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PII: S0304-3894(16)30897-4
DOI: http://dx.doi.org/doi:10.1016/j.jhazmat.2016.09.075
Reference: HAZMAT 18081
Please cite this article as: Rajesh M.Dhoble, Pratap Reddy Maddigapu, Sadhana
S.Rayalu, A.G.Bhole, Ashwinkumar S.Dhoble, Shubham R.Dhoble, Removal
of arsenic (III) from water by magnetic binary oxide particles (MBOP):
Experimental studies on fixed bed column, Journal of Hazardous Materials
http://dx.doi.org/10.1016/j.jhazmat.2016.09.075
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Removal of arsenic (III) from water by magnetic binary oxide
particles (MBOP): Experimental studies on fixed bed column
Rajesh M. Dhoblea, Pratap Reddy Maddigapub, Sadhana S. Rayalub*A.G. Bholec,
Ashwinkumar S. Dhobled, Shubham R. Dhoblee
a
Civil Engineering Department, G.H. Raisoni Academy of Engineering and Technology,
Nagpur, M.S., India. E-mail: rmdhoble@rediffmail.com
b
Environmental Materials Division, National Environmental Engineering Research Institute,
Nagpur (CSIR-NEERI) M.S., India. E-mail: p_maddigapu@neeri.res.in
b*
Environmental Materials Division, National Environmental Engineering Research Institute,
Nagpur (CSIR-NEERI) M.S., India. E-mail: s_rayalu@neeri.res.in
c
Department of Civil Engineering, Visvesvaraya National Institute of Technology, Nagpur, M.S., India.
E-mail: agbhole@yahoo.co.in
d
Department of Mechanical Engineering, Visvesvaraya National Institute of Technology, Nagpur, M.S.,
India. E-mail: asdhoble71@gmail.com
e
Electronics and Instrumentation Engineering, Birla Institute of Technology, Pilani, Rajashtan, India.
E-mail: f2013445@pilani.bits-pilani.ac.in
*
To whom correspondence should be addressed:
Phone: +91-9890367588; Fax: 0712 2247828; E-mail: s_rayalu@neeri.res.in
1
Graphical abstract
Schematic diagram of MBOP column study for the removal of As(III) from water
2
Highlights
As(III) removal was performed on magnetic binary oxide particles in column study
Fresh MBOP has higher breakthrough time and capacity than regenerated MBOP
TCLP and semi dynamic tests confirmed As(III) concentration were within limit
3
Abstract
Magnetic binary oxide particles (MBOP) were prepared by template method using chitosan in the
laboratory for the removal of As(III) from water. The prepared MBOP has super paramagnetic
property which is sufficient for magnetic separation. Column study was performed at two different
flow rates of 2.0 ml/min. and 5.0 ml/min and comparison was made with regenerated MBOP, commercial
activated carbon and commercial activated alumina. It is observed that fresh MBOP has higher
breakthrough time and capacity than regenerated MBOP by a factor of 1.25 and 1.37 respectively. In
Logit method, the values of K (adsorption rate constant) and N (adsorption capacity coefficient) were
obtained as 0.2066 (L/mg h) and 1014 (mg/L) for 5.0 ml/min. flow rate. All the drinking water parameters
are within the limit of BIS 10500-2012. Toxicity characteristic leaching procedure (TCLP) and semi
dynamic tests were performed for the mix ratios of 01:02:01, 01:02:05 and 01:02:10 and were found
1. Introduction
The global occurrence of arsenic in groundwater is a major and serious threat. Arsenic is
generally found in rock, soil, water, air, plant, animal tissues and can exist in four valency states:
3, 0, +3 and +5. As(III) exists primarily as nonionic H3AsO3 in natural waters at low oxygen
level, which is more difficult to remove when compared to As(V) species [1,2]. Several
researchers reported that many countries groundwater and surface waters are affected by arsenic
contamination of more than 10 g/L [3]. The entry of arsenic in groundwater is mainly due to
natural occurrences and from man-made activities. The natural arsenic sources are larger than the
anthropogenic sources and their ratio is 60 to 40 [4]. The toxicity of As(III) is about 60 times
