PROCESS ENGINEERING JOURNAL 1 (2017) 68–72

Process Engineering Journal

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Powder iron-containing adsorbents for arsenic removal: influence of heating

Marta Litynska *, Roman Antoniuk, Nataliia Tolstopalova, Igor Astrelin

National Technical University of Ukraine “Igor Sikorsky Kyiv Polytechnic Institute”, 37 Peremohy pr., Kyiv, 03056, Ukraine

ARTICLE INFO ABSTRACT

Article history: There is a variety of treatment methods for arsenic-containing waters, but adsorption is one of the
Received 8 October 2017 most popular among them, providing the removal of arsenic compounds from aqueous phase.
Received in revised form 30 October For sorption experiments, two iron (III)-containing adsorbents with different drying and roasting
2017 modes were used. Adsorbent roasted at 250°C demonstrated better As(V) removal properties than
Accepted 1 November 2017 adsorbent dried at 18°C. For all discovered impurities (Na2HAsO4, Na3AsO3 and
C16H13N2O11S2As) adsorbent dried at 18°C demonstrated worth sorption efficiency than the one
Keywords: processed at 250°C. Thus, the heating increases arsenic removal efficiency of iron-containing
Arsenic removal adsorbents, while the drying of iron (III) hydroxide at low temperatures gives insufficient result.
Adsorption © 2017 Process Engineering Journal.
Iron (III) oxyhydroxide
Arsenate
Arsenite

dimethylarsinic acid. Microbiological activity is the main reason of

1. Introduction these transformations. In addition, As(V) can replace P(V) in
different biological processes and after decompositions of aquatic
Arsenic occurs in nature in different oxidation states from −3 to plants, fishes and other organisms, arsenic enters water in organic
+5, but in natural waters +3 and +5 forms are predominant. Drinking form. Besides, arsenic can form soluble complexes with humic
water with arsenic content more than 10 μg/L is dangerous for compounds, which take place in humus layer of soil, peat bogs or in
consumption, causing different health problems. Arsenic water bodies with high humic content [3].
compounds occur in natural waters of many countries (Iran, China, There are a lot of treatment methods (reverse osmosis, ion
India, Chile, Mexico, Taiwan, Italy, etc.) and its concentration is exchange, coagulation, electrocoagulation, adsorption, etc.) for
often much higher than normative content [1]. Consequently, for arsenic-containing waters and all of them have advantages and
these countries arsenic removal is one of the most important stages disadvantages. Reverse osmosis has high energy consumption and
in drinking water treatment. is ineffective in As(III) removal, but doesn’t require big amount of
Speciation of arsenic compounds depends from geochemical chemicals and has small physical footprint. Ion exchange also
and climatic conditions; type of water body; chemical, hydrological doesn’t need a lot of space, but produces arsenic-containing water
and biological processes in water body; source of arsenic compound; after regeneration, which requires utilization. Coagulation by iron
pathways, etc. There are different natural and anthropogenic ways (III)-containing coagulants can effectively remove As(III), As(V) and
for arsenic compounds to get into natural waters (Fig. 1). organic matter, but has high chemicals consumption and high space
In natural waters arsenic can occur in organic or inorganic form, requirements. Now adsorption is one of the most popular methods
+5 or +3 oxidation state. In groudwaters, both inorganic As(III) and of arsenic compounds removal from aqueous phase. This method
As(V) may occur, but presence of As(III) is more frequent [2]. For has small physical footprint and doesn’t need permanent dosage of
surface water bodies, As(V) is more characteristic than As(III) due to chemicals. Some adsorbents can effectively purify water from all
aerobic conditions. Sometimes, especially during the warm period, forms of arsenic and many other pollutants. Also, it is possible to
arsenic is in organic forms, i.e. monomethylarsonic acid or apply different type of adsorbents in one filter [3].

* Corresponding author. E-mail address: [email protected]

© 2017 Process Eng. J. Process Engineering Journal is licensed under a "Creative Commons Attribution-NonCommercial 4.0 International License (CC BY-NC 4.0)".
 PROCESS ENGINEERING JOURNAL 1 (2017) 68–72 69

produced at incessant mixing by magnetic stirrer. After that slurry

was filtered and rinsed on the filter by distilled water.
One portion of rinsed iron (III) hydroxide was dried to complete
dryness in desiccator at the temperature of 18 °C and then
powdered.
Other portion was dried at the temperature of 105 °C during 10
h. Then it was crushed and after that roasted during 1 h at 250°C.
Cooled material was powdered.

