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Cobalt ferrite nanoparticles aggregated schwertmannite: A novel adsorbent

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DOI: 10.1016/j.jwpe.2014.07.002

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 Journal of Water Process Engineering 3 (2014) 1–9

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Journal of Water Process Engineering

journal homepage: www.elsevier.com/locate/jwpe

Cobalt ferrite nanoparticles aggregated schwertmannite: A novel

adsorbent for the efficient removal of arsenic
A. Dey, R. Singh, M.K. Purkait ∗
Department of Chemical Engineering, Indian Institute of Technology Guwahati, Guwahati 781039, Assam, India

a r t i c l e i n f o a b s t r a c t

Article history: Arsenic poisoning is causing a serious threat to the environment. The application of nanoparticles in
Received 3 June 2014 the abatement of arsenic is becoming an intense area of research nowadays. In the present study the
Received in revised form 29 June 2014 adsorption behavior of arsenic was studied in detail by synthesizing a novel adsorbent by aggregating
Accepted 15 July 2014
cobalt ferrite nanoparticles during the formation of iron oxide hydroxide, i.e. schwertmannite. Cobalt
ferrite nanoparticle enhances the magnetic properties of schwertmannite and makes it a better candidate
Keywords:
for arsenic removal. The various structural as well as morphological properties were investigated by
Arsenic
VSM, XRD, FTIR, BET and FESEM analysis. Batch adsorption experiments were carried out by varying
Cobalt ferrite
Nanoparticle
different process parameters such as contact time, adsorbent dose, pH, temperature and presence of
Schwertmannite other co-ions. Arsenic adsorption by cobalt ferrite nanoparticle aggregated schwertmannite (CNSh) was
Adsorption found to be highly pH sensitive. Maximum arsenic was adsorbed at around pH 5.3. Study of temperature
effect on arsenic adsorption confirmed the endothermic nature of the process. Other thermodynamic
properties were also calculated and found that physical adsorption was dominant with activation energy
of 5.1 kJ/mol. Kinetic study revealed that the pseudo second order model was followed by the adsorption
process having regression coefficient (R2 ) 0.99. The equilibrium study showed that the adsorption system
followed the Langmuir isotherm model with maximum adsorption capacity of 1011 ␮g/g which was
comparably efficient than several other adsorbents.
© 2014 Elsevier Ltd. All rights reserved.

1. Introduction additives and pharmaceuticals. Arsenic is one of WHO’s 10 chemi-

cals of major public health concern. The current recommended limit
Arsenic contamination is becoming an immense area of con- of arsenic in drinking-water by WHO is 10 ␮g/L.
cern nowadays. Despite their toxic effect, inorganic arsenic bonds Naturally arsenic occurs in different oxidation states. In water,
occur on earth naturally in small amounts. Humans may be exposed it may appear in both organic and inorganic forms. Inorganic forms
to arsenic through food, water and air. Exposure may also occur of arsenic such as As(III) and As(V) causes serious threat to human
through skin contact with soil or water that contains arsenic. Inor- health. As(III) is significantly more toxic and mobile than As(V). It is
ganic arsenic can cause various health effects, such as irritation of also more difficult to remove by conventional treatment methods.
the stomach and intestines, decreased production of red and white Therefore most of the separation techniques involves pre-oxidation
blood cells, skin changes and lung irritation, heart disruptions and of As(III) to As(V) for efficient arsenic removal, causing added
brain damage. Apart from this, inorganic arsenic can damage DNA. complexity. Abatement of arsenic contaminated water has thus
High doses of organic arsenic may cause certain effects to human become a major environmental issue. There are many conventional
health, such as nerve injury and stomach aches. The arsenic cycle and non-conventional technologies, so far investigated for arsenic
has broadened as a consequence of human interference and hence removal. The conventional methods of arsenic removal such as
large amounts of arsenic end up in the environment and in living oxidation–precipitation [1], coagulation–flocculation [2], adsorp-
organisms. Arsenic is used industrially as an alloying agent, as well tion [3,4], membrane filtration [5] and nanofiltration [6] proved
as in the processing of glass, pigments, textiles, paper, metal adhe- to be inefficient because of its limitation for industrial use. The
sives, wood preservatives and ammunition. Arsenic is also used in disadvantages of traditional methods are high cost, excess sludge
the hide tanning process and, to a limited extent, in pesticides, feed production, membrane fouling, and constant monitoring of the ions
concentration (ion exchange). Comparative study of all the above
mentioned processes reveals that adsorption is one of the most
∗ Corresponding author. Tel.: +91 361 2582262; fax: +91 361 2582291. effective method for arsenic removal from aqueous solutions, and
E-mail address: [email protected] (M.K. Purkait). is currently considered as an efficient and economic method for

