Environ Earth Sci (2016)75:381

DOI 10.1007/s12665-016-5282-5

ORIGINAL ARTICLE

Magnetite nanoparticles coated sand for arsenic removal

from drinking water
Sarita Kango1 Rajesh Kumar1

Received: 28 March 2015 / Accepted: 14 November 2015

Springer-Verlag Berlin Heidelberg 2016

Abstract In this paper, for the first time we describe the

removal of poisonous element arsenic (V) from drinking
water by nanoscale magnetite coated sand. The removal
efficiency of newly formed adsorbent was studied by
varying various parameters, for example, contact time, pH,
adsorbent dosage and initial As(V) concentration. Also, the
experiments were performed in the presence of co-existing
cations (Zn2?, Cd2?, Pb2?, Ni2?, Mg2?, Cr3? and Fe3?) to
study their influence on As(V) removal efficiency. The
adsorption kinetics data fitted well in both the pseudo-firstorder and pseudo-second-order kinetics with high correlation coefficients (R2 [ 0.99). Adsorption isotherm data are
fitted in Langmuir and Freundlich isotherm models. It is
observed that thus formed adsorbent shows significant
As(V) removal efficiency, and reduces the As(V) concentration below 5 lg/L from 6700 lg/L, which is much less
than the maximum contaminant level set by WHO (10 lg/
L). Here, the co-existing cations do not show any significant effect on As(V) removal efficiency. The observed
Freundlich adsorption capacity of 2.06 mg/g for As(V) removal is comparable with certain other adsorbents.
Keywords Adsorption kinetics  Adsorption isotherms 
As(V) removal  Magnetite nanoparticles

& Rajesh Kumar

rajesh.kumar@juit.ac.in
1

Department of Physics and Materials Science, Jaypee

University of Information Technology, Waknaghat, Solan,
Himachal Pradesh 173234, India

Introduction
Excess arsenic contamination in drinking water has resulted in human poisoning and death. It causes skin, cardiovascular, neurological, and respiratory disease as well as
lung, bladder and kidney cancer (NRC 2001; An et al.
2011; Guo et al. 2007). World Health Organization (WHO)
in 1958 categorized arsenic as a toxic substance. Since
1958, WHO has revised its guidelines for acceptable arsenic concentration in drinking water three times. In
the last edition (1993), WHO established 0.01 mg/L as a
provisional guideline value for arsenic in drinking water
with a view to further reduce its concentration (WHO
1993). Food and Agricultural Organization (FAO) in its
guidelines has also set 0.01 mg/L as the maximum adaptable value of arsenic for irrigation water (FAO 1985).
Following the latest guidelines of WHO and FAO, a
number of countries have adopted provisional guideline
value (0.01 mg/l) as their standard; however, still there are
many countries such as China, Bangladesh, India, Nepal,
etc. which have kept WHOs earlier guideline value, i.e.,
0.05 mg/L, as the maximum acceptable arsenic value
(Shrestha et al. 2006; WHO 1963). According to a study in
2007, over 137 million people in around 70 countries
including Bangladesh, India, Taiwan, China, Chile, Vietnam, Ghana and USA are affected by arsenic poisoning of
drinking water (USA Today.com 2007; Park et al. 2009).
To mitigate human exposure and to meet the low admissible level of arsenic in drinking water, the development of
technologies at reasonable cost is a big requirement.
The countries or part of the countries which are highly
affected by arsenic concentration are: Victoria (Australia)
where groundwater contains 1300,000 lg/L arsenic, and
surface water is 128,300 lg/L arsenic contaminated
(Hinwood et al. 1998). Ground water of northern Chile has

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19021,800 lg/L (Caceras et al. 1992); Bangladesh has

