Chemical Engineering Journal 248 (2014) 18–26

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Chemical Engineering Journal

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

Fixed-bed column performance of Mn-incorporated iron(III) oxide

nanoparticle agglomerates on As(III) removal from the spiked
groundwater in lab bench scale
Abir Ghosh a, Sharadindra Chakrabarti b, Uday Chand Ghosh a,⇑
a
Department of Chemistry, Presidency University (Erstwhile Presidency College), 86/1 College Street, Kolkata, India
b
Environmental System Management, Presidency University (Erstwhile Presidency College), 86/1 College Street, Kolkata, India

h i g h l i g h t s g r a p h i c a l a b s t r a c t

 Agglomerated Mn-incorporated Fitting breakthrough data with non-linear Thomas model and bed depth variation Bed Depth Service
Fe(III) oxide nanoparticles packed Time model with breakthrough data, obtained from the variation of bed depth for the arsenic removal
fixed bed column for As removal. from As(III) spiked groundwater suggested nice applicative possibility of agglomerated Mn-incorporated
 Design parameters on As removal Fe(III) oxide nanoparticles for designing arsenic removal filter.
from groundwater.
 Thomas model described the 5500

breakthrough data too well. 5000

 BDST model described the bed depth 4500

4000
variation data well.
Service time (min)

3500
 TCLP test suggested non-hazardous
3000 Thomas model fitting

waste. 1.2
Adams-Bohart model fitting

2500 1.0

2000
0.8

0.6
ct/c0

1500 0.4

1000 0.2

0.0

500 0 5000 10000 15000 20000 25000 30000 35000 40000

Time(min)
Influent concentration (mg L-1): 1 .0 1.40 1.72
0
-4 -3 -2 -1 0 1 2 3 4 5 6
Bed depth (cm)

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

Article history: Assessment of the breakthrough performance of agglomerated Mn-incorporated Fe(III) oxide nanoparti-
Received 16 December 2013 cle (MNFO) packed fixed-bed column on As(III) removal was conducted from the spiked groundwater.
Received in revised form 3 March 2014 Variable parameters examined were column bed depth, effluent discharge rate and input As(III) concen-
Accepted 4 March 2014
tration. Modeling of the breakthrough point (As concentration 6 0.01 mg L1) data by the Thomas and the
Available online 15 March 2014
Adams–Bohert models showed better fit of data with Thomas model (R2 = 0.98–0.99) than Adams–Bohert
model (R2 = 0.90–0.94). The Bed Depth Service Time (BDST) modeling of breakthrough data at variable
Keywords:
bed depths showed the length of mass transfer zone (D0), the adsorption capacity per unit volume
Arsenic(III)
Fixed-bed performance
(NBD) and the rate constant (kBD) values 9.65  107 cm, 3.34 mg cm3 and 2.74  103 L mg1 min1,
Mn-incorporated Fe(III) oxide respectively. Best fixed-bed column performance was noted (VB = 16.39 L) only for the highest EBCT
Breakthrough modeling (8.3 min) and lowest input As(III) concentration (1.0 mg L1). Thus, the MNFO fixed bed filtering column
Removal is capable to reduce not only high arsenic level but also other inorganic contaminants such as iron and
phosphate from the groundwater.
Ó 2014 Elsevier B.V. All rights reserved.

⇑ Corresponding author. Tel.: +91 33 2241 3893.

E-mail address: ucghosh@yahoo.co.in (U.C. Ghosh).

http://dx.doi.org/10.1016/j.cej.2014.03.010
1385-8947/Ó 2014 Elsevier B.V. All rights reserved.
 A. Ghosh et al. / Chemical Engineering Journal 248 (2014) 18–26 19

1. Introduction as an oxidizing agent to oxidize Mn (II) to Mn (III). The same meth-

od was used for the preparation of other Fe–Mn mixed oxide sam-
High concentration of arsenic (>10 lg L1) in groundwater is a ples simply increasing manganese mole proportions with iron(III)
worldwide problem [1], because drinking of such water for long solution 1:5 to 5:1 for the optimization of Fe:Mn ratio in MNFO
days causes a variety of carcinogenic effects on different organs for arsenic adsorption by batch experimental procedure at pH
of humans, which ultimately leads to death [2,3]. This problem is 7.2–7.3 and room temperature.
severe in Bangladesh and West Bengal in India [4,5]. Different
agencies including World Health Organization (WHO) fixed the 2.2. Standard As(III) solution
maximum permissible limit for arsenic (10 lg L1) [6] in drinking
water. It is thus essential to maintain the arsenic level 6 10 lg L1 The standard stock As(III) solution (1000 mg L1) was prepared
in drinking water before human consumption. by dissolving an appropriate amount As2O3 (purity: 99.9%) (BDH,
Among the two inorganic arsenic species in groundwater, ar- England) in 100 ml NaOH (4%) solution, which was diluted to
senic(III) is more mobile and toxic than arsenic(V) [7,8]. Cullen 1.0 L with As-free de-ionized water. The measured volume of this
and Reimer [8] reported that the inorganic arsenic is about 100 stock was diluted to a desired level with 0.2% HCl (v/v) before
times more toxic than the organic-arsenic species. Again, ar- working.
2 0
senic(V) (as H2AsO 4 and HAsO4 ) and arsenic(III) (as H3AsO3 and