more than As(V) due to its cellular uptake [5]. Arsenic might cause neurological damage to those
4
who drink arsenic contaminated water with slightly higher concentration than 0.1 mg/L and
The main objective for setting regulation of arsenic is to reduce the level as close to zero
and cost of technology. Based on the above considerations, different countries have suggested
permissible level of arsenic in drinking water. World health organization (WHO) suggested 10
g/L based on the potential health risk and the practical quantitation limit [7]. In USEPA,
Maximum Contamination Limit (MCL) of arsenic is 2-20 g/L by considering the risk of skin
cancer ranging from 1:10000 to 1:1000000. The arsenic standards are, in Australia (7 g/L),
France (15 g/L), Vietnam and Mexico (50 g/L) [8]. MCL of arsenic in drinking water is 10
g/L, 25 g/L, 5 g/L, 3 g/L and 50 g/L in Japan, Canada, New Jersey, American Natural
Resources Defense Council and China respectively [9, 10]. In India now the permissible limit for
In many research papers batch studies have been reported and are difficult to apply
directly to fixed bed column because isotherm cannot give accurate data to scale up [12]. Here in
this research work we run column experiments for the removal of As(III). The most important
aim to study the column experiments was to predict the breakthrough point, which allows further
the determination of operation period and regeneration time. Several researchers reported on
various adsorbents to remove As(III) from water in column study [13 and references there in].
Recently studies on various parameters which effects on synthesis of magnetic adsorbents were
carried out [14-18]. In this research manuscript, the Magnetic Binary Oxide Particle (MBOP)
beads were prepared using aluminium nitrate (Al(NO3)3.9H2O) and ferric nitrate
(Fe(NO3)3.9H2O) by template method using chitosan and is used for the first time in column
experiments for the removal of As(III). MBOP has sufficient super magnetic property which
5
removes the exhausted arsenic loaded MBOP from water by conventional magnet. The
exhausted MBOP were found safe for disposal in secured landfill. The present study was carried
out to evaluate the performances of fresh MBOP, regenerated MBOP, commercial activated
alumina and commercial activated carbon for the removal of As(III) in fixed bed mode. Further
fresh MBOP was compared with regenerated MBOP, commercial activated alumina and
activated carbon in fixed bed mode for the same flow conditions. The effect of flow rate on
adsorption was monitored in the column. For stabilization of arsenic waste, Toxicity
characteristic leaching procedure (TCLP) and semi dynamic tests were conducted to know the
2.1. Reagents
Reagents and chemicals used for the study were given separately in supplementary
material S1.
Adsorption material (MBOP) was synthesized using template method. Chitosan (27 g)
was dissolved in 900 mL of 5% acetic acid with constant stirring on mechanical stirrer for 1h.
beaker and 97.89 g of ferric nitrate (Fe(NO3)3.9H2O) was dissolved in 100 mL of distilled water
in another beaker. Solutions of aluminium nitrate and ferric nitrate were added simultaneously to
the chitosan gel under continuous stirring for 180 min. The resulted Al-Fe-chitosan gel slurry
was added drop by drop to NH4OH solution (50% v/v), under vigorous stirring, using a syringe
pump. The gel macro spheres were allowed to stabilize in NH4OH solution for 60 min. The
beads were separated from the NH4OH solution and washed using deionised water and dried at
70 oC for 24 h in oven. The dried beads were calcined at 450 oC for 6 h in muffle furnace.
6
Finally, the calcined product was subjected to multiple washings with deionised water and dried
at 80 oC [19]. The mechanism of MBOP (Fig. S1) formation is shown in supplementary material
S1.