http://dx.doi.org/10.1016/j.jwpe.2014.07.002
2214-7144/© 2014 Elsevier Ltd. All rights reserved.
2 A. Dey et al. / Journal of Water Process Engineering 3 (2014) 1–9

water treatment. Adsorption processes are effective techniques and from Loba chemie Ltd., India. Cobalt nitrate hexa hydrate (Co
they have been used in the wastewater treatment industries to (NO3 )2 ·6H2 O), hydrochloric acid (HCl) and sodium hydroxide
remove inorganic and organic pollution for its easy handling, min- (NaOH) were procured from Merck Ltd., India. All chemicals
imal sludge production and its regeneration capability. Dion et al. were of analytical grade and used without further purification.
[7] have discussed iron and aluminum based adsorption strate- Deionised water was used for all the reactions including synthe-
gies including their advantages and disadvantages for the efficient sis and adsorption study. In order to avoid any precipitation of iron
removal of arsenic. Various adsorbents such as activated carbon oxy-hydroxides prior to synthesis of CoFe2 O4 nanoparticles, the
[8], alum impregnated activated alumina [9], hydrous stannic oxide solution of Fe(III) and Co(II) were freshly prepared by dissolving
[10], granular ferric hydroxides [11], synthetic zeolites [12] were the required amount of metal salts in 0.01 M HCl solution.
reported in the literatures for the efficient removal of arsenic. Apart
from these the adsorbent derived from the agricultural wastes,
biomass and natural resources such as wheat straw [13] is also 2.2. Preparation of adsorbent
showing remarkable performance toward arsenic removal.
Since arsenic is causing serious threat to the mankind as well The procedure for the preparation of cobalt ferrite nanopar-
as environment, researchers are more concentrated on the devel- ticles aggregated schwertmannite (CNSh) consists of two steps.
opment of new technology as well as new adsorbents which are Step 1 includes the formation of CoFe2 O4 nanoparticles by co-
cheap, active and rapid toward arsenic adsorption. These objec- precipitation technique using Fe(III) and Co(II) ions and step 2 deals
tives are fulfilled with the development of nanosized adsorbents with the synthesis of modified schwertmannite using wet chemi-
which has the advantage of high surface area as well as high cal process where the nanoparticles were embedded on it. CoFe2 O4
tendency to adsorb toxic arsenic from water. Adsorption studies nanoparticles were prepared by the co-precipitation of an aqueous
based on metal oxides nanoparticles [14–16] have shown remark- solution of Co (NO3 )2 ·6H2 O (0.25 M, 25 ml) and Fe (NO3 )3 ·9H2 O
able results. However, it is necessary to find a way for separating (0.5 M, 25 ml) by drop wise addition of NaOH solution at a temper-
and recycling the nanoparticles effectively. Hence, preparation of ature of 80 ◦ C. Schwertmannite was synthesized by homogenous
magnetic nanoparticles is attractive in such applications because hydrolysis of Fe2 (SO4 )3 ·5H2 O using urea as the neutralizing agent.
magnetic nanoadsorbent can be effectively and simply separated An aqueous solution of Fe2 (SO4 )3 ·5H2 O (12.5 g in 250 ml of dis-
and recovered from the solution by using an external magnetic field tilled water) was stirred for 15 min and preheated to a temperature
[11]. That is why synthesis of nanomagnetic particles has recently of 70 ◦ C. 5 ml of the slurry containing the fresh nanoparticles was
gained attention to the researchers. Wastewater treatment with the added to the solution and well mixed at the desired preheated tem-
help of magnetic field requires relatively high magnetic sensitive perature. 250 ml of 5 M urea solution was prepared and added drop