H2AsO3 ) predominate in oxic and anoxic ground waters [9], 2.3. Water sample used for experiments
respectively. This type of speciation naturally has a profound effect
on its removal/remediation processes. Arsenic(III), for example, Groundwater was collected from a hand pump attached tube
exhibits as As(OH)3 (pK1 = 9.2) in the pH ranges of natural waters well (depth: 150 ft) of college street area, Kolkata (West Bengal),
which accounts for the fact that it does not thermodynamically India and analyzed for some water quality parameters including
interact with other elements, making more difficult to remove arsenic by the methods as described in ‘Standard Methods for
from water using various treatment processes. the Analysis of Water and Wastewater published by APHA, AWWA
Among the various treatment processes/technologies developed and WEF’ [27]. The parameters analyzed (mg L1, except pH) were
and refined over the years for As remediation, adsorption has pH (7.50), turbidity (0.60 NTU), total hardness (970), calcium
emerged as a particularly attractive candidate for As eradication (260.52), magnesium (709.48), iron (0.35), phosphate (0.10), ni-
chiefly due to its low cost, less space requirement for installation trate (0.427), chloride (17.60), fluoride (0.50) and total arsenic
and simple operation. It had been found that Fe-based adsorbents (0.02). This water sample despite contains arsenic above the
had received considerable attention in recent years to treat ar- WHO prescribed permissible level (0.01 mg L1) is spiked with ar-
senic-rich (>10 lg L1) groundwater [10–15]. Hydrous Ferric Oxide senic(III) solution up to a level of desire (1.0, 1.4 and 1.72 mg L1)
(HFO) is a promising adsorbent for both inorganic arsenic species for conducting experiments. It was spiked up with arsenic(III) solu-
[14,15]. The Fe-based inorganic hybrid adsorbents, especially bin- tion, because the ground waters of arsenic affected regions of West
ary metal oxides have shown enhanced efficacy in removing high Bengal (India) and Bangladesh are rich with reduced arsenic by 60–
arsenic from the contaminated groundwater [16–18]. Modification 90% of As(total). This water sample was fed onto the fixed-bed of
of HFO surface incorporating manganese ion had shown to en- MNFO packed column and allowed to pass gravitationally.
hance the specific surface area, which in turn increased its adsorp-
tion capacity compared to pure HFO [18]. Most materials were 2.4. Experimental setup
investigated for arsenic adsorption kinetics and equilibrium by
batch procedure. Agglomerated nanoparticles of Mn-incorporated Nanoparticle agglomerates of MNFO (size: 0.84–1.68 mm) were
Fe(III) oxide (MNFO) had also been synthesized, and investigated packed uniformly into glass tubes (height: 59 cm, internal diame-
for the arsenic(III) adsorption kinetics and equilibrium [18]. De- ter, id: 2.30 cm, cross sectional area: 4.153 cm2) over the glass
spite the parameters such as fixed-bed depth, effluent discharge wool sheet up to the desired bed depths as-shown in ‘Supporting
rate and inlet solution solute concentration are essential for Information (SI)’ section (Fig. S1). Here, MNFO particles were
designing the filter, yet the fixed-bed investigation for the arsenic packed carefully to minimize void spaces, channels and cracks in
removal has been found to be limited in literatures [19–26]. Since bed. Each MNFO packed tube was fitted with a cup at the top (res-
the batch results of arsenic(III) adsorption by synthetic MNFO ob- ervoir of feed solution) and a stopcock at the bottom for regulating
tained were found to be encouraging [18], it had been aimed that effluent discharge. The input solution (pH: 7.50 ± 0.10, tempera-
the MNFO packed fixed bed column parameters on As(III) removal ture: 30 ± 1 °C) was allowed gravitationally to flow down through
from groundwater should be investigated prior designing the pilot the fixed-bed clamped vertically with the help of strand. Before
scale filter for field test. feeding the input water, MNFO packed fixed-bed was washed five
The present work reports herein the efficiency assessment of ar- times with arsenic-free water (pH 7.5–7.8), and then the arsenic-
senic removal by MNFO packed fixed-bed column from the As(III)- rich water was input at a pre-fixed discharge rate of effluent. Efflu-
spiked groundwater samples on lab-bench scale with modeling of ent of each fixed-bed was collected by 1.0 L fractions, and analyzed
the breakthrough data using theoretical models such as Thomas, for the residual arsenic concentration by the standard method [27].
Adams–Bohert and Bed Depth Service Time (BDST). The variable parameters investigated were bed-depth, effluent dis-
charge rate and input arsenic concentration (C0) [19–26].
For conducting the effect of fixed-bed depth on breakthrough
2. Materials and methods curves, three separate fixed-beds of depth 1.0, 3.0 and 6.0 cm
(bed volume, BV: 4.15, 12.46 and 24.92 cm3), respectively, were
2.1. Agglomerated nanoparticles of Mn-incorporated Fe(III) oxide prepared by careful packing with 3.5, 10.5 and 21.0 g of MNFO.
(MNFO) synthesis Experimental water sample (arsenic C0: 1.72 mg L1) was allowed
to flow down with an effluent discharge rate (3.0 ± 0.1 ml min1;
Nanoparticle agglomerates of MNFO was synthesized [18] from empty bed contact time, EBCT: 1.3, 4.1 and 8.3 min.) through the
the mixture solution of equal molar iron(III) chloride (FeCl3) and specified fixed-beds.
manganese(II) chloride (MnCl2) (v/v = 5:1) by precipitating with For conducting the effect of effluent discharge rate on break-
1.0 M sodium hydroxide. Herein, sodium hypo chloride was used through curves, water sample of arsenic C0 = 1.72 mg L1 was fed
20 A. Ghosh et al. / Chemical Engineering Journal 248 (2014) 18–26