2.2. Adsorption experiments

For sorption experiments, Na2HAsO4, Na3AsO3 and

C16H13N2O11S2As solutions were used. Portions (200 mL) of
Na2HAsO4 solution (initial concentration of As(V) was 500 μg/L)
were placed in a conical flasks (volume of flask is 250 mL) with
screw caps. Sorbent dose was 0.25 g/L. Sorbent was dosed into
flasks. After that flasks are placed on the orbital shaker. Shaking
durations were: 5, 10, 20, 40, 90 and 120 min. After sorption,
solutions were filtered and analyzed.
Fig. 1 - Sources and pathways of arsenic compounds getting into As(V) concentration in filtrate was determined photometrically.
natural waters. The method is based on the methodology which applies ammonium
molibdate and ascorbic acid with subsequent measurement of
Different types of adsorbents can be used for arsenic removal, optical density at the wavelength of 840 nm [24].
such as: ferric hydroxide, iron (III) oxyhydroxide, iron (III) oxide, For As(III) sorption, Na3AsO3 solution (initial concentration of
magnetite, aluminium oxide, chitosan-based sorbents, CuO, zero- As(III) was 500 μg/L) was used. Other experimental conditions were
valent iron, zirconium compounds, zeolites, TiO2, Mn3O4, activated the same. Filtrate was oxidized to transform As(III) into As (V). After
carbons, different wastes and by-products, etc [1, 4-11]. that concentration was determined according to the previous
In addition, different combinations of these adsorbents can be procedure.
used, for instance: TiO2-impregnated chitosan bead, natural zeolite For experiments with organic arsenic compounds
(clinoptinolite type) modified by magnetite, Fe-sericite composite C16H13N2O11S2As solution was prepared. Initial content of
powder, porous silica modified by bis(3-triethoxysilylpropyl) C16H13N2O11S2As (Fig. 2) was 20 mg/L. Prepared solution has a red
tetrasulfide, multiwall carbon nanotube doped by zero valent iron, color.
hydrogel-biochar composite, zirconium-doped activated carbon Other conditions were analogical. Residual concentration was
fiber, egg shells coated by manganese oxide, aluminum determined by the measurement of filtrate optical density at the
oxyhydroxide-poly[(4-vinylbenzyl)trimethylammonium chloride] wavelength of 500 nm [25].
hybrid sorbent, zirconium oxide on alginate beads, Fe-Mn binary
oxide impregnated chitosan bead, chitosan/Cu(OH)2 and
chitosan/CuO composites, etc [12-23].
However, iron-containing sorbents are cheap, easy synthesized
and eco-friendlier than any other adsorbents. That’s why they are
still very popular for arsenic removal. NaOH solution is usually
used for precipitation of iron (III) hydroxide, but in our case
ammonia solution was used. It is well known that precipitation pH,
concentration and type of reagents and drying mode have very great
influence on the properties of iron compounds, but low-temperature
drying (under approximately room temperature) was never
previously discovered. Theoretically, this adsorbent can be more
hydrated and have better adsorbent properties than sorbents with
high-temperature drying. But different processes can take place and
affect adsorption characteristics. Thus, the comparison of two
heating modes (18°C and 250°C) can give interesting results.

2. Materials and methods

2.1. Synthesis of iron-containing powder sorbents

Fig. 2 - Structure of 5-hydroxy-3-[[2-
Iron (III) hydroxide was precipitated from concentrated FeCl 3 [hydroxy(oxido)arsoryl]phenyl]hydrazinylidene]-4-
solution by 5% solution of NH4OH at pH 10. Hydroxide was oxonaphthalene-2,7-disulfonate.
70 PROCESS ENGINEERING JOURNAL 1 (2017) 68–72