particles to be separated through a magnetic filter. To triumph over wise for about 2–4 h into the solution. When precipitation of crys-
this adsorbent separation problem, a novel technology using mag- tals begun, the color of the solution was changed from reddish black
netic seeding particles has been developed to enable the separation to brownish yellow and the reaction was continued until half of
of fine particles which are not magnetic materials. By modifying the the initial solution was vaporized. Thereafter, the resulting precip-
adsorbent surface characteristics with various desired species, and itates were washed repeatedly with deionised water to remove the
entrapping magnetic seeding particles during the nucleation stage unwanted impurities. The precipitate was then dried below 40 ◦ C.
enhances the selective recovery of colloidal and macromolecular
species. In this way magnetic properties of the adsorbent are greatly
improved via magnetic seeding aggregation. 2.3. Experimental methods
In this context schwertmannite which is an iron oxide hydrox-
ide with the chemical formula of Fe8 O8 (OH)6 SO4 has been found Batch adsorption experiments were carried out using 100 ml
to be an effective adsorbent for fluoride and phosphate removal arsenic solution in 250 ml conical flasks at ambient temperature.
[17]. But, it is very difficult to use as an adsorbent because of its Stock solution of 100 mg/L As(III) ion was prepared by dissolv-
very fine particle size. Thus, magnetic filtration can be considered ing an accurately weighed quantity of 100 mg of As2 O3 in 1 L of
for separation of fine schwertmannite particles from its suspended deionised water. Experimental solutions of desired concentrations
liquid. In the magnetic filtration, the conversion of the magnetic were obtained by successive dilution of the stock solution. The
property is important in order to increase the trapping efficiency effect of contact time on arsenic adsorption was observed by agi-
of adsorbent particles. tating different concentrations (200, 400 and 600 ␮g/L) of arsenic
In the present work, schwertmannite (Sh) which is an iron oxide solution with 1 mg/L of adsorbent at an ambient temperature of
hydroxide, was synthesized and the surface was modified using 25 ◦ C. Different amounts of adsorbent (0.25–2 g/L) were used to
cobalt ferrite (CoFe2 O4 ) nanoparticles (CNSh). The novel adsorbent investigate its effect on arsenic adsorption. The batch adsorption
prepared by magnetic seeding was characterized by XRD, FTIR, VSM studies at three different temperatures of 25, 40 and 60 ◦ C were
and FESEM. The efficacy of CNSh as an adsorbent had been studied performed to observe the temperature effects. Initial pH of the solu-
by varying different parameters such as contact time, adsorbent tion was varied from around 3 to 11 to determine the effect of pH
dose, pH, stirring speed, temperature and the presence of other co- on the extent of adsorption. Presence of co-ions on the adsorption
ions. Thermodynamic behavior as well as reaction kinetics were affinity of CNSh for arsenic adsorption was studied with varying
studied in detail. The most common adsorption isotherm model concentration of phosphate ions. Standard technique was used to
such as Langmuir and Freundlich were used to investigate the determine the remaining concentration of As(III) ions in the solu-
equilibrium behavior of the system. A regeneration technique was tion using atomic absorption spectrophotometer. The amount of
proposed in order to reuse the adsorbent for better economy. arsenic adsorbed per unit weight of adsorbent at time t,q1 (␮g/g)
and arsenic removal efficiency, R were calculated as:
2. Experimental
(C0 − Ct )V
qt = (1)
2.1. Materials M