on three separate fixed-beds of depth 6.0 cm each. The liquid was with empirical formula MnxFe2xO3yH2O. Thus, the MNFO mate-
collected with separate three discharged rates 3.0, 5.0 and rial used herein is nanostructured, microcrystalline and hydrated
7.0 ml min1 (EBCT: 8.3, 4.9, 3.5 min). material with high surface area, rough surface morphology and
For conducting the influence of input arsenic level on break- porous structure.
through curves, three separate water samples of arsenic C0 1.0,
1.4 and 1.72 mg L1 were separately fed, respectively, on three
3.3. Breakthrough curves
fixed-beds of each depth 6.0 cm with an effluent discharge of rate
3.0 ml min1 (EBCT: 8.3 min).
Experimental data obtained varying parameters such as the
depth of fixed-beds, the discharge rate of effluent and the arsenic
2.5. Desorption experiment
C0 of input water were presented in (Figs. 3–5) by plotting effluent
arsenic concentration versus throughput volume (L) of water as
Desorption of arsenic from MNFO surface (3.2 mg g1) was agi-
breakthrough curves.
tated (300 rpm) for 1 h at room temperature loading 0.50 g of that
Fig. 3 shows the concentration changes from the input C0
material with optimized 50 ml of 2.0 M NaOH solution succes-
(1.72 mg L1) of arsenic in feed water with increase of throughput
sively in three stages. In each stage, the liquid was decanted from
volume at different depth of the MNFO packed fixed-beds. It is seen
the settled solid material and again treated with alkali solution of
that the throughput volume at breakthrough point, where arsenic
same volume. The decanted liquid of each stage was analyzed for
(total) concentration in effluent (Cb) was 0.01 mg L1 had increased
arsenic [27].
with increasing depth of the fixed-beds. Increase of the throughput
volume (VB, L) of water at breakthrough point, however, did not in-
3. Results and discussion
creased proportionately with increasing depth of the fixed-beds in
columns. Fig. 4 displays the change of arsenic concentration in
3.1. Optimization of Fe to Mn mole proportion in MNFO for arsenic
effluent from the input C0 (1.72 mg L1) level in water with
removal
increasing discharge rate. It has been seen from the breakthrough
curves that the VB had increased with decreasing discharge-rate
MNFO materials varying Fe to Mn mole proportions from 5:1 to
of the effluent, which is owing to the increase of EBCT. That is, de-
1:5 when investigated for the arsenic removal using batch method
crease of the discharge-rate of effluent should increase the effi-
showed that the material with Fe:Mn ratio of 5:1 has highest ar-
ciency of arsenic removal of the MNFO packed fixed-beds.
senic adsorption performance (Fig. S2, SI section). Thus, the MNFO
Fig. 5 displays the change of arsenic concentration in effluent
sample (Fe: Mn  5:1) to be investigated for systematic arsenic
water against the volume of treated water from the input arsenic
adsorption was characterized only by a number of physicochemical
C0 = 1.0, 1.40 and 1.72 mg L1. It is seen that the VB of water at
methods.
breakthrough point had decreased with increasing C0 of input
water, indicating the reduction of arsenic removal efficiency of
3.2. Characterization of MNFO
MNFO packed fixed-beds. Trends of the results reported herein
are found to be almost similar with some other workers [19,24–
Characterizations of the synthetic MNFO were reported already
26]. The feed water (C0 = 1.72 mg L1) and the effluent water (dis-
from our laboratory [18]. The powder X-ray diffraction (XRD) pat-
charge rate: 3.0 ml min1) from the MNFO particles packed fixed
tern, thermo gravimetric and differential thermal (TG-DT) spectra,
beds at breakthrough point (Cb = 0.01 mg L1) were analyzed to as-
Föurior transform infra red (FTIR) spectra, Raman spectra, atomic
sess the improvement of water quality parameters. The analyzed
force microscopic (AFM) image, BET surface analytical plot and
parameters are given in Table 1, which showed the overall
pHzpc analysis have been shown (Figs. S3–S9) in SI section of this
improvement of drinking water quality. Further, the MNFO packed
manuscript. Transmission electron microscopic (TEM) image
filter reduced not only the concentration level of arsenic but also
(Fig. 1) and XRD pattern (Fig. S3) data analyses revealed that the
iron and phosphate.
average particle size of this hydrous material was around 5–
6 nm. The BET surface area (m2 g1), pore size (nm), pore volume
(cm3 g1) and pHzpc analyzed of this material were 186.28, 8.12, 3.4. Breakthrough and exhaustion point capacities
0.31 and 7.2 ± 0.2, respectively. The scanning electron micro-
graphic (SEM) image with EDS spectrum (Fig. 2) and TG spectrum Value of the adsorption capacity at breakthrough point (qB,
(Fig. S4) analyses showed that the percentage (parenthesis) of Fe mg g1), which can be calculated has been defined as the amount
(41.7), Mn (7.6), O (49.4) and H2O (22.56) in MNFO (Fe:Mn  5:1) of arsenic bound by unit bed mass of used solid (Eq. (1)), when

