Proceedings of the 4

th
International Conference on Nanostructures (ICNS4)
12-14 March, 2012, Kish Island, I.R. Iran
Nanoparticle zerovalent iron effects on Arsenic(V) removal

H. Koohpayehzadeh Esfahaani
a*
, A. Torabian
a
, T. Yazdanparast
c

a
Department of Environment Engineering, Tehran University , Tehran, Iran
b
Department of Environment Engineering, Tehran University , Tehran, Iran
c
Department of Fisheries and Environmental, University of Science and Technology , Tehran, Iran
*hkesfahaani@gmail.com

Abstract: Arsenic is one of the most toxic Elements presents in the groundwater and surface water, that threat human
and other animals health. Arsenic removal has done with different kinds of methods. In this test has investigated
arsenic removal from drinking water with nanoparticle zirovalent iron (NZVI) down to standard limit (0.01 mg/lit). In
this experience arsenic mixed with NZVI in ultrasonic then separates from water with VATMAN paper 0.45 m. Then
survived arsenic in the water measured with ICP device with As>0.01mg/lit measurement. In this article effect of
mixed time, pH, NZVI dose and arsenic dose has investigated. After many tests 1mg arsenic can be removed 100%
with 0.05g NZVI in 8min.PH and time mixing change investigated in this article. Arsenic has removed 100% in high
range of pH from 5 to 10. Ions chloride, sulphate and chromium dont have influence in arsenic removal level instead
of present carbonate, bicarbonate and phosphate ions.
Keywords: Arsenic; Nanoparticle Zirovalent Iron (NZVI); mix time; pH; competition ions;
Introduction
Arsenic is a highly toxic metal for humans, animals and
plants [1]. Entering high amounts of this substance in
human body cause skin cancer, lung, and bladder. Given
that Arsenic exists in soil and water and is created by
human activities like farming and mining and etc, many
areas of the planet are infected with this matter [2].
To protect against toxicity of this substance, the
World Health Organization and many international
legislator institutions suggested 0/01 mg/l for the
maximum permissible concentration of arsenic in
water[3]. Arsenic toxicity depends on the composition of
this element. The most important types of arsenic in
nature which is in found in ground waters and the surface
waters are inorganic samples which are for HAsO32 and
H2AsO3 for arsenit and HAsO42 and H2AsO4 for
arsenate[4].
There are different ways to remove arsenic from water
[5]. Methods like absorption on activated carbon and
activated alumina have lessened these problems to some
extent [6]. But removal of arsenic by zero valent iron in
different forms such as powder chips and ... was highly
regarded because of high reactivity [7,8]. The removal of
arsenic with NZVI has achieved promising results [9].
In this paper we attempt to evaluate remove the amount
of removal of arsenic from water by NZVI. PH, amount
of nanoparticles, and the mixing time and the amount of
arsenic, are important factors in this study. Also, the
impact of sulphate ions, chlorate, chromium, phosphate
and carbonate has been studied on the removal of arsenic.
Little studies have been done in this area. Sushil Kanel et
al was performed the study of removal of trivalent arsenic
by zero valent iron nanoparticles in which the effect of
silicate ions, phosphate and sulfate are considered [10].
Morgada et.al, 2009 have investigated the removal of
pentavalent arsenic with zero valent iron nanoparticles
with the effect of ultraviolet light and acid Humic. [11]
Su et.al, 2001 have done some studies on the effect of
many ions on removal of arsenate by zero valent iron
[12]. In this study the impacts of wide range of ions in
underground water on the removal of arsenate by
nanoparticles has been investigated. Also the amount of
removal of arsenic on isotherms has been adopted by
Ferndlich and Langmier.
Experimental
NZVI which is used in this research is the business
product of RIPI, which is made under standard
conditions. According to announced characteristics, these
covered black nanoparticles have 65% iron and their size
is 8-18 nm and their effective level is 59-79 m2/g.
Necessary arsenate is derived from sodium arsenate
salt Na2HAsO4.7H2O. In addition, in order to prevent
sedimentation, the desired solutions are built on daily
concentration of 100 mg/l and are diluted for the relevant
tests. Chloride and sulphate solutions at 200 and 400 mg/l
concentrations are made of NaCl MgCl
2
CaCl
2
Na
2
SO
4