503200 lg/L British Geological Survey (1999); British
Geological Survey 2001); and Vietnam has 13050 lg/L
concentration of arsenic (Berg et al. 2001). Northwestern
Argentina contains 12610,650 lg/L arsenic in spring
water, and 521045 lg/L in river water (De Sastre et al.
1992); Brazil contains 0.4350 lg/L arsenic in surface
water (Matschullat et al. 2000); and Mexico has arsenic
contamination from 21 to 1070 lg/L in wells (Armienta
et al. 1997; Gomez-Arroyo et al. 1997; Diaz-Barriga et al.
1993). Arsenic contaminated water in Canada is up to
3000 lg/L (Grantham and Jones 1977); in India up to
3880 lg/L (Samanta et al. 1999; Chakraborti et al. 2001;
Neriowlm 2004); in Pakistan up to 906 lg/L (Mukherjee
et al. 2006); in USA up to 210 lg/L (Southwick et al.
1983); and in Switzerland up to 170 lg/L (Pfeifer and
Zobrist 2002).
Arsenic is generally introduced into water through the
dissolution of arsenic contaminated minerals and ores such
as niccolite, cobaltite, scorodite, orpiment and arsenopyrite
(Turk et al. 2009, 2010). Human activities such as agricultural use of arsenic pesticides, herbicides, fertilizers,
gold and coal mining (EPA 2000), discharge from coal
fired thermal power plants, etc., are also sources of arsenic
contamination.
In aqueous environment, depending upon the pH and
redox conditions arsenic can exist in ?5, ?3,0 and -3
oxidation states, but it is predominantly found in trivalent
arsenite such as H3AsO03, H2AsO3-, HAsO32- and AsO33and pentavalent arsenate such as H3AsO4, H2AsO4-,
HAsO42- and AsO43- states (Park et al. 2009; Datta and
Pratip 1997; Katsoyiannis and Zouboulis 2004). Both these
states are known to be acutely toxic by Environmental
Protection Agency (EPA). At natural pH value, arsenite
(As(III)) exists as H3AsO03 and H2AsO3. Arsenate (As(V))
exists as HAsO42- at higher pH while H2AsO4- and
H3AsO4 are predominant at acidic and extremely acidic
conditions. Generally, both arsenite As(III) and arsenate
As(V) are found in soil and subsurface environment
(Goldberg and Johnston 2001). Arsenate As(V) is dominant
in oxidizing conditions, for example surface natural water
being oxygen-rich environment contains arsenate (As(V));
while arsenite As(III) is predominant in reducing conditions such as in groundwater (Ying et al. 2009).
In order to remove both As(V) and As(III) from water,
USEPA (2000) evaluated various treatment technologies
such as chemical precipitation (Magalhaes 2002), bioremediation (Katsoyiannis et al. 2004), ion exchange
(Korngold et al. 2001), coagulation and filtration (Wickramasinghe et al. 2004), reverse osmosis (Mondal et al.
2006), electro-coagulation (Parga et al. 2005) and adsorption (Mohan and Pittman 2007). Most of these methods
have several disadvantages such as requirement of

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Environ Earth Sci (2016)75:381

expensive equipments, sludge production, time consuming

and complexity. Among these adsorption and coagulation
are believed cost effective methods; however, coagulation
needs skilled operators and shows more effectiveness only
on some specific iron and aluminium salts. However, the
adsorption method due to its low cost, simplicity in design,
sludge free operation, ease of operation and potential of
regeneration has gained popularity. Moreover, adsorption
based methods are capable of removing arsenic to a much
lower level than any other method (Benjamin 1983), and
show easy separation of the small amount of toxic elements
from large volume of water. Many types of adsorbents such
as activated alumina (AA), iron based sorbents (IBS),
granular ferric hydroxide, zero-valent iron, iron coated
sand (Jekel 1994; Driehaus et al. 1998; Lackovic et al.
2000; Farrell et al. 2001; Su and Puls 2001, 2003; Manning
et al. 2002a, 2002b; Nikolaidis et al. 2003; Hussam and
Munir 2007), magnetic ion exchange resins (Sinha et al.
2011), synthetic goethite (Lakshmipathiraj et al. 2006)
chitosan based adsorbents (Gupta et al. 2013; Elwakeel
2014), graphene oxide composites (Chandra et al. 2010;
Kemp et al. 2013), magnetic nanochains (Das et al. 2014)
etc. are commonly used for arsenic removal from water.
Iron oxides adsorbents have been widely investigated to
remove arsenic from aqueous solutions due to the higher
affinity of arsenic to iron oxides. The higher affinity of
arsenic is evidenced from an observation in which arsenic
exists on the surface of iron oxide even in natural environment (Nishida et al. 2004). Recently, the use of
nanoparticles in environmental remediation processes is
increased due to their small size and high surface area. Iron
oxide nanoparticles, due to higher affinity to arsenic, have
gained growing interest in water purification (Yavuz et al.
2006; Dixit and Hering 2003) Among different iron oxide
nanoparticles, magnetite (Fe3O4) nanoparticles have
proved to be potential adsorbents owing to their higher
adsorption capacity for arsenic removal.
In the process of arsenic removal, the magnetite
nanoparticles when used as bare are dispersed in arsenic
contaminated solution, which after treatment are separated
either by applying an external magnetic field or by centrifugation and filtration (Yavuz et al. 2006). However, the
separation of nano sized magnetite is a difficult process and
thus limits their use in column operations. Also, the use of
magnetite nanoparticles alone as a filter cartridge would be
expensive. The possible way to overcome the problem of
separation of magnetite from aqueous solution is to use a
support system or substrate for magnetite nanoparticles. In
other words, the sand provides a support to magnetite
nanoparticles as the nanoparticles are coated on its surface;
therefore, now it is easier to separate out the sand (coated
with magnetite nanoparticles) as compared to the bare nano
sized magnetite particles by using a simple filter such as