Fig. 1. Transmission electron microscopic (TEM) image of MNFO material.

 A. Ghosh et al. / Chemical Engineering Journal 248 (2014) 18–26 21

Fig. 2. SEM image of MNFO sample with EDS spectrum.

1.8 2.0

1.6
Arsenic concentration(mg.L-1)

1.4 1.5
Arsenic concentration (mg.L )
-1

1.2

1.0
1.0

0.8

0.6
0.5
0.4

0.2
0.0
0.0 0 5 10 15 20 25 30 35 40 45 50 55 60 65 70
0 10 20 30 40 50 60 70 Water passed (L)
-1
Water passed (L) Flow rate (ml m ): 7 .0 5.0 3 .0
Bed depth (cm): 1.0 3.0 6.0
Fig. 4. The plots of released arsenic concentration versus discharged water volume
Fig. 3. The plots of released arsenic concentration versus discharged water volume on arsenic removal by MNFO packed fixed-bed in lab-bench scale at different
on arsenic removal by MNFO packed fixed-bed depth in lab-bench scale from As(III) effluent discharge rate from As(III) spiked groundwater.
spiked groundwater.

the arsenic concentration in effluent reduces to 0.01 mg L1 (the

break-point concentration, Cb). where VE is the volume (L) of water passed up to the point of bed
Z VB exhaustion (Eq. (2)). The significance of the other terms (C0, C and
ðC 0  CÞ
qB ¼ ð1Þ m) had already been defined earlier.
0 mdV Volumes of the throughput water at breakthrough (VB) and at
where C0 and C are the arsenic concentrations (mg L1) in input and exhaustion point (VE) obtained from the breakthrough curves,
effluent solution, respectively; m is the mass (g) of solid packed for and also values of the adsorption capacities calculated by Eqs. (1)
the fixed-bed, and VB is the effluent volume (L) at breakthrough and (2) at those points are given in Table 2.
point. The residence time or the empty bed contact time (EBCT, min) is
Values of the adsorption capacity at exhaustion point usually defined as the ratio between the bed depth (H, cm) of
(qE, mg g1) of the fixed-bed, which can also be calculated, can MNFO in the column and the linear flow-rate (c, cm3/cm2/min).
be expressed as the amount of arsenic bound by MNFO when the H
arsenic concentration in column effluent reduces to 95% of the EBCT ¼ ð3Þ
c
C0 (Eq. (2)).
Z VE
The parameter given by Eq. (3) was calculated from the exper-
C0  C imental data and shown in Table 2. Obviously, the EBCT increased
qE ¼ ð2Þ
0 mdV with increasing the bed depth (H) in column.
22 A. Ghosh et al. / Chemical Engineering Journal 248 (2014) 18–26

Ct 1
1.8 ¼ ð4Þ
C 0 1 þ eðK Th q0 mxK Th C 0 tÞ
1.6
Arsenic concentration(mg.L )
-1