The reagents used in the experiment ferric nitrate nonahy- C0 − Ct

R= × 100 (2)
drate (Fe (NO3 )3 ·9H2 O), arsenic trioxide (As2 O3 ) were purchased C0
 A. Dey et al. / Journal of Water Process Engineering 3 (2014) 1–9 3

Fig. 1. Characterization of adsorbent; (a) point of zero charge pHzpc , (b) XRD, (c) FTIR, (d) VSM and (e) FESEM micrograph of the CoFe2 O4 nanoparticles aggregated
schwertmannite.

where C0 is the initial arsenic concentration (␮g/L), Ct is the con- spectroscopy (FTIR); Make: Perkin Elmer, USA, Model: LR 64912C.
centration of arsenic at any time t, V is the volume of solution (L) FTIR analysis was performed using the KBr supported technique in
and M is the mass of adsorbent (g). the range of 450–4000 cm−1 with a scanning rate of 40 and a res-
olution of 4 cm−1 . A wide angle X-ray diffractometer (XRD; Make:
2.4. Characterization techniques and measurement Bruker, Model: D8) was used to study the crystallite structure of
the synthesized adsorbent. Scanning was done from high angle 2
The prepared adsorbent (CNSh) were characterized for the pres- value between 20◦ and 75◦ at a speed of 0.5 s/◦ in continuous mode
ence of various functional groups by Fourier transform infrared at an increment of 0.05. XRD patterns were obtained using radiation
4 A. Dey et al. / Journal of Water Process Engineering 3 (2014) 1–9

(Cu K␣ = 0.154 nm). Field emission scanning electron microscopy

(FESEM; Make and model: Zeiss LSM 510 Meta) was used to exam-
ine the morphological structure and to measure the average particle
size. The analysis was done by LEO 1430 vp at 5 kV at magnifica-
tion of 59.46 KX. The magnetic properties were investigated by the
vibrating sample magnetometer (VSM; Make and model: Lakeshore
7410). The hysteresis loops were measured under a magnetic field
strength of 15,000 Gauss at room temperature. The data were taken
with 80 points/loop with a scan speed 10 s/point.
The point of zero charge (pHzpc ) of CNSh used for adsorption
experiment was determined by using solid to liquid ratio of 1:1000.
For this, 0.1 g of CNSh was added to 100 ml of 0.01 M NaCl solution
with varying pH from around 3–11 and stirred for 48 h. Final pH
of the solution was plotted against initial pH of the solution and
pHZPC was measured. A digital pH meter (Eutech Instruments, pH
510) was used to measure the pH of the solution. Shaking incuba-
tor (Daihan Labtech Co. Ltd) was used for shaking all the adsorption
experiments. Arsenic (III) concentration of the solution was deter-
mined by Atomic absorption spectrophotometer (Model No. 240
FF, Varian, Netherlands).

Fig. 2. Effect of contact time and initial concentration of arsenic on the extent of
3. Results and discussion adsorption.

3.1. Characterization of CNSh

Significant change in the extent of adsorption was not observed
(>1%) even further increase in contact time up to 240 min. There-
The point of zero charge was plotted and shown in Fig. 1(a).
fore, rest of the experiments were conducted for 240 min. For the
It was observed from the figure that pHzpc value of CNSh was at
initial concentration of up to 400 ␮g/L, more than 93% adsorption
pH 3.7 which concluded that the adsorbent surface had a posi-
was observed, whereas for 600 ␮g/L, the percentage removal was
tive charge in aqueous medium. Fig. 1(b) shows the XRD pattern
89%. From the figure it is evident that for lower initial concentration
of CoFe2 O4 nanoparticle aggregated schwertmannite. The novel
of arsenic, the extent of removal is more. The percentage removal
adsorbent did not show any relevant peak corresponding to the
of arsenic decreases with increase in initial concentration. This is
cubic spinel phase of the cobalt ferrite. This was because of the fact
because of the fact that with increase in concentration, there will
that small amount of the nanoparticles aggregated into the new
be increased competition for the active adsorption sites and as the
adsorbent structure where the ratio of CoFe2 O4 nanoparticles to the
time proceed the number of active sites were decreased and then
schwertmannite ranged from 5 to 6. The broad peak at 2 = 35.45
adsorption becomes increasingly slowdown.
which corresponds to the (3 1 1) miller indices confirmed that the
structure of schwertmannite was modified with CoFe2 O4 nanopar-
ticles. From the FTIR spectra as shown in Fig. 1(c), it was seen that 3.2.2. Effect of adsorbent mass
the spectrum of the adsorbent is dominated by the prominent peak The effect of adsorbent mass on the extent of arsenic adsorp-
at around 3400 cm−1 and 1625 cm−1 corresponds to the stretching tion for the initial concentration of 200 ␮g/L was depicted in Fig. 3.
of OH− bond. Other intense bands at 1370 and 1120 cm−l corre- The adsorbent mass was varied from 0.25 g/L to 2 g/L. The maxi-
sponds to the formation of a bidentate bridging complex between mum arsenic removal of around 95% was observed with the doses
SO4 −2 and Fe3+ . The vibrations at around 710 cm−1 relates to the of 1 g/L and then the rate of increase is marginal. The sharp increase
Fe O stretching. in adsorption rate at the beginning is because of greater surface area
Fig. 1(d) shows the VSM plot of CNSh. From the literature it and availability of higher adsorption sites. After the critical dose the
was found that the schwertmannite is paramagnetic in nature.
However, the aggregation of CoFe2 O4 nanoparticles enhances the
magnetic properties of the schwertmannite and the magnetization
curve of the CNSh confirms the ferromagnetic nature with satura-
tion magnetization value of 13.95 emu/g and the coercivity value
of 969.55 G. FESEM micrograph as shown in Fig. 1(e) reveals the
spherical to ellipsoidal morphology of the particles with hedge
like aggregates which leads to dense porous network. The needle-
like structures with average width and thickness of 10–20 nm and
length of 80–90 nm radiate from the particle surfaces to give “pin-
cushion” morphology to the material.