3. Results and discussion 0.91 mg/L with removal efficiencies of 94% and 95.5%, respectively.
But even after 5 min of the adsorption, both sorbents showed high
Adsorbent roasted at 250°C (A2) demonstrated better As(V) efficiency (91.7% for A1 and 92.4% for A2).
removal properties than adsorbent dried at 18°C (A1) (Fig. 3).
During 120 min sorption, A2 reduced As(V) concentration from 500 100
to 115 μg/L (77% removal), but in A1 case, As(V) content decreased 90
only to 207 μg/L (58.6% removal). 80

Removal efficiency, %
70
60
100 18 °C
50
90 250 °C
40
80
30
Removal efficiency, %

70
20
60
18 °C 10
50
250 °C 0
40 0 20 40 60 80 100 120
30 Tim e, m in
20
10
0
0 20 40 60 80 100 120 Fig. 4 - As(III) elimination by adsorbent roasted at 250°C (A2) and
Tim e, m in
adsorbent dried at 18°C (A1).

Fig. 3 - As(V) removal by adsorbent roasted at 250°C (A2) and

adsorbent dried at 18°C (A1). 100

90
A1 needed too much time (about 5 days) to dry at the 80
temperature of 18°C. Therefore, different stabilization processes
70
Removal efficiency, %

could take place, which could quite efficiency reduce the sorption of
60
the adsorbent. After 2 h sorption, capacities of adsorbents were 1.17
18 °C
and 1.54 mg As(V)/g for samples dried at 18°C and 250°C, 50
250 °C
respectively. But equilibrium capacity could be much higher. 40
According to Ref. [26], some materials had worth or better 30
adsorption properties, for example, iron oxide coated sands had
20
lower As(V) capacity (0.008−0.043 mg/g), ferrihydrite capacity was
10
0.25−111.02 mg/g (conditions had very big influence), but TiO2 was
0
more effective (4.65−37.46 mg/g). Thus, A1 and A2 adsorption
0 20 40 60 80 100 120
efficiency was comparable with other popular adsorbents for arsenic
Tim e, m in
removal.
Also, these two samples had different structure. A1 was much
more amorphous than A2, because A1 didn’t undergo thermal
decomposition. During the heating, iron (III) hydroxide lost water Fig. 5 - C16H13N2O11S2As removal by adsorbent roasted at 250°C
and became more crystalline due to the formation of FeO(OH) and (A2) and adsorbent dried at 18°C (A1).
Fe2O3. But in the case of As(III), the difference was not so significant
(Fig. 4). Thus, heating mode during adsorbent preparation had very
During the first phase (10−15 min), A1 showed better results significant influence on sorption of inorganic As(III) and As(V), but
than A2, but later A2 reduced arsenic concentration more for arsaryl compound the difference was mitigated. During heating,
significantly than A1. During 120 min sorption, A2 removed 71.6% precipitated amorphous ferrihydrite lost water and changed its
(residual arsenic concentration was 142 μg/L) and A1 removed only structure. It became more crystalline and iron content increased in
63.8% (residual content was 181 μg/L). These adsorbents sorbent with decreasing of water and OH-group content.
demonstrated same As(III) capacities (1.28 and 1.43 mg/g for A1 and Consequently, in this case for As(III) and As(V), high iron content
A2, respectively), which were comparable with such sorbents as iron was more important than availability of OH-groups. But OH-groups
oxide coated sands (0.028−0.136 mg/g), nanoscale zero-valent iron were perspective in terms of ion exchange (OH− and arsenate or
(2.47 mg/g), modified calcined bauxite (1.37 mg/g), etc. [26]. arsenite anions could be interchanged). Thus, it is expediently to
A1 and A2 removed C16H13N2O11S2As very effectively and continue experiments with other drying temperatures, for example,
demonstrated the extent levels for water treatment (Fig. 5). 50 or 75°C. Amorphous iron (III) hydroxide continues to be
During 120 min of sorption, A1 reduced concentration of amorphous after these heating modes, but exsiccation is quicker,
C16H13N2O11S2As from 20 to 1.21 mg/L and A2 reduced content to hence influence of different stabilization processes can be lower.
 PROCESS ENGINEERING JOURNAL 1 (2017) 68–72 71