1.4
where Ct and C0 are the solute concentrations (mg L1) in effluent
1.2 and input solution at time (min) t = t and t = 0, respectively; kTh is
the rate constant (L mg1 min1), v is the flow rate (L min1), q0 is
1.0 the total adsorption capacity (mg g1), and x is the mass (g) of the
0.8
adsorbent. Values of the kTh and the q0 can be determined from
the slope and the intercept of the plot of (ct/c0) versus time, t.
0.6 The breakthrough data shown in (Figs. 3–5) obtained at pH 7.5
(±0.1) at varying different parameters such as fixed-bed depth,
0.4
effluent discharge rate and input arsenic concentration were ana-
0.2 lyzed by the Thomas model non-linear fit (Figs. 6–8) and Thomas
model linear fit (SI section) methods (Fig. S10) with the Thomas
0.0 model, respectively. Non-linear and linear model fitting parame-
0 20 40 60 80 100 120
ters as-calculated from their respective slope and intercept have
Water passed (L) been presented in Tables 2 and S1, respectively. Breakthrough data
-1
Influent concentration (mg L ): 1 .0 1.40 1.72 fits were too well with non-linear Thomas model (R2 = 0.98–0.99,
v2  103 = 0.6–1.0) than the linear Thomas model fit (R2 = 0.95–
Fig. 5. The plots of released arsenic concentration versus discharged water volume
0.98) which is presumably due to the change of insight character
on arsenic removal by MNFO packed fixed-bed depth in lab-bench scale varying
input arsenic concentration from As(III) spiked groundwater. of the model when non-linear equation converts to its linear form.
The closeness between Thomas modeled and experimental data
fitting is high, which has also been realized from the values of high
3.5. Modeling of breakthrough data regression co-efficient (R2 = 0.98–0.99) and too low chi-square er-
ror (v2  103 = 0.6–1.0). It had been seen that the values of kTh
As the process does not occur at a steady state when input and those of q0 decreased with increasing depths of the fixed-beds.
solution passes across the fixed-bed under defined operating con- The change of parameters is found to be identical with the results
ditions, it is too difficult to describe the dynamic behavior of solute reported by Roy et al. [26], despite their bed depths were much
in a fixed-bed. However, the modeling of data has been made using higher than the present. Decrease of the kTh with increasing depth
the mathematical models such as Thomas [28], Adams–Bohert [29] of the MNFO packed beds is due to the increase of mass transport
and Bed Depth Service Time (BDST) [30], which were developed to resistance and the axial dispersion.
describe and possibly to predict the dynamic behavior of the bed in Again, Table 2 showed the increase of kTh and decrease of q0 val-
column performance, and have been used by various authors [19– ues with increasing the discharge rate of effluent, i.e. the decrease
26] to describe the dynamic behavior of the break through curves. of the EBCT. The trends of results reported are found to be similar
with some other workers [19–21,26]. Increase of the kTh value with
3.5.1. Thomas kinetic modeling increasing the discharge rate of effluent indicates the decrease of
The Thomas model [28] which was developed based on mass transport resistance and axial dispersion [26]. The decrease
assumption that the mass transport resistance is proportional to of q0 with increasing discharge rate of effluent i.e. decreasing EBCT
the axial dispersion and thickness of the liquid film on the particle is obvious as the adsorption capacity is directly proportional to the
surface, is expressed by Eq. (4). contact time.

Table 1
Some parameters on water quality analyzed for input and effluent water at breakthrough point.

Parameters pH Total hardness Ca Mg Fe (total) As (total) Phosphate Turbidity Nitrate Chloride Fluoride
a
Feed water 7.5 970 260.52 709.48 0.35 1.72 0.10 0.60 0.427 17.60 0.50
Effluent water 7.1 540 129.6 410.4 0.15 0.01 0.015 0.40 0.111 9.6 0.30
a
Spiked from initial 0.02 mg L1, Turbidity in NTU and others are in mg L1 excepting pH.

Table 2
Thomas kinetic model parameters estimated on arsenic removal by MNFO packed fixed-bed column.

Thomas model parameters

Parameters Bed depth (cm) Effluent discharge rate (ml min1) Input As(III) concentration (mg L1)
1.0 3.0 6.0 3.0 5.0 7.0 1.00 1.40 1.72
VB (L) 1.50 5.00 11.05 11.05 6.4 4.03 16.39 14.10 11.05
VE (L) 9.5 30.0 62.12 62.12 38.90 22.04 103.45 75.02 62.12
qB (mg g1) 0.73 0.81 0.89 0.89 0.52 0.32 0.77 0.93 0.89
qE (mg g1) 0.24 0.25 0.26 0.26 0.16 0.09 0.24 0.25 0.26
kTh  104 (L min1 mg1) 2.96 2.03 1.86 1.86 7.15 4.36 1.50 1.78 1.86
q0 (mg g1) 12.91 5.67 3.37 3.37 1.48 3.80 3.34 3.36 3.37
EBCT (min) 1.3 4.1 8.3 8.3 4.9 3.5 8.3 8.3 8.3
R2 0.99 0.99 0.99 0.99 0.99 0.99 0.98 0.99 0.99
v2 (103) 0.6 1.0 0.7 0.9 6.0 0.9 1.0 1.0 8.0
 A. Ghosh et al. / Chemical Engineering Journal 248 (2014) 18–26 23

Thomas model fitting Thomas model fitting

Adams-Bohart model fitting Adams-Bohart model fitting
1.2 1.2

1.0 1.0

0.8
0.8
c t /c0

0.6
0.6

c t /c 0
0.4
0.4

0.2
0.2

0.0
0 4000 8000 12000 16000 20000 24000 0.0
Time (min) 0 5000 10000 15000 20000 25000 30000 35000 40000
Bed depth (cm): 1.0 3.0 6.0 Time (min)
-1
Influent concentration (mg L ): 1 .0 1.40 1.72
Fig. 6. Non-linear Thomas and Adams–Bohart models fit of breakthrough data
obtained by varying fixed bed-depth for arsenic removal by MNFO fixed-bed in lab-
Fig. 8. Nonlinear Thomas and Adams–Bohart kinetic model fit of breakthrough data
bench scale from the As(III)-spiked ground water.
obtained by variation of input arsenic concentration for arsenic removal by MNFO
packed fixed-bed in lab-bench scale from As (III)-spiked ground water.