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381

paper filter rather than using magnetic field as required in

case of bare magnetite nanoparticles. In the present study,
we have used sand as the substrate for magnetite
nanoparticles. The magnetite nanoparticles coated sand is
used for removing As(V) from aqueous solutions. Since in
natural water other ions are also present which normally
affect arsenic removal due to their competing behavior for
adsorption. Therefore, in this study, the effect of various
competing cations such as cadmium, zinc, iron, nickel,
chromium, magnesium and lead on arsenic removal efficiency has also been investigated. The magnetite coated
sand may be effective in column studies as it overcomes
the problem of separation of nanosized magnetite from
aqueous solutions.

reaction the base NH4OH solution was added dropwise

until a pH close to 10.0 was attained. Addition of NH4OH
solution resulted in black colour of the mixture due to
coprecipitation of Fe2? and Fe3?. After the completion of
reaction, the mixture was sealed in a vessel, and aged for
2 days at room temperature. The mixture after filtration
was dried in a horizontal tube furnace at around 85 C
temperature under Ar gas flow. In this process the magnetite nanoparticles were coated on sand surface. The
magnetite nanoparticles coated sand was washed with
distilled water until run-off was clear; then it was again
dried at 85 C for 3 h in argon gas environment. Finally,
magnetite nanoparticles coated sand was cooled to room
temperature and stored in polyvinyl chloride (PVC) plastic
bottles for further use.

Materials and methods

Materials characterization

Materials

The morphology of magnetite coated sand was analyzed

using Field Emission Scanning Electron Microscopy
(FESEM), Hitachi S-4700. The adsorbent was characterized using powder X-ray diffractometer (XRD), XRD 6000
Shimadzu analytical instrument. The XRD data was col , scan angle
lected using CuKa radiation of k = 1.54 A
2h = 1580 and scan rate 0.02 per second.

All chemicals and reagents used in this study were of

analytical grade, which were used as received. The
As(V) stock solution (100 mg/L) was prepared by dissolving sodium arsenate dibasic heptahydrate (HAsNa2O47H2O) in milli-Q water. Working solutions of
As(V) were prepared freshly according to experimental
requirement from the stock solution. The pH of working
solution was adjusted by standard 0.1 M HCl and 0.1 M
NaOH solutions, respectively. The adsorbent, magnetite
nanoparticles coated sand, was prepared using iron (III)
chloride hexahydrate (FeCl36H2O), iron (II) chloride
(FeCl2) in 2:1 ratio, and NH4OH solutions. The co-ions
(Zn2?, Cd2?, Pb2?, Ni2?, Mg2?, Cr3? and Fe3?) were
produced in the solution by dissolving Zinc chloride
(ZnCl2), cadmium chloride monohydrate (CdCl2H2O),
lead (II) chloride (PbCl2), nickel chloride (NiCl26H2O),
magnesium chloride hexahydrate (MgCl2), chromium(III)
chloride hexahydrate (CrCl36H2O) and iron(III) chloride
hexahydrate (FeCl36H2O). The sand was procured from
Beas River in Mandi, district, Himachal Pradesh, India.
Preparation of magnetite nanoparticles coated sand
Initially, the sand was sieved to 0.60.9 mm mesh sieves.
After sieving, it was treated with 1.0 M HCl solution for
24 h, washed several times with distilled water, and dried
at 100 C temperature. It was further treated with
HNO3:HCl (1:3) for 5 min in order to create roughness/dangling bonds on its surface, and rinsed in a stream
of water to remove surface residues. The obtained clean
sand was added to a stock solution of FeCl3 and FeCl2 in
2:1 ratio. The mixture was stirred for 30 min at 70 C
temperature under argon gas flow. For coprecipitation

