rodenticides and medicines and sometimes in a negative way as poison and carcinogenic
substance. Arsenic poisoning from different sources had cost many lives. According to a study, nearly
137 million people around the world were affected with arsenic in drinking water [1]. Since the ages
many researchers had spent the significant time in finding out the cause, source, and remediation of
arsenic. High arsenic concentration has been reported frequently in the USA, China, Chile, Bangladesh,
Taiwan, Mexico, Argentina, Poland, Canada, Hungry, Japan and India. Among all the countries

* Corresponding author. Tel.: +81-90-2895-7494; +81-89-946-9681; fax: +81-89-977-4364.

E-mail address: elvisshukla@gmail.com.

1878-0296 2013 The Authors. Published by Elsevier B.V.

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.2013.02.039

280

Elvis Anup Shukla et al. / Procedia Environmental Sciences 17 (2013) 279 284

Bangladesh and West Bengal of India are at high risk. Inorganic arsenic compound will be adsorbed
rather quickly through lungs and intestines while uptaking through skin is comparatively slow [2]. Cancer
of skin, bladder, liver and kidneys, lungs and prostrate glands, as well as coronal heart diseases and so
called Black foot disease are some adverse result from chronic As exposure.
Historically, arsenic plays ambivalent role in healing, murder and suicide purpose. Arsenic minerals
were mined by early Indian, Chinese, Egyptian and Greek civilization [3]. There is written evidence from
222 BC China concerning pharmaceutical products made from realgar (AsS) [4]. But it was in 1250 AD
that Saint Albertus Magnus synthesized arsenic for the first time by heating soap with orpiment (arsenic
trisulfide As2S3) [5, 6]. Since Arsenic is ubiquitous in environment, present usually in small amounts in
rocks, soil, water and air [7], common in pyrite, galena, chalcopyrite [8], it is continually threatening the
human life. The most common arsenic mineral is arsenopyrite, (FeAsS 2).The average concentration of As
in igneous and sedimentary rocks is approximately 2mg As kg , and common concentrations in most
rocks range from 0.5 2.5 As kg [9]. The average concentration of arsenic in soil is about 5 6mg As kg
which is higher than that of rocks but may vary from region to region. Weathering of rocks may mobilize
arsenic salts to arsenous acid and arsenic acid [10].
Various treatment methods such as ion exchange, reverse osmosis, ultra filtration, adsorption,
coagulation precipitation and adsorption co-precipitation by metals (predominately ferric chloride)
followed by coagulation have been proposed for removal of arsenic from water [11, 12]. In the present
study, an attempt is made to study the arsenic reclamation in aqueous medium using adsorption technique.
The iron modified artificial zeolite is used as adsorbent. Zeolite is known to be a good adsorbent for
heavy metals, such as lead and cadmium, copper, zinc and nickel due to the negative charges on the
surface or cation exchange capacity (CEC) [13, 14]. Mineralogists classify zeolites as tectoaluminosilicates, having a three dimensional network structure. Zeolites are composed mainly of silicon
(Si) and aluminium (Al) tetrahedra (4-coordinated aluminium). Zeolite can be found in nature (natural
zeolite) and can be synthesized from pure chemical reagents (synthetic zeolite) or from industrial byproducts (artificial zeolite). Many researchers and scientists around the world had made tremendous
efforts to synthesize zeolite from coal fly ash [15, 16]. The CEC of artificial zeolite is higher than the
natural zeolite, but because there is no positive charge on its surface, it is difficult for the anionic
pollutants to adsorb. Thus, in this study we try to modify the artificial zeolite with iron solution, and then
characterize it by X-ray diffraction, TG-DTA techniques (data not included) and chemical properties by
measuring CEC, exchangeable iron, and arsenate adsorption. The main objective of this study is to make
a cost effective adsorbent from coal fly ash which can have both cationic and anionic adsorption
capability.
2. Materials and Methods
2.1. Iron modification method
Artificial zeolite synthesized from coal fly ash, produced by the Maeda Corporation with calcium
saturation (AZ) was used in this experiment. Analytical grade of iron nitrite (Fe(NO3) 3) produced by
Nacalai tesque was used for the enrichment method. A solution of 0.01M of Fe(NO3) 3 was prepared. Five
grams of AZ was mixed with 200 mL of 0.01 M Fe (NO3)3 solution, and was shaken reciprocally for 1
hour, and followed by centrifugation at 3500 rpm by KUBOTA 5200. The supernatant was discarded, and
another 200 mL of the same solution was added again, and was followed by shaking and centrifugation.
Adding of the Fe (NO3)3 solution was totally done for three times. The sample was then washed by free
ion water three times, and was dried at 40 C. The sample was denoted as Fe-AZ. Original AZ sample
was washed with free ion water three times and was used as a blank.