Thomas model fitting

Adams-Bohart model fitting to the residual active sites of adsorbent and concentration of adsor-
1.2
bate. That is, the rate of the adsorption is proportional to the frac-
tion of adsorption capacity of the adsorbent still remains on the
1.0 adsorbent. Although the original work of Adams and Bohart dealt
with gas–charcoal adsorption, its overall approach had been ap-
plied for the quantitative description of the present system.
0.8
 
Ct Z
¼ exp K AB C 0 t  K AB NAB ð5Þ
0.6 C0 F
ct /c 0

where kAB is the kinetic constant (L mg1 min1), F is the linear flow
0.4 rate calculated by dividing the discharge rate of effluent by the
cross-sectional area (cm min1) of column, Z is the bed depth
(cm) of the column, and NAB is the saturation concentration
0.2
(mg L1). The other parameters have their usual meanings as de-
scribed for the Thomas model (Eq. (4)).
0.0 The breakthrough data shown in (Figs. 3–5) obtained by varying
0 2000 4000 6000 8000 10000 12000 parameters such as depth of fixed-beds, discharge rate of effluent
Time (min) and arsenic C0 of inflow water, respectively, for the arsenic removal
-1
Flow rate (ml m ): 7 .0 5.0 3 .0 from water by the fixed-beds made by MNFO particle packing were
analyzed by the non-linear fitting (Figs. 6–8) and linear fitting
Fig. 7. Nonlinear Thomas and Adams–Bohart kinetic models fit of breakthrough (Fig. S11) methods with the Adams–Bohart model (Eq. (5)). The
data obtained by varying effluent discharge rate for arsenic removal by MNFO fixed-
model parameters such as kAB and NAB were evaluated from the
bed in lab-bench scale from As(III)-spiked ground water.
respective slope and intercept of the plots of non-linear fits (Ta-
ble 3) and linear fits (Table S2). It had been seen that the non-linear
Moreover, the values of kTh and q0 i.e. the rate of adsorption and model fit (R2 = 0.93–0.95) is poor than the linear model fit
the adsorption amount per unit weight by MNFO increased with (R2 = 0.95–0.98). The values of kAB and NAB decreased with increas-
increasing C0 of arsenic in water (Table 2). This is due to the in- ing the depth of fixed-beds, which are found to be different from
crease of mass transfer tendency with increasing the C0 of arsenic the results as-reported by Vaishya and Gupta [23] of arsenic(V) re-
in water as fresh arrival of water enhanced the solute loading per moval at different bed depths. Like the Thomas model, the rate of
unit area at a given time, making available more number of arsenic the reaction becomes sluggish with increasing depth of fixed-beds
ion per unit active adsorption site. As a result, the saturation of the (equal cross-section of each column), indicating increase of the
adsorbent’s site also becomes faster, leading to the decrease in mass transfer resistance. The depression of total adsorption capac-
exhaustion volume and time. ity which was found with increasing the discharge rate of effluent
is due to the fact that the adsorption capacity is directly propor-
tional to the contact time (EBCT) of a continuous flow system. In-
3.5.2. Adams–Bohart kinetic modeling crease of NAB value with increasing input concentration (C0) of
Adams and Bohart established [29] a fundamental Eq. (5) arsenic onto the fixed-bed was noted, which is due to the increase
describing the relationship between Ct/C0 and t based on the of solute load per unit surface site of the adsorbent with fresh ar-
assumption that the rate of the adsorption reaction is proportional rival of solution in continuous flow process. However, the fits of
24 A. Ghosh et al. / Chemical Engineering Journal 248 (2014) 18–26

Table 3
Adams–Bohart kinetic model parameters estimated for arsenic removal by MNFO packed fixed-bed column.