Mukherjee, Removal of arsenic from groundwater in West

4. Conclusion
Bengal, India using CuO nanoparticle adsorbent,
Environmental Earth Sciences 73 (2015) 3593-3601.
Two iron (III)-containing adsorbents with different drying and [8] O. Eljamal, K. Sasaki, S. Tsuruyama, T. Hirajima, Kinetic
roasting modes were used for arsenic removal from aqueous Model of Arsenic Sorption onto Zero-Valent Iron (ZVI),
solutions. Adsorbent roasted at 250°C (A2) demonstrated better Water Quality, Exposure and Health 2 (2011) 125–132.
As(V) removal properties than adsorbent dried at 18°C (A1). During [9] R. Vera, C. Fontas, E. Anticó, Titanium dioxide solid phase
for inorganic species adsorption and determination: the
120 min sorption, A2 reduced As(V) concentration from 500 to 115
case of arsenic, Environmental Science and Pollution
μg/L (77% removal), but in A1 case As(V) content decreased only to
Research 24 (2017) 10939–10948.
207 μg/L (58.6% removal). But in the case of As(III), the difference [10] K. Babaeivelni, A.P. Khodadoust, D. Bogdan, Adsorption
was not so significant. During 120 min sorption, A2 removed 71.6% and removal of arsenic (V) using crystalline manganese
(residual arsenic concentration was 142 μg/L) and A1 removed only (II,III) oxide: Kinetics, equilibrium, effect of pH and ionic
63.8% (residual content was 181 μg/L). strength, Journal of Environmental Science and Health Part
A1 and A2 removed C16H13N2O11S2As very effectively and A Toxic/Hazardous Substances & Environmental
Engineering 49 (2014) 1462-1473.
demonstrated the same results. During 120 min sorption, A1
[11] S. Fiore., T. Marengo, C. Briens, F. Berruti, Arsenic removal
reduced concentration of C16H13N2O11S2As from 20 to 1.21 mg/L and from drinking water by means of low-cost biochars derived
A2 reduced content to 0.91 mg/L with removal efficiencies of 94 and from miscanthus and coconut shell, Conference: Biochar:
95.5%, respectively. But even after 5 min of the adsorption, both Production, Characterization and Applications (2017) 25-
sorbents showed high efficiency (91.7% for A1 and 92.4% for A2). 30.
Consequently, in the case of all discovered impurities [12] S.M. Miller, M.L. Spaulding, J.B. Zimmerman,
Optimization of capacity and kinetics for a novel bio-based
(Na2HAsO4, Na3AsO3 and C16H13N2O11S2As), adsorbent dried at
arsenic sorbent, TiO2-impregnated chitosan bead, Water
18°C (A1) demonstrated worth sorption efficiency than the Research 45 (2011) 5745-5754.
adsorbent roasted at 250°C (A2). There were different explanations [13] M. Vaclavikova, Magnetic Zeolite as Arsenic Sorbent. In
for this. A1 needed quite much time (about 5 days) to get dried at Stefusova et al (Eds), Water Treatment Technologies for the
the temperature of 18°C. As a result, different stabilization processes Removal of High-Toxicity Pollutants (2009), (pp. 51-59).
could take place. It could reduce sorption efficiency of the adsorbent. [14] J. Kim, C. Lee, S.M. Lee, Lalhmunsiama, J. Jung, Chemical
Also, these two samples had different structure. A1 was much more and toxicological assessment of arsenic sorption onto Fe-
sericite composite powder and beads, Ecotoxicology and
amorphous than A2, because A1 did not undergo thermal
Environmental Safety 147 (2017) 80-85.
decomposition. During heating, iron (III) hydroxide was [15] H. Vojoudi, A. Badiei, S. Bahar, G.M. Ziarani, F. Faridbod,
dehydrated and became more crystalline due to the formation of M.R. Ganjali, Post-modification of nanoporous silica type
FeO(OH) and Fe2O3. SBA-15 by bis(3-triethoxysilylpropyl)tetrasulfide as an
Thus, the heating increases arsenic removal efficiency applying efficient adsorbent for arsenic removal, Powder
