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Applied Geochemistry
journal homepage: www.elsevier.com/locate/apgeochem
Natural Red Earth as a low cost material for arsenic removal: Kinetics
and the effect of competing ions
Anushka Upamali Rajapaksha , Meththika Vithanage, Lakmal Jayarathna, Chanaka Kapila Kumara
Chemical and Environmental Systems Modeling Research Group, Institute of Fundamental Studies, Hantana Road, Kandy 20000, Sri Lanka
a r t i c l e
i n f o
Article history:
Available online 6 January 2011
a b s t r a c t
This study investigates the effect of reaction time and competing ions on As retention on Natural Red
Earth (NRE). The initial As [As(III) or As(V)] concentrations were varied between 105 and 104 M
for competitive adsorption studies while samples were spiked with 2.67 lM As for kinetic studies.
2
Batch experiments were performed for solutions with different concentrations of PO3
4 , NO3 and SO4
(5.26 105, 8.06 104, and 2.60 103 M, respectively) as competing ions for the two systems. One
system had controlled conditions (pH 5.5, 0.01 M NaNO3) while the second is uncontrolled (no pH control
and no NaNO3). Kinetic data were best described by a pseudo-second order model demonstrating strong
interaction between As species and >FeOH and AlOH sites on the NRE surface. The equilibrium solid
phase concentrations for As(III) and As(V) were observed as 20 and 12.5 lg/g, respectively. The time
taken to equilibrium was the same (90 min) for both As species. Competitive adsorption isotherm exper2
iments showed a greater effect of PO3
4 on the reduction of adsorption of both As species than with SO4
and NO
.
Arsenic(III)
agreed
with
the
Langmuir
equation
signifying
monolayer
formation
while
As(V)
3
adsorption was in accord with a Fruendlich isotherm indicating multilayer adsorption. FTIR spectra indicated an inner sphere bonding of arsenate and FeO sites with PO3
4 while an outer-sphere weak complexation was observed with NO
3 . The substrate appears to show a potential for a similar rate of
adsorption under both controlled and uncontrolled conditions indicating its possible use in domestic
water lters to remove As from water.
2011 Elsevier Ltd. All rights reserved.
1. Introduction
Arsenic is an ubiquitous element found in the atmosphere, lithosphere, hydrosphere and biosphere. A combination of natural processes and a range of anthropogenic activities release As to the
environment. However, most environmental As problems originate
as a result of mobilization under natural conditions. Arsenic
enrichment of surface and groundwater is great in many parts of
the world, including Bangladesh, West Bengal, India, China, Argentina, Taiwan, Vietnam, Mongolia (Smedley and Kinniburgh, 2002;
Smedley et al., 2005; Agusa et al., 2006; Mohan and Pittman, 2007).
Numerous remediation methods have been reported in the literature for removal of As from water, which include coagulation,
adsorption and separation by ion exchange resin (Jakariya, 2000;
Thirunavukkarasu and Viraraghavan, 2003). In the coagulation process, As removal relies on adsorption and co-precipitation of As
into metal hydroxides (Thirunavukkarasu and Viraraghavan,
2003). The ion exchange method is not economically attractive
Corresponding author. Tel.: +94 812232002; fax: +94 812232131.
E-mail addresses: anushka@ifs.ac.lk, upamalirajapaksha@yahoo.com (A.U. Rajapaksha).
0883-2927/$ - see front matter 2011 Elsevier Ltd. All rights reserved.
doi:10.1016/j.apgeochem.2011.01.021
for water having high total dissolved solids (TDS > 500 mg/L) or
SO2
(>25 mg/L) (US EPA, 1999). The dominant process used to
4
date, is adsorption onto earth materials (Altundogan et al., 2000;
Anderson et al., 1976; Goldberg, 1986; Jain and Leoppert, 2000;
Manning and Goldberg, 1996; Thirunavukkarasu and Viraraghavan, 2003; Weerasooriya et al., 2003; Daus et al., 2004; Gen-Fuhrman et al., 2004; Vithanage et al., 2007b, 2009). However, most of
these studies have been carried out under laboratory controlled
conditions where pH was kept at a prescribed level and background electrolyte was added to activate the surface sites of the solid material. In such cases, adsorption characteristics could be
different from situations where the adsorbent is applied in household lters under natural conditions. This study was carried out to
investigate the effect of laboratory controlled and uncontrolled
conditions on adsorption, to identify the feasibility of using Natural
Red Earth (NRE) as a low cost adsorbent for As removal from potable water. It is important to note that the uncontrolled system was
tested with the objectives of observing any effect of purging with
N2 and addition of NaNO3 in the laboratory on the NRE-As system
since in household lter systems it is impossible to purge N2 and
the use NaNO3. However, use of the uncontrolled system did not
solely simulate a natural household system.