3.2. Adsorption studies

3.2.1. Effect of contact time and initial arsenic concentration

The variation in percentage removal of arsenic with contact time
at different initial concentrations ranging from 200 to 600 ␮g/L is
shown in Fig. 2. It may be observed from the figure that the rapid
adsorption of arsenic took place within 60 min and then adsorp-
tion becomes slow and almost attains equilibrium after 180 min. Fig. 3. Variation of arsenic adsorption with adsorbent dose.
 A. Dey et al. / Journal of Water Process Engineering 3 (2014) 1–9 5

Fig. 5. Variation of log(qe m/Ce ) versus 1/T.

Fig. 4. Effect of pH on the percentage adsorption of arsenic.

experiments at various temperatures using the following equations

[18]:
rate of adsorption decreases due to the fact that although there is an
increasing number of active sites but shortage of adsorbate is takes G◦ = H ◦ − TS ◦ (3)
place in the solution. With increase in time, the number of active q m S ◦ −H ◦
e
sites on the adsorbent and the bulk arsenic concentration were log = + (4)
Ce 2.303R 2.303RT
decreased and reached in equilibrium. Therefore the amount of
residual arsenic concentration was stagnant with further increase where m is the adsorbent dose (g/L), qe is the amount of arsenic
in adsorbent dose. Similar observation is also found in the literature adsorbed per unit mass of adsorbent (␮g/g). Ce is equilibrium con-
[20]. centration (␮g/L) and T is temperature in Kelvin. qe /Ce is called the
adsorption affinity. The enthalpy of adsorption (H◦ ) and entropy
(S◦ ) are calculated from the slope and intercept of log(qe m/Ce )
3.2.3. Effect of pH
versus 1/T plot (Fig. 5). Once these two parameters are obtained,
The pH of the medium plays an important role in affecting
G◦ is determined from Eq. (3). The values of H◦ , S◦ and G◦ for
the extent of arsenic adsorption. To determine the optimum pH
the initial arsenic concentrations of 200 ␮g/L are shown in Table 1.
required for the maximum removal of arsenic, equilibrium sorption
The Gibbs free energy change (G◦ ) is −ve and H◦ is positive, indi-
with initial arsenic concentration of 200 ␮g/L was studied over a pH
cating that the adsorption process is spontaneous and endothermic.
range of around 3–11. The effect of pH on arsenic adsorption at the
The low value of S◦ implied that no remarkable change in entropy
end of 240 min was shown in Fig. 4. The percentage arsenic adsorp-
occurred during the adsorption process. In addition the positive
tion was increased with pH, reaching maximum at pH around 5.3,
value of S◦ reflects an increase in randomness at the solid/solution
and then decreased slowly up to the pH value of 9. Beyond pH
interface during the adsorption. The low value of H◦ indicates that
9, the percentage removal decreased sharply. Initially, as the pH
the physisorption dominates in the understudy adsorption system.
increased from around 3 (pH < pHzpc = 3.7), the arsenic adsorption
However, in order to further confirm the assertion that the
increased due to the positive surface charge of CNSh which attracts
physical adsorption is the predominant mechanism, the values of
the negatively charged arsenite ion and became maximum at pH
activation energy (Ea ) and sticking coefficient (S*) were determined
around 5.3. There is a sharp decrease in % arsenic removal beyond
from the experimental data by using a modified Arrhenius type
pH 9. This is attributed to the fact that as the pH > pHzpc , the sur-
equation as follows [19].
face of the adsorbent becomes negatively charged and there was
a strong competition of hydroxide ions to the active sites of CNSh S∗ = (1 − )e(−Ea/RT ) (5)
which results in the electrostatic repulsion of anionic arsenite ion
The S* is a function of the adsorbate/adsorbent system under
by the negatively charged adsorbent surface. The arsenic removal
investigation. Its value lies in the range 0 < S* < 1 and is completely
efficiency does not show much variation in the pH range of 5.3–9.2.
dependent on temperature of the system. The parameter S* indi-
This was due to the replacement of hydroxyl ions by the arsenite
cates the potentiality of an adsorbate to remain on the adsorbent
ion as the hydroxyl ion concentration was less in that pH range.
system. The  was calculated by using following equation:
At highly basic condition of pH > 9.2, the hydroxyl ion concentra-
tion was much more which leads to the formation of H2 AsO3− and Ce
 =1− (6)
AsO3− species and hence leads to the sharp reduction of removal C0
percentage [25].
Activation energy (Ea ) and sticking probability (S*) were esti-
mated from the plot of ln(1 − ) versus 1/T and were shown in
3.2.4. Temperature effect and thermodynamic study Table 1. The lower value of Ea and S* confirms the physisorption
To investigate the effect of temperature on the adsorption behavior of the present adsorption system.
capacity, the experiments were carried out for initial arsenic
concentrations of 200 ␮g/L at three different temperatures of 3.2.5. Effect of phosphate ions
25 ◦ C, 40 ◦ C and 60 ◦ C, respectively. It has been observed that Presence of phosphate as co-anions has a significant effect on
with increase in temperature, the % arsenic adsorption increases arsenic adsorption onto many adsorbents. The effect of phosphate
marginally from 94.8 to 95.8% indicating the endothermic nature ions on the arsenic removal efficiency was investigated by varying
of adsorption. The thermodynamic parameters such as change in the concentration of phosphate ion from 0.2 to 1 mM and shown
standard free energy, enthalpy, and entropy are calculated from in Fig. 6. From the figure it can be confirmed that the removal of
6 A. Dey et al. / Journal of Water Process Engineering 3 (2014) 1–9