Analysis of adsorption kinetics and adsorption

equilibrium
Adsorption measurements were evaluated performing
batch experiments at room temperature (30 2 C) for
the contact time of 30420 min at pH from 2.0 to 12.0.
All the batch experiments were carried in 150 ml conical
flasks containing 50 ml of As(V) solution (115.35 mg/L)
and 0.251.5 g of as formed magnetite nanoparticles
coated sand. The conical flasks were shaken at an agitation speed of 200 rpm in an incubator shaker. Thereafter, the solutions were filtered through 0.45 lm
durapore filter papers. The filtrate was digested in various
concentrations of HNO3; here in the whole of this study
we quote the minimum/optimum concentration (1 %) of
HNO3 which is found sufficient to digest the samples.
The filtrate after digestion in HNO3 solution was analyzed for residual As(V) concentration by using ICP-MS
(Perkin Elmer Elan DRC 6000). The effect of various
competing ions Zn2?, Cd2?, Pb2?, Ni2?, Mg2?, Cr3? and
Fe3? on the removal efficiency of As(V) was also
investigated performing the aforementioned method. The
experiment was also performed separately for sand and
magnetite nanoparticles with initial As(V) concentration
of 5 mg/L and adsorbent dose (sand or magnetite) of
0.2 g/20 ml to understand the role of surface coated
magnetite nanoparticles.

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Environ Earth Sci (2016)75:381

The As(V) removal efficiency of magnetite nanoparticles coated sand was calculated using the formula:
Removal efficiency %

C0  Ce
100
C0

And the amount of As(V) adsorbed (mg) per unit mass

of adsorbent (g) was determined using the formula:
qe

C0  Ce
V
M

where C0 and Ce are initial and final As(V) concentrations

(mg/L), respectively, V is the volume of solution and M is
the mass of adsorbent.
The adsorption kinetics and isotherms were also investigated in batch experiments. Firstly in order to estimate the
rate at which adsorption of arsenic takes place, and to
predict the rate controlling step, experimental data was
fitted in pseudo-first-order and pseudo-second-order
kinetics models. Equations (3) and (4) represent pseudofirst-order and pseudo-second-order kinetics models,
respectively (Pillewan et al. 2011).
logqe  qt logqe 

kads
t
2:303

t
1 t

qt h qe

3
4

and
h kq2e

where qe (mg/g) and qt (mg/g) are amount of As(V) adsorbed per unit mass of adsorbent at equilibrium and time t,
respectively. The kads and k are pseudo-first-order and
pseudo-second-order adsorption rate constants, respectively, and h is initial adsorption rate (mg g-1 min-1).
Secondly, the experimental adsorption isotherm data
was compared with theoretical Freundlich and Langmuir
isotherm models. Equation (6) represents linear form of
Freundlich isotherm model (Freundlich 1906).
1
logqe log KF logCe
n

123

1
1 bC0

where C0 is initial concentration of As(V) and b is Langmuir constant. The value r \ 1.0 shows favourable
adsorption, whereas r [ 1.0 shows unfavourable
adsorption.
Desorption and readsorption experiment
To test the reusability of magnetite nanoparticles coated
sand the adsorption/desorption studies for As(V) were
repeated up to 10 cycles. Desorption experiments were
carried out by using 0.5 m of sodium hydroxide solution.
First of all As(V) solution of 1 mg/L concentration was
agitated with 1 g adsorbent for 7 h of contact time. After
agitation the solution was filtered and the arsenate-loaded
adsorbent was washed several times with distilled water in
order to remove any excess of unabsorbed arsenate ions.
The adsorbent was then agitated with 40 ml of 0.5 m
sodium hydroxide solution for a period of 7 h equal to
adsorption time. The solution was then filtered and washed
with distilled water in order to remove excess of NaOH.
The adsorbent was again treated with 40 ml of As(V)
solution of 1 mg/L to study the readsorption behaviour of
the adsorbent. The above adsorption and desorption
experiments were repeated for 10 cycles. The As(V) desorption percentage was calculated by using Eq. (9):
%Desorption