, MgSO
4
.7H
2
O salts. Carbonate salts solution are
obtained in 150 and 300 mg/ L concentrations of CaCO3
and Na2CO3 salts, and phosphate salts solutions are
obtained in 100 and 500 mg/l concentrations of
Na
2
H
2
PO
4
.H
2
O, KH
2
PO
4
and K
2
HPO
4
salts, and
chromium salt solutions are obtained in 0.5 and 1 mg/l
concentrations of K
2
Cr
2
O
7
salt. All above salts are the
products of Merck Company in Germany, and the
solution has been prepared from dionized water with less
than 0.1 Microzimens electrical conductivity. Arsenate
solution with concentration of 1 mg/l for 1, 2, 5, 8 and 10
minutes are in contact with NZVI, and NZVI with 0.01,
0.02, 0.04 and 0.05 g values were used. For suitable
mixing and dispersion of NZVI in solution, ultrasound
device "Power Sonic 240" with average wavelength are
used. In order to change PH, nitric acid and NACL are
used, and 5, 7, 9 and 10 values pH are considered for this
1169

Proceedings of the 4
th
International Conference on Nanostructures (ICNS4)
12-14 March, 2012, Kish Island, I.R. Iran
study. Also in order to measure the PH, PH meter
Motrohom- which is the product of Hetch Company of
America, is used. Nanoparticles are used for the
separation of nanoparticles of Watman .45 micrometers
paper filter. In order to follow the adsorption process,
Frendlich and Langmuir isotherm equations, the
adsorbent with of 0.05 g value and in 10 minutes contact
time and pH = 7 and arsenate with 0.5, 1, 5 and 10 mg
concentrations have been tested. To measure the effect of
chloride and sulphate ions in the absorption process two
200 and 400 mg/L, 100 and 500 mg/l concentrations for
the phosphate and 150 and 300 mg/l concentrations for
carbonate, and 0.5 and 1 mg/l concentrations for
chromate ion was used. This part of experiments has been
done at concentrations of 1 mg/l of arsenic and 0.05 g of
zero valent iron nanoparticles, the mixing time of 8
minutes, and medium-wave ultrasonic devices with pH =
7 have been used.

Results and Discussion
According to results of various researches it indicated
that the dominant process of removal of arsenic in aerobic
and anaerobic (anoxic) systems is different. Reactions
which lead to the removal of arsenic in the presence of
oxygen are faster than the reactions which perform
without of oxygen.
In the presence of dissolved oxygen, iron hydroxides
are formed quickly on the surface of iron particles and are
formed in suspended particles within the solution. In such
circumstances, the main absorption process should be
considered as removal of As (III) and As (V) [13].
Electronically potential of As (III) - As (V) and As (0)
- As (III) pairs in oxidation and deduction reactions of
more than the same amount is in H2O-H2. And this
indicates that this pentavalent and trivalent arsenic are
stronger absorbents than water, and thermodynamically,
their deduction to As(0) is which are insoluble are
restored to As (0). Regarding the contents, it possible by
zero valent iron. In

Figure1- NZVI dosage and mixing time dose effects
on Arsenic removal
As it is shown in Figure (1), the efficiency of removal
of arsenic increases with increase in the contact time and
increase in the concentration of NZVI. Results shows that
the NZVI are able to remove arsenic in a short time. But
it seems that the concentration of nanoparticle is more
effective than contact time and the effect of contact time
diminishes with increasing in the concentration of NZVI.
The removal of arsenic increases over time because after
some times, the pitting and corrosion on the surface of
iron increased over time and thus absorption of cross area
increases over time and the active position to absorb
arsenic changes and the number of products from the
reaction of iron in the watery environment increases,
which leads to increased efficiency of removal. Increased
concentrations of NZVI leads to increase in the active
surface sites and increase in the possibility of attracting
more collision between nanoparticles and increase in
oxidation and deduction reactions [14,15].

Figure2- pH and mixing time dose effects on Arsenic
removal
Figure (2) shows the simultaneous effect of PH and
mixing time on removal arsenic; according to the figure it
can be inferred that increase in the efficiency has direct
relationship with contact time and is inversely related to
increases in pH. It is observed that in experiments with
concentration of 0.05 g of nanoparticle (of the best
performance of concentration) and in 8 minutes of contact
time, changes in pH do not affect the testing process. It
can be concluded that nanoparticles of zero capacity iron
is capable of removal of arsenate in the wide range of PH.
The results of simultaneous influences of
concentration of NZVI and pH on the removal of arsenic
can be observed in figure (3).