Table 1
Thermodynamic parameters for the adsorption of arsenic on CNSh at different temperatures.

Temperature (◦ C) H◦ (KJ/mol) S◦ (KJ/mol) S* Ea (KJ/mol) −G◦ (KJ/mol)

−3
25 5.3 0.042 6.49 × 10 5.1 7.20
40 7.84
60 8.68

Fig. 6. Effect of phosphate ion concentration on the extent of adsorption of arsenic.

Fig. 7. Pseudo first order kinetic model for the adsorption of arsenic.
arsenic was decreased by more than 20% when phosphate concen-
trations were 0.5 mM. The decrease in arsenic adsorption was due
agree with the experimental data (qe,exp ). Therefore, it may be con-
to competitive adsorption of arsenic and phosphate ions. The con-
cluded that the kinetics of understudy adsorption system was not
centrations of competing anions in this study were much higher
probably following the pseudo first order kinetic model and hence
than those likely to be encountered in groundwater. Thus, CoFe2 O4
not the diffusion controlled phenomena.
nanoparticles aggregated schwertmannite were able to remove
arsenic even at exceptionally high concentrations of the competing
3.2.6.2. Pseudo second order kinetic model. The sorption kinetics
anions used in this study.
may be represented by pseudo-second-order model [21] as:

3.2.6. Kinetic study dqt

= k2 (qe − qt )2 (9)
The kinetics of arsenic adsorption was evaluated by using dt
pseudo-first-order and pseudo-second-order models. The various where k2 is the equilibrium rate constant for pseudo-second-
parameters were calculated from the plots of the various kinetic order sorption (g/␮g min). Integrating Eq. (9) using the necessary
model equations and summarized in Table 2. Between these two boundary conditions and rearranging rate law model for a pseudo-
models the criterion for their applicability is based on judgment on second-order reaction is given as:
the respective regression coefficient (R2 ) and agreement between
t 1 t
experimental and calculated value of qe . = + (10)
qt k2 qe 2 qe