released AsVmg=L
 100
initially adsorbed AsVmg/L)
9

where qe is the amount of As(V) adsorbed per unit mass of

magnetite nanoparticles coated sand at equilibrium (mg/g), Ce
is equilibrium concentration of As(V) in the solution phase
(mg/L), KF is adsorption capacity indicator, and
n (1 \ n \ 10) is adsorption intensity. We know that if
n = 12, the adsorption is considered to be good; and if
n = 210, the adsorption is considered to be better; and finally
if n \ 1, then the adsorption is considered unfavourable.
Equation (7) represents linear form of Langmuir isotherm model (Wang et al. 2012).
Ce Ce

bqm
qe qm

where qm (mg/g) is maximum adsorption capacity, and

b (L/mg) is Langmuir adsorption constant related to the
affinity between the solute and adsorbent.
To predict the adsorption efficiency of the process, a
dimensionless quantity r is also calculated by using the
formula:

Results and discussion

Characterization of adsorbent
Figure 1 shows FESEM images of uncoated and magnetite
nanoparticles coated sand. In Fig. 1a uncoated sand particles are shown. The inset in Fig. 1a shows surface of a
uncoated sand particle, which indicates a clear surface of
the sand particle. In Fig. 1b magnetite coated sand particles
are shown. In this image, the surface of the sand particle is
covered by nanosized magnetite particles as shown in inset
(Fig. 1b). As a rough estimation, the size of magnetite

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381

Fig. 1 FESEM images of a uncoated sand, b magnetite nanoparticles coated sand and c schematic of magnetite nanoparticles coating on sand
particles

(PDF no. 821533) confirming the coating of Fe3O4

nanoparticles on the sand surface. Other peaks at diffraction angles 2h = 8.78, 12.47, 20.88, 26.61, 36.46,
40.35, 45.68, 50.192, 54.89, 60.03, 68.22, 75.80 and
77.65 correspond to the characteristic peaks of quartz sand
(JCPDS PDF no. 898934).
Effect of contact time: adsorption kinetics

Fig. 2 XRD pattern of magnetite nanoparticles coated sand

nanoparticles ranges from 20 to 60 nm. The coating of

magnetite nanoparticles on the sand particles surface is
schematically shown in Fig. 1c.
Figure 2 represents a powder XRD pattern of magnetite
nanoparticles coated sand. The characteristic peaks
approximately at diffraction angles 2h = 17.81, 30.5,
35.63, 42.82, 53.67, 57.36, 62.89 and 67.38 could be
assigned to the (111), (220), (311), (400), (422), (333),
(440), (442) planes of Fe3O4 according to the JCPDS data

The effect of contact time on the %As(V) removal efficiency and adsorption capacity (qt = mg/g) was investigated by varying the contact time from 30 to 420 min at
initial As(V) concentration of 1 mg/L. The removal efficiency and adsorption capacity with contact time are shown
in Fig. 3a and b respectively. From Fig. 3a, it can be seen
that merely in 30 initial minutes of contact time, 87 % of
As(V) is removed by magnetite nanoparticles coated sand,
whereas in next 330 min the removal efficiency reached to
99.84 %. Figure 3b shows that within initial 30 min
0.0348 mg/g of As(V) was adsorbed by adsorbent and at
equilibrium 0.0399 mg/g of As(V) was adsorbed.
Depending upon the %As(V) removal efficiency and
adsorption capacity with respect to contact time, the whole
removal process can be divided in two steps: fast and
slower adsorption steps. In the fast adsorption step, the

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Environ Earth Sci (2016)75:381

Fig. 3 Effect of contact time on a %As(V) removal efficiency and b adsorption capacity (qt = mg/g)

Fig. 4 Adsorption kinetics a pseudo-first-order and b pseudo-second-order model for As(V) removal by magnetite nanoparticles coated sand

adsorbent has all its surface sites vacant for the adsorption,
and the As(V) is easily adsorbed on these adsorption sites
(Chowdhury and Yanful 2010). With the lapse of time, the
available active sites are occupied by As(V) and the process of adsorption gets slower; and after 330 min an
equilibrium is attained as shown in the Fig. 3. However, to
ensure the complete adsorption all the batch experiments
were performed for a contact time of 420 min.
Experimentally observed adsorption kinetics data was
fitted in pseudo-first-order and pseudo-second-order
kinetics models. Figures 4a and b show linear plots of
pseudo-first order and pseudo-second-order kinetics models, respectively. The calculated corresponding parameters
kads, k, h, qe and correlation coefficient R2 obtained from
these plots are given in Table 1. The results show that
experimental data is fitted well in both the pseudo-firstorder and pseudo-second-order kinetics model with higher
values of correlation coefficients (R2 [ 0.99).
We have also performed arsenic removal experiments
separately for sand and magnetite nanoparticles with initial