Figure3- pH and NZVI dosage effects on Arsenic
removal
As noted, increase in pH leads to decrease in the
efficiency of removal, but the effect of increase in NZVI
is more effective in the removal process of arsenate, and
with the proper amount of NZVI, pH value does not
affect the removal process. Increasing the active surface
sites for arsenate absorption and increases in oxidation
and deduction reactions caused by increasing
concentrations of zero valence iron nanoparticles,
eliminates the impact of repulsion force caused by
homonymous electron between arsenate and zero valence
iron nanoparticles in high PHs. Results of Hung-Yee Shu
Studies revealed that in alkali conditions, ferrous ions
changes to solution due to contact between nanoparticle
surface and hydroxyl radicals, and leads to the
precipitation of hydroxyl. The sedimentation occupies the
exterior active positions of nanoparticles and prevented
1170

Proceedings of the 4
th
International Conference on Nanostructures (ICNS4)
12-14 March, 2012, Kish Island, I.R. Iran
from further activity [16]. Sushil Raj Kanel showed that
increases in PH to 11 percent leads to decrease in arsenate
removal from the 100 to 37.9 percent, Due to the
repulsion force between nanoparticles and arsenate
because of negative electron. Also, increases in the
removal of arsenic from 15 percent to 99 percent are due
to concentration of zero valence iron nanoparticles
removal from 0.05 to 5 g/L [17,11]. Also in other
researches such as Hung-Yu-She et al on the removal of
Azo dye (Acid Black 14), Niuo-Shao-FEng et.al on
Hexavalent chromium removal, Yung et.al on nitrate
removal and Giasuddin et.al on Humic acid removal by
NZVI, reduced efficiency of absorption due to increase in
PH and increased efficiency with increased concentration
of NZVI has been reported [18, 19, 20] which are
consistent with the results of this research.
nZVI=0.05
y = 2.3691x 17.003
R
2
= 0.9494
2
1
0
1
2
3
4
5
6
7
0 2 4 6 8 10 12

Figure4- Frendlich isotherm for Arsenic removal with
NZVI
nZVI=0.05
y = 9.564x 0.010
R = 0.998
1
0
1
2
3
4
5
6
7
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7

Figure5- Langmuir isotherm for Arsenic removal with
NZVI
according to figure 4 and 5, comparison of correlation
coefficients obtained from the study of Frendlich and
Langmuir arsenate absorption isotherms, it is conducted
that arsenate follow these isotherms in the correlation
coefficient of 949% in Frendlich isotherm and in the
correlation coefficient of 998% in Langmuir isotherm.
Table (1) shows the removal of arsenic from water by
the iron nanoparticles in the presence of different
amounts of different ions in the water. Also shows the
concentrations of arsenic ion before and after the reaction
in the presence of added ions. Presence of chloride,
sulphate and chromate ions at different concentrations
does not affect the absorption of in this reaction and this
ion can reach to less than standard amounts. But the
presence of phosphate, carbonate and bi-carbonate ions
reduces the amount of arsenic and above all, phosphate
ions has great impact on the removal of arsenic.
Table1- Arsenic dosage within other ions
Sushil Raj Kanel et.al, and Su and Puls has achieved
similar results in 2001 [10,12].
Conclusions
Due to extensive defined areas in the world and
especially in west and north- west of Iran which have
contaminated groundwater, application of low cost and
high performance method can be highly effective. Iron
nanoparticles in very low scale and in short time and
without advanced facilities is capable to remove arsenic
in different conditions, so that Changes in pH and the
presence of ions has not important effect on the efficiency
of this method and this is one the important capabilities of
this method.

Acknowledgment
This research has been carried out in the form of MS
thesis and with financial support of Ph.D Torabian and
laboratory facilities of the University of Tehran in the
Faculty of Environment.