Adams–Bohart model kinetic parameters

Parameters Fixed-bed depth (cm) Effluent discharge rate (ml min1) Input As(III) concentration (C0, mg L1)
1.0 3.0 6.0 3.0 5.0 7.0 1.0 1.40 1.72
F (cm min1) 0.72 0.72 0.72 0.72 1.20 1.68 0.72 0.72 0.72
NAB (mg L1) 17.5 7.34 5.72 0.19 0.14 0.11 46.5 47.0 50.7
KAB  104 (L mg1 min1) 9.8 8.1 6.9 0.16 0.22 0.40 6.00 6.4 7.5
R2 0.93 0.95 0.93 0.93 0.90 0.90 0.94 0.94 0.93
v2 (103) 0.932 4.6 4.1 0.75 1.2 1.5 0.52 0.73 0.82

breakthrough data with the Adams–Bohart model are weaker than

that with Thomas model. 5500

5000
3.5.3. Bed Depth Service Time (BDST) modeling
4500
The Bed Depth Service Time (BDST) model was developed (Eq.
(6)) by Hutchins [30] based on the assumptions that the intrapar- 4000

Service time (min)

ticle mass-transfer resistance and external film resistance are neg- 3500
ligible. This model could be applied to estimate the design
3000
parameters of fixed-bed column data from the physical measuring
the bed capacity at different breakthrough values. This BDST Eq. (6) 2500
can be presented by Eq. (7). 2000
   
ZNBD 1 C0 1500
tb ¼  ln 1 ð6Þ
C0m K BD C 0 Cb
1000

t b ¼ mZ  K ð7Þ 500

  0
NBD -4 -3 -2 -1 0 1 2 3 4 5 6
m¼ ð8Þ
C0m Bed depth (cm)
  Fig. 9. The Bed Depth Service Time (BDST) plot of arsenic removal data by MNFO
1 C0
K¼ ln 1 ð9Þ packed fixed-bed columns obtained in lab-bench scale from As(III)-spiked ground
K BD C 0 Cb water.
 
m C0
D0 ¼ ln 1 ð10Þ
K BD NBD Cb
Table 4
where tb is the service time (min) at breakthrough point, NBD is the The BDST model parameters estimated for the arsenic removal by MNFO packed
adsorption capacity per unit BV (mg cm3), and Z is the bed depth fixed-bed column.
(cm) of adsorbent. C0 and Cb are the adsorbate concentrations BDST model parameters
(mg L1), respectively, in input solution and at the breakthrough
C0 Cb D0 (cm) kBD NBD
point; m is the discharge rate (mL min1) of effluent; and kBD (mg L1) (mg L1) (L mg1 min1) (mg cm3)
(L mg1 min1) is the rate constant of the adsorption reaction. The
1.72 0.01 9.65  107 2.74  103 3.34
m of Eq. (8) stands for the slope of the BDST line, and K is the inter-
cept of the plot of Eq. (6), which is expressed by Eq. (9). The length
of mass transfer zone (D0) can be expressed by Eq. (10).
Fig. 9 shows the well linear tb versus Z plot of the breakthrough adsorption performance and number of BVs treated before break-
data obtained by varying the bed depths of MNFO particles packed through [31]. Number of the BVs treated before breakthrough
columns, indicating the validity of BDST model for the present sys- can be calculated by the following relation (Eq. (11)).
tem. The values of NBD and kBD were evaluated from the slope (m)
Volume of water treated at breakthrough point ðLÞ
and intercept (K) of the tb versus Z plot in accordance to Eq. (6). BV ¼ ð11Þ
Volume of adsorbent bed ðLÞ
Length of the mass transfer zone (D0) had also been calculated by
inserting the value of kBD, NBD and m in Eq. (10). The parameters re- More the number of BVs before the breakthrough point better is
lated to the BDST model as-estimated are depicted in Table 4, the column performances. The AER should also indicate the effi-
which indicated the high adsorption capacity and the rate of ciency of column performance. The AER value which indicates also
adsorption reaction. High NBD (3.34 mg cm3) and kBD the good performance of a fixed bed is given by relation (Eq. (12)).
(2.74  103 L mg1 min1) and too low D0 (9.65  107 cm) sug-
gested the good prospect for scaling up of MNFO particle packed
Mass of adsorbent ðgÞ
AER ¼ ð12Þ
filter for the treatment of high arsenic ground waters. Volume of water treated ðLÞ
Values of the estimated processed BVs and AER for the present
4. Performance indicator system are shown in Table 5. It has been seen that the column with
highest bed depth (6.0 cm), lowest effluent discharge rate
Performance of a fixed bed column can be indicated by the (3.0 ml min1) and lowest input arsenic concentration (1.0 mg L1)
number of processed BVs and adsorption exhaustion rate (AER). in water showed the highest number of processed BV (0.65) and
For a fixed-bed mass, there is a direct relationship between the lowest AER (0.20 g L1) indicating best performance of the
 A. Ghosh et al. / Chemical Engineering Journal 248 (2014) 18–26 25

fixed-bed column. Modeling of the breakthrough data had also for GR grade chemicals (Merck, Mumbai), the cost kg of MNFO esti-
shown that the arsenic removal from the contaminated ground mated to be about $31.0. Incorporation of 10% additional expendi-
water is found to be maximum for the case of highest depth of ture for man power, electricity and water etc., the total cost
the fixed-bed and slowest discharge rate of effluent. Although expected to be $ (31.0 + 3.1) = $ 34.10/kg of MNFO. To assess the
the arsenic removal capacity noted to be higher for the higher in- economical viability, a comparative chart has been drawn up
put arsenic concentration, but the exhaustion rate of fixed-bed col- which clearly manifests our claim in this regard (Table 6)
umn was faster than the other lower input concentrations of [15,17,33–36]. Based on the efficiency, it could be said that MNFO
arsenic used in this experiment indicating the decrease of column is an efficient cost-effective inorganic sorbent materials.
performance.