3.2.6.1. Pseudo first order kinetic model. This model assumes that Fig. 8 shows that the plot of t/qt versus t which gives a straight
the rate of change of solute uptake with time is directly proportional line with slope of 1/qe and intercept 1/k2 qe 2 . Using the value of qe
to difference in equilibrium concentration and the amount of solute calculated from the slope, the value of k2 is determined from the
adsorbed with time. The rate constant of adsorption is expressed intercept. The calculated value of k2 , qe and their corresponding
as a first-order rate expression given as [20]. regression coefficient (R2 ) values are presented in Table 2. The value
of regression coefficient (R2 ) is approximately 0.99 for all the three
dqt
= k1 (qe − qt ) (7) concentration which confirms that, the sorption kinetics of arsenic
dt follows a pseudo second order model. It may also be found from
where qt and qe are the amount of arsenic adsorbed (␮g/g) at con- Table 2 that the calculated qe values are well matched with that
tact time t (min) and at equilibrium, k1 is the pseudo-first-order rate of experimentally obtained qe . Thus it may be concluded that the
constant (min−1 ). After integrating with the initial and final bound- adsorption of arsenic on CoFe2 O4 nanoparticles aggregated schw-
ary conditions at t = 0, qt = 0 and at t > 0, qt = qt and rearranging Eq. ertmannite can be better explained by pseudo-second-order kinetic
(7), the rate law for a pseudo-first-order reaction becomes model than that of first-order kinetic model.
ln(qe − qt ) = ln qe − k1 t (8)
3.2.7. Equilibrium study
Fig. 7 shows the plot of ln(qe − qt ) versus t which gives a straight Adsorption properties and equilibrium parameters, commonly
line with slope of −k1 and intercept ln qe . Adsorption rate constant known as adsorption isotherms, describes the interaction between
k1 and equilibrium adsorption capacity qe was calculated corre- the molecules of adsorbate and adsorbents. Isotherm also helps to
sponding to various arsenic concentration and are shown in Table 2. provide information about the optimum use of adsorbents. So, in
The regression coefficients (R2 ) for the pseudo first order kinetic order to design an adsorption system to remove arsenic from solu-
model are relatively low and the calculated qe values (qe,cal ) do not tions, it is essential to establish the most appropriate correlation for
 A. Dey et al. / Journal of Water Process Engineering 3 (2014) 1–9 7

Table 2
Different kinetic model parameters for arsenic adsorption at 25 ◦ C.

Initial arsenic concentration (␮g/L)

200 400 600

Pseudo first order qe,expt (␮g/g) 189.7 375.2 532.8

kinetics qe,cal (␮g/g) 101.3 206.34 345.12
k1 (min−1 ) 0.026 0.0288 0.028
R2 0.96 0.93 0.97

Pseudo second qe,cal (␮g/g) 196.17 392.5 594.4

order kinetics k2 × 10−4 (g/␮g min) 7.952 3.563 2.24
R2 0.99 0.99 0.99

Fig. 9. Langmuir isotherm of arsenic adsorption onto the CNSh.

Fig. 8. Pseudo second order kinetic model for the adsorption of arsenic.