References
[1] Web page: Digital Grac, La Plata. (2002)
Prospect of Rural Latin American Communities
for Application of Low-cost Technologies for
Water Potabilization, OAS Project AE 141/2001,
M.I. Litter (Editor),
http://www.cnea.gov.ar/xxi/ambiental/agua-
pura/default.htm.
[2] Z. Lin, R.W. Puls (2000),Adsorption, desorption
and oxidation of arsenic affected by clay minerals
and aging process. Environ. Geol. 39 (7):p. 753-
759.
[3] World Health Organization, Guidelines for
drinking water quality,( 2004) vol. 1,
Recommendations,3rd ed., Geneva,
[4] R.S. Oremland, J.F. Stolz,( 2003) The ecology of
arsenic, Science 300.:p. 939944.
[5] http://www.epa.gov/safewater/arsenic.htm.
[6] I. Rau, A. Gonzalo, M. Valiente,(2000)
Arsenic(V) removal from aqueous solutions by
iron(III) loaded chelating resin, J. Radioanal. Nucl.
Chem. 246.:p. 597 604.
[7] J.A. Lackovic, N.P. Nikolaidis, G.M. Dobbs,
(2000) Inorganic Arsenic Removal by Zero-Valent
Iron. Environ. Eng. Sci. 17 29-39.
[8] Kanel, S.B, J.-M. Grenche, and H. Choi,(2005)
removal of arsenic (III)from groundwater by
nanoscale ziro-valent iron. Environ. Sci. technol,.
39: p. 1298-1291
[9] Kanel, S.R., J,-M. Greneche, and H. Choi,(2006)
Arsenic(v) removal from groundwater using
nanoscale zero-valent iron as a colloidal reactive
barrier material. Environ. Sci. Technol,. 40: P.
2050-2045
[10] Auffan, M., Rose, J., Proux, O., Borschneck, D.,
Masion, A., Chaurand, P., Hazemann, J.L.,
Chaneac, C., Jolivet, J.P., Wiesner, M.R., Geen,
A.V., Bottero, J.Y., (2008). Enhanced adsorption
of arsenic onto maghemites nanoparticles: As(III)
Cr2O72- PO43- CO32- HCO3- Cl- SO42- Added Ions
0.5 100 150 150 200 200 Dose 1 Ion doses
before
action(mg/l) 1 500 300 300 400 400 Dose 2
<10 100 35 25 <10 <10 Dose 1
Arsenic
dose after
action
(mg/l)
<10 503 65 53 <10 <10 Dose 2
1171

Proceedings of the 4
th
International Conference on Nanostructures (ICNS4)
12-14 March, 2012, Kish Island, I.R. Iran
as a probe of the surface structure and
heterogeneity.Langmuir 24 2007,:p. 32153222
[11] Morgada, M. E., I. K. Levy, V. Salomone, S. S.
Farias, G. Lopez, M. L. Litter,( 2009) Arsenic(v)
removal with nanoparticulate zerovalent iron:
Effect of UV and humi acids. Catalysis Today 143:
p. 261-268
[12]SU, CH., R. W. Plus,(2001) Arsenate and Arsenite
removal by zerovalent iron: effects of phosphate,
silicate, carbonate, borate, sulfate, chromate,
molybdate, and nitrate, relative to chloride.
Environ. Sci. technol,35: p. 4562-4568
[13] Zhang, W.-X.,(2003) Nanoscale iron particles for
environmental remediation: An overview. Journal
of Nanoparticle Research5.:p. 323-332
[14] Petrisevski, B. and S. Shamma,( 2007) arsenic in
drinking water. Who collaboration center, .
[15] Alan, H. W., O. Rounald.S, J.A. Davis and S.A.
Watking,(2002) arsenic in drinking water :
overview of current knowledge and relation of the
CALFED solution area with recommendation for
needed research. Sanfransisco estuary and
watershed science.
[16] Shu, H.-Y., M.-C. Chang, H.-H. Yu, and W.-H.
Chen,( 2007) reduction of an azo dye acid black
24solution using synthesized nanoscale zerovalent
iron particles. Journal of Colloid and Interface
Science, 314: p. 97-89
[17] Choi, H. and R. Sushil,(2005) removal of arsenat
from groundwater by nano scale ziro-valent iron.
Department of Environmental Science and
Engineering: p. 512-500
[18] Kanel, S.R., J,-M. Greneche, and H. Choi,
Arsenic(v) removal from groundwater using
nanoscale zero-valent iron as a colloidal reactive
barrier material. Environ. Sci. Technol, 2006. 40:
P. 2050-2045
[19] Yang, G.C.C. and H.-L. Lee,(2005) Chemical
reduction of nitrate by nanosized iron:kinetics and
pathways. Waater Research Journal, 39:P. 894-884
[20] Shao-feng, N.,I. Yong, X. Xin-hua, and I. Zhang-
hua,(2005) Removal of hexavalent chromium from
aqueous solution by iron nanoparticles. Journal of
Zhejiang University SCIENCE, 10:P. 1027-1022

1172