8. A theoretical prediction based on experimental results

5. Toxicity leaching procedure (TCLP) Test of arsenic-rich solid
Design of a domestic filter from the experimental results is
According to the U.S. EPA [32], if the leached arsenic concentra- shown in ‘supporting information’ (Fig. S12) based on the assump-
tion from the contaminated solid waste is P 5.0 mg L1, the solid tion that any family with five members should drink 10 L water per
waste should be marked as the hazardous waste, and that would day (@2 L water per member). Thus, the water requirement/year
require special precaution for disposal of the waste material. Thus will be 365  10 = 3650 L (1 year = 365 days). The experimental
the solid waste (12 mg As g1) was mixed with TCLP fluid (acetate results which were acquired indicated that if the flow rate adjusted
buffer, pH = 4.93 ± 0.05) in 1:20 proportion (w/w) into a well is 7.0 ml min1, the outlet water per day should be 10.08 L. Fig. 7
capped polythene bottle and agitated by a thermostatic shaker showed the breakthrough volume 4.03 L (Table 2) for the fixed-
for 18–20 h at (30 ± 1) °C. The filtered fluid when analyzed for bed column of depth 6.0 cm made by packing 21 g MNFO into a
the arsenic showed that the leached arsenic concentration in the glass tube (diameter: 2.30 cm). If both the depth of fixed-bed and
used fluid was found to be 3.9 (±0.02) mg L1, which is lower than bed radius are multiplied by 10, then depth and radius will be
the limit as-specified by US EPA [32]. Thus, the arsenic-rich solid 60 cm and 11.5 cm respectively. The BV should increase from
waste which was generated here can be marked as a non-hazard- 24.93 cm3 to 2493.53 cm3. From the experimental results fixed-
ous material and that can be disposed off safely in the surface bed (BV 24.93 cm3) made by uniform packing of 21 g MNFO when
landfill. used generated 4.0 L water with arsenic of concentra-
tion 6 0.01 mg L1. Thus, a fixed-bed of BV 24,930 cm3 if made
6. Regeneration by uniform packing of 21 kg MNFO would produce 4000 L water
with arsenic below its permissible level. Thus, a filter bed made
Desorption of arsenic from the As-MNFO was found to be a dif- by packing 21007.1 g MNFO will give [(4  21007.1)/21] total
ficult proposition due to the strong interaction of arsenic by the so- 4001.35 L, i.e. 10.96 L per day. So, the designed filter will give
lid material. The percentage of regeneration of As-MNFO (3.2 mg) drinking water of potable standard for a period of 1 year.
showed 45.0, 25.0 and 13 at first, second and third stages, respec-
tively. That is, the regeneration of As-MNFO is possible up to an ex-
9. Conclusion
tent of 83%, indicating reuse of this material.
Aiming to investigate the efficiency of MNFO packed fixed-bed
7. Approximate cost for treatment of high arsenic ground water, the results with varia-
tion of filter design parameters such as bed depth (or bed volume),
The cost calculation of the present product (MNFO) has been effluent discharge rate and input arsenic concentration were re-
made based on the sequential reactions used for the preparation. ported. Modeling of the breakthrough data for scaling up to the
Taking the price of the used reagents from the standard price list industrial scale showed that the non-linear Thomas kinetic model

Table 5
The column performance indicators at different fixed bed-depth, effluent rate and input arsenic concentration.

Performance indicators
Parameters Bed depth (cm) Effluent rate (ml min1) Input As(III) concentration (mg L1)
1.0 3.0 6.0 3.0 5.0 7.0 1.00 1.40 1.72
Processed BV 0.42 0.47 0.52 0.44 0.25 0.16 0.65 0.56 0.44
AER (g L1) 0.36 0.35 0.33 0.33 0.53 0.95 0.20 0.27 0.33

Table 6
Approximate cost calculation and comparison with some other adsorbent.

Adsorbent Product cost* ($ kg1) Cost(/mol As(III) sorbed) ($ mol1 (kg1 of solid)) qma (mg g1) References
Present oxide 34.1 44.2 51.82 [18]
Hydrous ferric oxide 20 60.6 25 [15]
Hydrous zirconium oxide 60 153.5 31 [35]
Hydrous titanium oxide 136 323.8 31.7 [36]
Activated carbon 7.6 6333.0 0.09 [33]
Hydrous stannic oxide 9.0 42.5 15.9 [34]
Nanostructure Fe(III)–Zr(IV) mixed oxide 25 28.7 64.5 [17]
a
qm – Monolayer adsorption capacity from Langmuir isotherm model.
*
10% Additional expenditure for man power, electricity and water etc. to be added.
26 A. Ghosh et al. / Chemical Engineering Journal 248 (2014) 18–26

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