iron-containing adsorbents and the drying of iron (III) hydroxide at Technology 319 (2017) 271-278.
[16] H. Alijani, Z. Shariatinia, Effective aqueous arsenic
low temperatures gives insufficient result.
removal using zero valent iron doped MWCNT
synthesized by in situ CVD method using natural α-Fe2O3
REFERENCES as a precursor, Chemosphere 171 (2016) 502-511.
[17] M.L. Sanyang, W.A.W.A.K. Ghani, A. Idris, M. Bin Ahmad,
Hydrogel biochar composite for arsenic removal from
[1] M. Litynska, N. Tolstopalova, I. Astrelin, Neutralization of wastewater, Desalination and Water Treatment 57 (2016)
arsenic pollutants, contained in natural waters: The 3674-3688.
theoretical analysis of solubility of some arsenates and [18] D. Zhao, Y. Yu, J.P. Chen, Fabrication and testing of
optimization of the processes, Journal of Water and zirconium-based nano-particle doped activated carbon
Environmental Nanotechnology 2 (2017) 1-8. fiber for enhanced arsenic removal in water, RSC Advances
[2] H. Garelick, H. Jones, A. Dybowska, E. Valsami-Jones, 6 (2016) 27020-27030.
Arsenic pollution sources, Reviews of Environmental [19] S. Mubarak, M. Zia-ur-Rehman, M.N. Chaudhry, Modified
Contamination 197 (2009) 17-60. Eggshells as Cost Effective Adsorbent for the Treatment of
[3] M. Litynska, I. Astrelin, N. Tolstopalova, Ways of Arsenic Arsenic(III) Contaminated Industrial Effluents, Asian
Compounds Getting into Natural Waters, Modern Journal of Chemistry 27 (2015) 1995-2000.
Environmental Science and Engineering 3 (2017) 50-60. [20] J. Pérez, L. Toledo, C.H. Campos, J. Yañez, B.L. Rivas, B.F.
[4] B. Xie, M. Fan, K. Banerjee, Modeling of arsenic(V) Urbano, Arsenic sorption onto an aluminum
adsorption onto granular ferric hydroxide, American oxyhydroxide-poly[(4-vinylbenzyl)trimethylammonium
Water Works Association 99 (2007) 92-102. chloride] hybrid sorbent, RSC Advances 6 (2016) 28379–
[5] K. Debiec et al., The influence of thermal treatment on 28387.
bioweathering and arsenic sorption capacity of a natural [21] O.H. Kwon, J.O. Kim, D.W. Cho, R. Kumar, S.H. Baek, M.B.
iron (oxyhydr)oxide-based adsorbent, Chemosphere 188 Kurade, B.H. Jeon, Adsorption of As(III), As(V) and Cu(II)
(2017) 99-109. on zirconium oxide immobilized alginate beads in aqueous
[6] R. Brion-Roby, J. Gagnon, J.-S. Deschênes, B. Chabot, phase, Chemosphere 160 (2016) 126–133.
Development and treatment procedure of arsenic- [22] J. Qi, G. Zhang, H. Li, Efficient removal of arsenic from
contaminated water using a new and green chitosan water using a granular adsorbent: Fe-Mn binary oxide
sorbent: kinetic, isotherm, thermodynamic and dynamic impregnated chitosan bead, Bioresource Technology 193
studies, Pure and Applied Chemistry 89 (2017) 840-852. (2015) 243–249.
[7] K. Mcdonald, K.J. Reddy, N. Singh, R.P. Singh, S. [23] K.Z. Elwakeel, E. Guibal, Arsenic(V) sorption using
72 PROCESS ENGINEERING JOURNAL 1 (2017) 68–72 35

chitosan/Cu(OH)2 and chitosan/CuO composite sorbents, arsenic-containing waters (in Ukrainian), Young Scientist 9
Carbohydrate Polymers 134 (2015) 190–204. (2017) 270-281.
[24] State Standard 4152-89. Drinking water. Determination of [26] D. Mohan, C. U. Pittman Jr, Arsenic removal from
arsenic mass concentration (in Russian). water/wastewater using adsorbents - A critical review,
http://www.internet-law.ru/gosts/gost/19530/. Journal of Hazardous Materials 142 (2007) 1–53.
[25] M. Litynska, R. Antoniuk, N. Tolstopalova, I. Astrelin,
Application of arsenic aromatic compounds in modeling of

Please cite this article as: M. Litynska, R. Antoniuk, N. Tolstopalova, I. Astrelin, Powder iron-containing adsorbents for
arsenic removal: influence of heating, Process Eng. J. 1 (2017) 68−72.