649
650
dq
k1 qe qt
dt
logqe qt log qe
k1 t
2:303
Table 1
Kinetic parameters.
qexp (lg/g)
Exp
Pseudo-rst
As(III) UC
As(III) C
As(V) UC
As(V) C
order model
19.516
22.944
10.948
14.109
qcal (lg/g)
12.434
10.522
8.320
3.462
k2 (lg/g min0.5)
k1 (min1)
0.024
0.038
0.036
0.026
R2
v2
0.903
0.953
0.880
0.889
41.538
10.719
4.628
31.289
0.996
0.999
0.984
0.999
1.344
0.454
2.483
0.757
0.888
0.723
0.675
0.826
2.932
1.533
8.190
0.327
h (lg/g min)
1.728
4.232
0.713
4.535
C
7.232
15.104
4.060
10.778
dq
ks qe qt 2
dt
t
1
t
qt ks q2e qe
as:
h ks q2e
qt kid t 1=2 C
Cads
kMCmax
1 kM
Cads
Asini Asfin
AS
651
Cads kf M1=n
1
log M
n
10
2
3
Fig. 5. Langmuir adsorption isotherm for As(III) with NO
3 , SO4 and PO4 at 0.01 M
NaNO3, pH = 5.5 Symbols represent experimental results and the solid line
represents calculated results using a non-linear least square t.
3
Fig. 3. Experimental results of adsorption isotherms for As(III) with NO
3 and PO4
constructed under controlled and uncontrolled conditions.
2
3
Fig. 6. Freundlich adsorption isotherm for As(III) with NO
3 , SO4 and PO4 at 0.01 M
NaNO3, pH = 5.5.
3
Fig. 4. Experimental results of adsorption isotherms for As(V) with NO
3 and PO4
constructed under controlled and uncontrolled conditions.
652
Table 2
2
3
Langmuir isotherm constants for As(III) with NO
3 , SO4 and PO4 .
k (dm3 mol1)
Experiment
NO
3
PO3
4
SO2
4
R2
As(III) C
As(III) UC
3.530 10
2.867 103
7
1.478 10
1.607 107
0.974
0.915
As(III) C
0.404 103
2.456 107
0.952
As(III) UC
0.375 103
3.017 107
0.961
As(III) C
0.670 103
3.002 107
0.966
As(III) UC
0.505 103
3.736 107
0.949
Table 3
2
3
Freundlich isotherm constants for As(V) with NO
3 , SO4 and PO4 .
kf (mol m2/(mol dm3)1/n)
R2
NO
3
As(III) C
As(III) UC
2.606 104
2.973 104
0.937
0.973
PO3
4
As(III) C
3.893 103
0.989
As(III) UC
1.273 103
0.990
As(III) C
1.029 105
0.989
As(III) UC
8.113 103
0.969
Experiment
SO2
4
Fig. 7. The FTIR spectra of As(III) adsorbed on NRE with competing ions for 600
670 cm1.
653
Fig. 8. The FTIR spectra of As(III) adsorbed on NRE with competing ions for 3600
3720 cm1.
PO3
4 ion could have affect on structural OH sites and form innersphere surface complexation (Tyrovola et al., 2006). This could lead
to formation of a strong bond with surface OH sites and show a
shifting to the low wavenumbers (Figs. 7 and 8). Nitrate facilitates
orientation of surface OH sites and, therefore, bond strength decreases resulting in a shift to a high wavenumber. In the presence
of AlOH surface sites, Al should strongly distort the symmetry of
As and the AsOAl vibration is shifted to very low wavenumbers
when comparing AsOH vibration. However, in the presence of Fe
OH surface sites, the AsOFe band exhibits a small shift for AsOH
vibration. Therefore, in the presence of PO3
4 , As interacts with both
surface AlOH and FeOH sites however, in the presence of SO2
4 , it
is only the FeOH sites.
3.4. Possible sorption mechanisms
Prior studies have suggested that As(V) and As(III) is bound to
the Fe oxide minerals by forming an inner-sphere complexes, in
which the As(III) or As(V) exchange with surface-OH or -OH2
groups that are directly coordinated to structural Fe(III) at the Fe
oxide surface (Escudero et al., 2009). However, considering the
characteristics of NRE, the presence of different functional groups
on the NRE surface and the As species present at the particular
pH, the authors propose the mechanisms for As(III) and As(V)
adsorption on NRE in the presence of PO3
4 as given in Fig. 9ac.
In the case of As(V), similar to PO3
4 , the absorbed arsenate anion is usually coordinated to two adjacent structural Fe3+ cations
on the NRE surface (Fig. 9a) which is called a bidentate binuclear-bridging complex. Based on the observations from the Freundlich isotherm tting, a further multilayer complex formation
of As(V) in the presence of PO3
is proposed (Fig. 9b). Although
4
both bidentate binuclear-bridging complexes and monodentate
complexes have been postulated for As(III) adsorption in previous
studies (Manning et al., 1998; Su and Puls, 2001; Escudero et al.,
2009), the present authors postulate a monodentate complex for
the As(III)-NRE system in the presence of PO3
considering the
4
reduction of adsorption (Fig. 9c).