the equilibrium curve. The most useful equilibrium isotherms are where b(L/␮g), is the Langmuir constant and C0 (␮g/L) is the
the Langmuir and the Freundlich isotherms. Langmuir isotherm is initial concentration in the liquid phase. The value of RL indicates
based on the assumption that there are a specific number of active the shape of the isotherm to be either unfavorable (RL > 1), linear
sites which are homogenously distributed on the adsorbent surface. (RL = 1), favorable (0 < RL < 1) or irreversible (RL = 0). For the adsorp-
These sites are equivalent and the adsorption involves the attach- tion of arsenic onto the understudy adsorption system, RL values
ment of only one layer of molecules to the surface, i.e. monolayer obtained were in the range of 0.08–0.05. This indicated that the
adsorption. It also assumes that there is no interaction between adsorption was more favorable.
adsorbed molecules. The equation of Langmuir isotherm is repre- The Freundlich isotherm model is an exponential equation that
sented as follows [22]: applies to adsorption on heterogenous surfaces with interaction
between adsorbed species and not restricted to the formation of
qm bCe monolayer. This model assumes that as the adsorbate concentra-
qe = (11)
1 + bCe tion increases, the concentration of adsorbate on the adsorbent
surface also increases and correspondingly that sorption energy
where qe is the amount adsorbed at equilibrium (␮g/g), Ce is
exponentially decreases on completion of the sorption centers of
the equilibrium concentration of the arsenic (␮g/L), constant b is
an adsorbent. The expression for Freundlich isotherm is given as
related to the energy of adsorption (L/␮g), and qm is the Langmuir
[23]
monolayer adsorption capacity (␮g/g). When 1/qe is plotted against
1/Ce (Fig. 9), straight line with slope 1/bqm and intercept 1/qm is
qe = KF Ce 1/n (13)
obtained. The calculated values of Langmuir constants b and qm
are listed in Table 3. The essential characteristics of the Langmuir where KF [(␮g/g) (L/␮g)1/n ] is roughly an indicator of the adsorp-
isotherm can be expressed in terms of a dimensionless constant tion capacity and 1/n is a measure of intensity of the adsorption.
separation factor RL that is given by [23]: Higher the 1/n value, more favorable is the adsorption. KF and n
1 values were calculated and shown in Table 3. As seen from Table 3,
RL = (12) high regression correlation coefficient (R2 = 0.99) is shown by the
1 + bC0
Langmuir model. This indicates that the Langmuir model is suit-
able for describing the adsorption equilibrium of arsenic by the
Table 3 modified schwertmannite. The maximum monolayer adsorption
Langmuir and Freundlich isotherm constants for the adsorption of arsenic on CNSh capacity (qm ) determined from the Langmuir isotherm is 1011 ␮g/g.
at 25 ◦ C.
The extent of adsorption is far better than several other adsorbents
Langmuir isotherm constant Freundlich isotherm constant used for arsenic removal [3]. A comparison of adsorption capacities
qm (␮g/g) b (L/␮g) R2 KF (␮g/g) (L/␮g)1/n n R2 of various adsorbent used for arsenic removal is shown in Table 4.
It may be conclude from the table that the adsorption capacity of
1011 0.018 0.99 175.56 3.67 0.93
present CNSh adsorbent is better that few other adsorbents.
8 A. Dey et al. / Journal of Water Process Engineering 3 (2014) 1–9

Table 4
Comparison of arsenic adsorption capacity of CNSh with some reported adsorbents.

Adsorbent Concentration range (␮g/L) Surface area (m2 /g) Models used to calculate qe qe (mg/g) References

Activated alumina 1000 370 Langmuir 0.18 [24]

Manganese ore – – Langmuir 0.53 [25]
Iron oxide coated sand 100 10.6 Langmuir 0.041 [26]
Iron oxide uncoated sand 100–800 – Langmuir 0.006 [27]
Iron oxide coated cement (IOCC) 700–1350 – Langmuir 0.6 [28]
Pine wood char 10–100 2.73 Langmuir 0.0012 [29]
Copper (II) oxide 500–1000 52.11 Langmuir 1.0862 [3]
CNSh 200–600 – Langmuir 1.011 Present work

4. Conclusion

CNSh was found to be a potential adsorbent for arsenic removal

from water. The sorption of arsenic onto CNSh was found to be
highly pH dependent. More than 95% arsenic was adsorbed for
up to 200 ␮g/L initial arsenic concentrations using 1 g/L adsorbent
dose and a contact time of 240 min. The percentage adsorption
was decreased gradually with increase in initial arsenic concentra-
tion. Thermodynamic studies revealed that the adsorption process
of arsenic was spontaneous and endothermic in nature with H◦
value 5.3 kJ/mol confirming the physicochemical adsorption pro-
cess. The pseudo second order kinetic model was found to best
correlate with the experimental data for arsenic adsorption. Equi-
librium study showed excellent fit to Langmuir isotherm model
than Freundlich isotherm model with an adsorption capacity of
1011 ␮g/g which indicates monolayer sorption on the surface of
the nano-adsorbent. The spent adsorbents were regenerated with
NaOH solutions and regenerated adsorbents showed very good
adsorption efficiencies. Finally, the prepared adsorbent may be
selected as an alternate to the existing one used for arsenic removal.
Fig. 10. Mass of adsorbent required for complete removal of arsenic from arsenic References
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