123

As(V) concentration of 5 mg/L and adsorbent dose (sand or

magnetite) of 0.2 g/20 ml. With sand particles arsenic was
reduced only to 4.501 mg/L from 5 mg/L initial arsenic
concentration. On the other hand, magnetite nanoparticles
reduced arsenic concentration below 1 part per trillion as
the amount was not detectable in the sample by ICP-MS
(ICP-MS instrument lower detection limit was 1 ppt).
Arsenic removal efficiency of sand is found to be 9.98 %
and of magnetite nanoparticles is approximately *100 %
as arsenic was not detectable in the sample. Thus on the
basis of results obtained, we can say that sand is not able to
remove arsenic. It is only magnetite nanoparticles which
are responsible for arsenic removal.
Effect of solution pH on As(V) removal
Since the pH, due to its effect on the metal speciation in
water (Escudero et al. 2009), is considered as an important
factor in adsorption based wastewater treatment experiments. Therefore, in this work the effect of pH on

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381

Table 1 Pseudo-first-order and pseudo-second-order kinetic parameters for As(V) removal by magnetite nanoparticles coated sand calculated
from linear plots
Pseudo-first-order parameters
-1

Pseudo-second-order parameters

kads(min )

qe (mg/g)

k (g mg-1 min-1)

h (mg g-1 min-1)

qe (mg/g)

R2

0.0142

0.992

0.00874

3.754

0.00621

0.0406

0.999

As(V) removal efficiency by magnetite nanoparticles

coated sand was studied. The batch experiments were
conducted within the pH range 2.012.0 at fixed adsorbent
dose, and contact time of 420 min with initial As(V) concentration of 1 mg/L at room temperature. The change in
the solution pH during the adsorption experiments was
recorded, and was observed to be within 0.1 of the initial
pH values. Figure 5 shows the effect of solution pH on
As(V) removal efficiency by magnetite nanoparticles
coated sand. Here, it is observed that for the pH range
2.07.0 there is slight decrease in As(V) removal efficiency, while for the increased pH from 7.0 to 12.0, there is
a drastic decrease in As(V) removal efficiency from 99.99
to 39.33 %. It indicates that magnetite nanoparticles coated
sand adsorb As(V) more efficiently in an acidic pH range
than in basic pH range. The observed variation in
As(V) removal efficiency at different pH values may be
attributed to different affinities of magnetite nanoparticles
coated sand for different As(V) species viz. AsO43-,
HAsO42-, H2AsO4-, H3AsO4 dominating at different pH
values. It is reported that the pH range of 2.36.9 contains
H2ASO4- as the predominant form of As(V), whose
adsorption energy may be lower than that of HAsO42- and
AsO43- ion which results in comparatively more favourable adsorption of H2AsO4- than that of HAsO42- and
AsO43- ions (Chowdhury and Yanful 2010; Nordstrom and
Archer 2003). Except for the adsorption energy, different
surface charge of magnetite particles at different pH also

Fig. 5 Effect of pH on %As(V) removal efficiency

effects As(V) removal efficiency. The surface of magnetite

particles is positively charged in the pH range 4.07.7 and
has a point of zero charge at 7.8 pH, and is negatively
charged in 7.99.5 pH range. Therefore, in the acidic pH
range the As(V) being negatively charged is adsorbed more
efficiently on the positively charged magnetite nanoparticles coated sand due to electrostatic attraction (Yean et al.
2005).
Effect of adsorbent dose
To analyze the effect of adsorbent dose on both the
%As(V) removal efficiency and adsorption capacity
(qe = mg/g), the adsorbent dose was varied from 5 to 30 g/
L at fixed initial As(V) concentration of 1 mg/L and pH 7.0
as shown in Fig. 6. From Fig. 6 it can be seen that
%As(V) removal efficiency increases from 94.7 to 99.99 %
corresponding to the adsorbent dose from 5 to 30 g/L.
However, the adsorption capacity decreases from initial
value 0.189 mg/g (corresponding to 5 g/L of adsorbent
dose) to 0.033 mg/g (corresponding to 30 g/L of adsorbent
dose). The observed increase in the As(V) removal efficiency is expected due to the available more active sites
because of the higher concentrations of adsorbent (Pandey
et al. 2009; Kaczala et al. 2009). On the other hand, the
decrease in adsorption capacity is attributed to the interference between binding sites, and higher adsorbent dose or
insufficiency of As(V) ions in the solution with respect to
available binding sites (Fan et al. 2008; Rome and Gadd