4. Conclusions
Arsenic retention on NRE demonstrated a pseudo-second order
behavior while arsenite and arsenate reach maximum adsorption
around 90 min for both uncontrolled and controlled conditions.
However, As(III) adsorbed better onto NRE than As(V) with all
654
increased the rate of adsorption of both As(III) and As(V), the existence of PO3
signicantly reduced As adsorption capability and
4
rate. The ndings of this study suggested that the laboratory
uncontrolled condition had a small effect on As adsorption on
NRE and that could be due to the absence of an ionic strength adjuster in the system. The results show that the ability of NRE to absorb As does not appear to be affected much by the high
concentration of anions. Therefore, in natural systems, the presence of anions will not reduce the effectiveness of NRE to absorb
As. As a consequence, it is concluded that the NRE could be potentially effective in removing As from potable water, and could be
effectively used in making domestic lters.
Acknowledgements
We would like to extend our thanks for the support given by
Prof. Prosun Bhattacharya and Prof. Jean Jiin-Shuh. Reviewers and
editorial comments helped to improve the manuscript quality
and clarity.
References
Agusa, T., Kunito, T., Fujihara, J., Kubota, R., Minh, T.B., Trang, P.T.K., Iwata, H.,
Subramanian, A., Viet, P.H., Tanabe, S., 2006. Contamination by arsenic and
other trace elements in tube-well water and its risk assessment to humans in
Hanoi, Vietnam. Environ. Pollut. 139, 95106.
Altundogan, H.S., Altundogan, S., Tumen, F., Bildik, M., 2000. Arsenic removal from
aqueous solutions by adsorption on red mud. Waste Manage. 20, 761767.
Anderson, M.A., Ferguson, J.F., Gavis, J., 1976. Arsenate adsorption on amorphous
aluminium hydroxide. J. Colloid Interface Sci. 54, 391399.
Dahanayake, K., Jayawardana, S.K., 1979. Study of red and brown earth deposits of
north-west Sri Lanka. J. Geol. Soc. India 20, 433440.
Daus, B., Wennrich, R., Weiss, H., 2004. Sorption materials for arsenic removal from
water: a comparative study. Water Res. 38, 29482954.
Dutta, P.K., Ray, A.K., Sharma, V.K., Millero, F.J., 2004. Adsorption of arsenate and
arsenite on titanium dioxide suspensions. J. Colloid Interface Sci. 278, 270275.
Ece, Q.I., Coban, F., Gungor, N., Suner, F., 1999. Clay mineralogy and occurrence of
ferrian smectites between serpentinite saprolites and basalts in biga Penisula,
Northwest Turkey. Clays Clay Miner. 47, 241251.
Escudero, C., Fiol, N., Villaescusa, I., Bollinger, J., 2009. Arsenic removal by a waste
metal hydroxide entrapped into calcium alginate beads. J. Hazard. Mater. 164,
533541.
Frau, F., Biddau, R., Fanfani, L., 2008. Effect of major anions on arsenate desorption
from ferrihydrite-bearing natural samples. Appl. Geochem. 23, 14511466.
Gen-Fuhrman, H., Tjell, J.C., McConchie, D., 2004. Adsorption of arsenic from water
using activated neutralised red mud. Environ. Sci. Technol. 38, 24282434.
Goh, K.H., Lim, T.T., 2004. Geochemistry of inorganic arsenic and selenium in a
tropical soil: effect of reaction time, pH, and competitive anions on arsenic and
selenium adsorption. Chemosphere 55, 849859.
Goldberg, S., 1986. Chemical models of arsenate adsorption on Al and Fe oxide
minerals. Soil Sci. Soc. Am. J. 50, 11541158.
Guan, X., Dong, H., Ma, J., Jiang, Li., 2009. Removal of arsenic from water: effects of
competing anions on As(III) removal in KMnO4Fe(II) process. Water Res. 43,
38913899.
Ho, Y.S., McKay, G., 1999. Pseudo-second order model for sorption processes.
Process. Biochem. 34, 451465.
Ho, Y.S., Porter, J.F., Mckay, G., 2002. Equilibrium isotherm studies for the sorption
of divalent metal ions on to peat: copper, Nickel and Lead single component
systems. Water Air Soil Pollut. 141, 133.
Jain, A., Leoppert, R.H., 2000. Effect of competing anions on the adsorption of
arsenate and arsenite by ferrihydrite. J. Environ. Qual. 29, 14221430.
Jakariya, M., 2000. The Use of Alternative Safe Water Options to Migrate the Arsenic
Problem in Bangladesh: A Community Perspective. <http://bicn.com/acic/
resources/infobank/jakariya/sec07.htm>.