Elvis Anup Shukla et al. / Procedia Environmental Sciences 17 (2013) 279 284

2.2. Sample characterization

The sample AZ and Fe-AZ were subjected for the physical characterization by using X-ray powder
diffraction (Rigaku Ultima IV X-ray Diffractometer), and TG-DTA /thermal gravimetric-differential
thermal analysis (Rigaku Thermoplus TG 8100) techniques. Exchangeable Fe was measured by extraction
of the sample with 1M CH3COONH4 solution, followed by Fe analysis by atomic absorption
spectrophotometry (AAS, Hitachi Z-5000). Extraction with 1M HCl was done to measure total iron
content in the samples.
Cation exchange capacity (CEC) was measured by a modified Schofield method: saturation with
0.5M CaCl2 solution, followed by washing of excess CaCl2 with 80% ethanol, and extraction of Ca with
NH4Cl solution. The amount of adsorbed calcium (CEC) was analyzed by AAS.
2.3. Batch experiment method
The 2mM arsenate stock solution was made using disodium hydrogen arsenate heptahydrate
(Na2HAsO4.7H2O) produced by Nacalai tesque. The adsorption experiment was conducted by mixing
each 50 mg of Fe-AZ sample with different concentration of Na2HAsO4 solution varying from 0 to 70
M with total volume of 100 mL. The initial pH was kept at 6 under 10mM NaCl background solution.
The mixtures were shaken for 24 hours at 100 rpm by oscillator shaker TAITEC TS-10, and then were
centrifuged at 9000 g for 20 to 30 minutes by KUBOTA 6930. The clear supernatant was separated and
was subjected for arsenate analysis by AAS (Hitachi Z-5000).
3. Results and Discussion
3.1. Sample Characterization
Change in the colour of artificial zeolite from grey (AZ) to reddish brown (Fe-AZ) was observed (Fig
1). This indicates the presence of iron in the sample. Figure 2 shows the X-ray diffraction pattern of the
samples AZ and Fe-AZ. Peaks of Na-P1 [Na6(Si10Al6O32).12H2O), quartz (SiO2), mullite, and calcite
(CaCO3) were prominent in the original AZ sample indicating that the sample contains mainly Na-P1 type
zeolite. Quartz and mullite were hardly dissolved during zeolitization process and thus peaks were visible.
Moreover, during saturation process calcium reacted with CO32- ion and thus calcite may be formed.
Similar patterns were observed for Fe-AZ also, but the calcite peaks were absent. This indicates that
calcite was dissolved by Fe(NO3)3 solution during the Fe saturation process. The decrease in the peak
intensity of Na-P1 for the Fe-enriched samples (Fe-AZ) may be due to partial dissolution of zeolite even
though Na-P1 peaks are still observed clearly.

(a)
Fig. 1. Change in the colour (a) AZ, (b) Fe-AZ

(b)

281

282

Elvis Anup Shukla et al. / Procedia Environmental Sciences 17 (2013) 279 284

Fig. 2. X-ray powder diffraction patterns of the samples: a: AZ, b: Fe-AZ

The chemical properties of the samples are shown in Table 1. Fe-AZ shows significant increase in the
total iron content. Iron may be bonded as polymeric form; however, the amount of exchangeable iron was
very low, and that indicates a strong Fe bound on zeolite structure. Hence, this material is stable and has
potential to be applied in environmental conditions. The CEC decreased from 324.75 cmol kg-1 to 221.25
cmol kg-1 indicating that the negatively charged sites of zeolite were attacked by the adsorbed iron.
Table 1. Chemical properties of the samples.
Sample
Exchangeable Fe (cmol kg-1)

AZ
UD*

Fe-AZ
0.001

Total Fe (cmol kg-1)

5.47

144.92

324.75

221.25

CEC (cmol kg-1)

*UD: undetectable

3.2. Adsorption study

The arsenate adsorption isotherm of Fe-AZ sample plotted with abscissa is equilibrium concentration
(C) and ordinate is amounts of As adsorbed (Fig 3a). At low concentration, the amount of adsorption is
high. On plotting the adsorption data according to the Langmuir adsorption equation a clear straight line
was observed (Fig 3b). Thus the maximum adsorption was calculated using the Langmuir formula:

283

Elvis Anup Shukla et al. / Procedia Environmental Sciences 17 (2013) 279 284

X= (XmKC) / (1+KC)

(1)

Where X is the amount of arsenate adsorbed, K is a constant related to binding energy, Xm is maximum
adsorption of arsenate on allophane, and C is the equilibrium arsenate concentration.
The maximum adsorption is calculated to be 40 molg -1 (Table 2). This cannot be labelled as very
good adsorbent, but coal fly ash when converted to zeolite and modified with iron can be produced as an
effective adsorbent. However, more research is needed in the modification method. In case of original AZ
sample, no adsorption was observed. This means that iron enrichment procedure by using 0.01M
Fe(NO3)3 gives better result.

(a)

(b)

Figure.3 (a) Arsenate adsorption isotherm on Fe-AZ. (b) Langmuir plots for the adsorption of arsenate

On the surface of Fe-AZ, much Fe-OH groups were generated, as the result of modification that acts as
adsorption site. Arsenate is a representative of anions, so the sample may have capacity to adsorb other
anionic pollutants such as phosphorous or chromium and other heavy and toxic metals. These will be
carried(a)out in further study. Because at the low initial (b)
concentration the adsorption of arsenate is high
(more than 75%) iron modified artificial zeolite can thus be used at the final stage of the purification
process.
Table 2. Adsorption maxima (Xm) and binding energy constant (K) for sites described by linear Langmuir plots.
Adsorbent

Xm
(molg-1)

K
(M)-1

R2

Fe-AZ

40.48

0.17

0.996

4. Conclusions
Iron enrichment on artificial zeolite changed its physical and chemical properties and created new
anion adsorption site that did not exist in the original one.
Significant adsorption of arsenate at a very low concentration can make iron enriched zeolite an
effective absorbent.

284

Elvis Anup Shukla et al. / Procedia Environmental Sciences 17 (2013) 279 284

The Fe-AZ proved to be financially viable as it was made from the coal fly ash and it thus gives a
new channel in the field of fly ash recycle.

References
[1] Smedley PL, Kinniburgh DG. A review of the source, behaviour and distribution of arsenic in natural waters. Applied
Geochemistry 2002;17(5):517 568.
[2] Savory J, Wills MR. Arsenic. In: E.Merian (ed.) Metalle in der Ummell, Verlag Chemie, Weinheim-Deerfirid Beach/Florida
Basel; 1984, p. 315 334.
[3] Azcue JM, Nriagu JO, Schiff S. Arsenic speciation in pore waters of Moira Lake, Ontario. Environ. International 1994;20: 517527
[4] Lin. Book of abstracts. In: Segh, editor. Third international conference on arsenic exposure and health effects, San Diego, Ca,
July 12-15; 1998, p. 173.
[5] Schroter W, Lautenschlager KH, Bibrack H. Taschenbuch der Chemie. Frankfurt: Harri Deutsch; 1983, p. 383-384.
[6] http://www.webelements.com/arsenic/history.html
[7] Onishi H. Arsenic. In: Wedepohl KH, editor. Handbook of geochemistry. Berlin: Springer; 1969;II_3:33.
[8] Goldschmidt VM. The principles of distribution of chemical elements in minerals and rocks. J Chem Soc London 1937;655673.
[9] Kabata-Pendias A, Pendias H. Trace Elements in Soils and Plants, CRC, Boca Raton; 1984, p. 315.
[10] Irgolic KT, Greschonig H, Howard AG. Arsenic. In: Analyst the Encyclopedia of Analytical Science, Academic, London; 1995.
[11] Harper TR, Kingham NW. Removal of arsenic from wastewater using chemical precipitation methods. Water Environ Res
1992;64(3):200 203.
[12] Viraraghavan T, Jin YC, Tonita PM. Arsenic in water supplies. Int J Environ Stud 1992;41:159 167.
[13] Ibrahim HS, Jamil TS, Hegazy EZ. Journal of Hazardous Materials 2010;182:842-847.
[14] Miyaji F, Masuda S, Suyama Y. Journal of the Ceramic society of Japan 2010;118(1383):1062-1066.
[15] Henmi T. Synthesis of hydroxySoil Sci. Plant. Nut. 1987;33:517-521.
[16] Molina A. Ploole C. A comparative study using two methods to produce zeolites from fly ash, Minerals Engineering
2004;17:167-17.