Fig. 6 Effect of adsorbent dose on %As(V) removal efficiency and

adsorption capacity (qe = mg/g)

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Environ Earth Sci (2016)75:381

Fig. 7 Effect of initial As(V) concentration on %As(V) removal

efficiency and adsorption capacity (qe = mg/g)

1987). The point of intersection of the plots representing

removal efficiency and adsorption capacity is generally
considered as the optimum dose because it shows balance
between %As(V) removal efficiency and adsorption
capacity. In our case, the intersection point is obtained at
the value 10 g/L of adsorbent dose. However, as observed
from the experimental data the 10 g/L dose of adsorbent is
not sufficient to reduce arsenic concentration to a required
10 lg/L level; therefore, here 25 g/L of adsorbent dose was
selected to achieve the WHO standards. It may be noted
that the dose of adsorbent includes the weight of real
adsorbent (magnetite nanoparticles) and weight of sand

particles; therefore, in this study it is the total weight of

sand and adsorbent and is obviously higher as compared
with that of real adsorbents. Since in the present case, the
real adsorbent is the magnetite; therefore, we also conducted experiments by using bare magnetite nanoparticles.
In this case, the adsorbent dose was varied as 50 mg/L,
100 mg/L, 200 mg/L, 500 mg/L and 1 g/L. We observed
that 200 mg/L of magnetite nanoparticles were sufficient to
reduce As(V) concentration below 10 lg/L from initial
As(V) concentration of 1 mg/L. This amount of the
adsorbent required to reduce arsenic concentration below
allowable limit is less than the commercially available
adsorbent (Chowdhury and Yanful 2010). Also, as compared with another reported results (Das et al. 2014) where
they have reduced the As concentration to 16.1 mg/L while
taking its initial concentration as 100 mg/L and using
adsorbent dose of 1 g/L, our adsorbent shows better
performance.
Effect of initial As(V) concentration
The effect of initial As(V) concentration on the
%As(V) removal efficiency and adsorption capacity of
magnetite nanoparticles coated sand was also studied. The
corresponding plots are shown in Fig. 7. It is observed
that when the initial As(V) concentration increases from 1
to 15.35 mg/L, the As(V) removal efficiency decreases
from 99.99 to 99.53 %, and the adsorption capacity

Fig. 8 Adsorption isotherm a Freundlich fit and b Langmuir fit for As(V) adsorption by magnetite nanoparticles coated sand

Table 2 Freundlich and Langmuir adsorption isotherm parameters for As(V) adsorption by magnetite nanoparticles coated sand calculated from
linear plots
Freundlich isotherm parameters

Langmuir isotherm parameters

KF (mg/g)

b (L/mg)

qm (mg/g)

R2

2.065

2.39

0.984

216.99

0.639

0.00460.0003

0.993

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Table 3 Comparison of
adsorption capacities of some
adsorbents for As(V) removal

Page 9 of 12

Adsorbents

Freundlich parameters
KF (mg/g)

381

References

Laterite soil

0.055

4.23

Magnetite reduced graphite oxide-MnO2 nanocomposites

5.69

3.87

Maji et al. (2007)

Luo et al. (2012)

MgFe-based hydrotalcite

0.007

1.14

Turk et al. (2009)

Magnetite nanoparticles

0.034

1.81

Turk et al. (2010)

Chitosan coated sand

2.49

Gupta et al. (2013)

Ironchitosan coated sand

2.50

Gupta et al. (2013)

Magnetite nanoparticles coated sand

2.06

2.39

Present study

Fig. 9 Effect of co-existing cations on As(V) removal efficiency

increases from 0.039 to 0.611 mg/g. Similar to the case of

higher dose of adsorbent, here also when the initial
As(V) concentration is lower it will find abundant active
adsorbent sites, and thus the system shows higher removal
efficiency. In case when As(V) concentration is increased,
the concentration of adsorbate is increased; however, the
available active sites remains same as that in previous
case. Therefore, the %As(V) adsorbed amount will reduce
as shown by the decreasing trend of removal efficiency of
As(V).

Fig. 10 %As(V) a adsorption and b desorption behaviour of

magnetite nanoparticles coated sand up to 10 cycles

Adsorption isotherms
In order to describe equilibrium between adsorbed
As(V) ions and As(V) ions in solution, we used Freundlich
and Langmuir isotherm. Adsorption isotherm data was
fitted in Langmuir and Freundlich isotherm models given
in the Eqs. (6) and (7). The adsorption equilibrium isotherms are shown in Fig. 8a and b. Table 2 summarizes the
values of various corresponding parameters of both Langmuir and Freundlich isotherms. Here in this table, the
correlation coefficients (R2) represent the goodness of fit.
The value of R2 in the Langmuir model is greater than 0.99,
it is 0.98 in case of Freundlich model, therefore the
adsorption data can be described well by Langmuir model
rather than Freundlich model. According to Langmuir

model, the adsorption occurs on a homogeneous surface.

The value of Freundlich parameter n = 2.39 lying within
the limit of better adsorption, i.e., 2 \ n \ 10 indicates that
As(V) exhibits better adsorption on magnetite nanoparticles coated sand. It can be seen from Table 2 that the
maximum adsorption capacity (KF) for As(V) in our case is
2.06 mg/g. The obtained adsorption capacity is comparable
with other adsorbents. The comparison of adsorption
capacity of magnetite nanoparticles coated sand with
reported adsorbents is listed in Table 3. Further, the values
of r (0.00460.0003) are found less than unity for all
As(V) concentrations ranging from 1 to 15.35 mg/L, which
interprets highly favourable adsorption of As(V) on magnetite nanoparticles coated sand.

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Page 10 of 12

Effect of co-existing ions on As(V) removal

As the presence of ionic species may affect the arsenic
adsorption by adsorbent due to interference with As(V) uptake through competitive binding or adsorption (Bhaskar
et al. 2006); therefore, to study the individual effect of
cations (Zn2?, Cd2?, Pb2?, Ni2?, Mg2?, Cr3? and Fe3?) on
As(V) removal efficiency by magnetite nanoparticles coated
sand, batch equilibrium experiments were conducted in
presence of these cations. The As(V) % removal efficiency in
the presence of these co-existing ions was compared with
blank samples having no co-existing ions. Figure 9 represents the effect of presence of co-existing cations on
As(V) removal efficiency by adsorbent. Here, we found that
the studied cations at concentration of 100 mg/L showed
little to no interference with As(V). However, the cations
effect on As(V) removal efficiency was found in the order of
Cr3? [ Mg2? [ Ni2? [ Pb2? [ Cd2? [ Zn2? [ Fe3?.
Desorption and readsorption efficiency of adsorbent
Figure 10a and b shows the adsorption and desorption
behaviour of magnetite nanoparticles coated sand respectively. It can be seen from Fig. 10a that in first cycle

Environ Earth Sci (2016)75:381

99.99 % of As(V) was removed and with increase in

number of reuse of adsorbent, its adsorption efficiency
decreases. After 10 cycles of reuse of adsorbent only
20.3 % of As(V) was adsorbed due to degradation of
adsorbent. Figure 10b shows that initially in the first cycle
of desorption, 85.3 % of As(V) was desorbed with 0.5 M
of NaOH solution and then desorption increased up to 4
cycles and then decreased. The As(V) desorption occurs
within 7590 % in all the 10 cycles.
The schematic representation of adsorption mechanism
of As(V) species, i.e., H2AsO4- and HAsO42- on the
surface of magnetite coated sand particle is shown in the
Fig. 11.

Conclusion
A low cost and efficient adsorbent has been successfully
synthesized by coating magnetite nanoparticles on sand.
The obtained adsorbent shows significant efficiency for
As(V) removal from aqueous solutions. At optimum conditions, 99.99 % of As(V) removal is achieved. The presence of co-existing ions in aqueous solution does not show
any measurable effect on the As(V) removal efficiency by

Fig. 11 Schematic diagram for As(V) adsorption mechanism by magnetite nanoparticles coated sand

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Environ Earth Sci (2016)75:381

magnetite nanoparticles coated sand. The magnetite

nanoparticles coated sand due to solving the problem of
separation of adsorbent in column filters can be a promising and an effective adsorbent for As(V) removal from
drinking water for rural areas.
Acknowledgments This work was supported by the Department of
Science and Technology (DST), Delhi (Project number: FTP/PS-40/
2011) and Nanotechnology Lab, Jaypee University of Information
Technology, Waknaghat, Solan-173234, India.

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