Characterisation techniques used for MBOP prepared by template method using chitosan
time (EBCT), breakthrough time and breakthrough capacity for the reduction of As(III)
concentration from aqueous solution on fresh MBOP, regenerated MBOP, commercial activated
alumina and activated carbon in a fixed bed column reactor. In a column of 1.0 cm of internal
diameter and 25 cm total height, the flow was controlled at the feed reservoir from the bottom
side using a peristaltic pump. The column was packed with the adsorbent and glass wool at both
the ends to prevent the flow of adsorbent particles into the outlet. The column was then fed
continuously with As(III) containing water of 1.0 mg/L concentration at desired volumetric flow
rate (2.0 ml/min. & 5.0 ml/min.) using peristaltic pump (Electro Lab, Mumbai, India) from
bottom side of the tube (upflow) for uniform distribution, to avoid channeling, fouling of
adsorbent and increasing the time of contact. The effluent was collected at the top at definite
interval of time and examined for As(III) concentration. The schematic representation of the
experimental setup and study was illustrated in Fig.1. Exhausted bed was regenerated insitu
using optimal regeneration media and regeneration conditions as done in batch studies [19]. For
the regenerated adsorbent, same procedure and conditions were adopted as the fresh adsorbent
column study and the empty bed contact time (EBCT), breakthrough point, breakthrough
capacity and saturation capacity in fresh and regenerated adsorbents were determined. For
7
comparison with fresh MBOP, commercial activated alumina and commercial activated carbon
The fixed bed column was designed by Logit method [20, 21]. In this method the curve is
Co (KNX)
ln (CoC) = + K Co t (1)
where C is the concentration of solute (mg/L) at any time t, Co is the initial concentration of
solute (mg/L), V is the approach velocity of flow (cm/h), K adsorption rate constant (L/mg h), X
is the depth of bed and N is the adsorption capacity coefficient (mg/L). Logit method is applied
Many researchers reported various methods to incorporate arsenic bearing waste into
polymeric matrices [22], concrete [23], soils [24], in landfills [25, 26], and in bricks [27] to
dispose safely. Toxicity characteristic leaching procedure (TCLP) and semi dynamic tests were
The purpose of this test is to know whether the exhausted MBOP is hazardous or non-
hazardous which helps for disposal consideration. As per USEPA 1992, when the leachate
concentration of arsenic waste is less than 5.0 mg/L, the waste is classified as non-hazardous and
suitable for disposal in a municipal solid waste landfill and if more than 5.0 mg/L then waste is
In the TCLP study, the binder material (cement) and fine aggregate (sand) were mixed
with arsenic loaded MBOP solid waste in a definite ratio as cement: fine aggregates: arsenic
8
loaded MBOP solid waste (01:02:01, 01:02:05 and 01:02:10). Three different solidified waste
matrices were prepared by mixing different compositions of binder materials. Water was added
in a proportion to make slurry of these binders and arsenic rich waste materials. Complete
preparation of solid matrices [28] for the test is mentioned in the supplementary material S1.
contaminants from monolithic solidified waste forms. The term semi-dynamic means that the
leachate is replaced periodically after intervals of static leaching. In this study, the
stabilized/solidified waste samples were leached in a closed vessel without agitation using
distilled water at a leachant to solid mass ratio of 10:1 which help to minimize leachant
composition changes and extract more species for analysis. Leachate was collected after a fixed
The X-ray diffraction analysis of fresh MBOP does not showed any peaks relevant to
chitosan, as it was eliminated in the calcination step at 450 oC, whereas peaks at 2 = 31.0 and
36.0 indicates the presence of -alumina phase. No specific crystalline iron oxide peaks were
observed in XRD. The absence of iron oxide peaks was attributed to the higher dispersion of
supported iron oxide phase. Further, the XRD pattern remained almost the same after As(III)
adsorption over MBOP, indicating the structural integrity (Fig. S2a and b). It has been reported
that the adsorption of arsenic on amorphous metal oxide is through the formation of inner sphere
surface complexes which are mainly attached as bidentate linkages with some monodentate
linkages [19, 29]. The FTIR spectrum of fresh MBOP (Fig. S2c) indicates the presence of
9
predominant peaks at 3512.38 cm-1 and 3321.24 cm-1 (-OH and -NH stretching vibrations),
2900.67 cm-1 and 2342.24 cm-1 (-CH stretching vibration), 1648.20 cm-1 (-NH bending vibration
in -NH2), 1378.91cm-1 (-NH deformation vibration in -NH2). The low intensity band at 1062.40
cm-1 is ascribed to FeOH structural vibration. The band between 400 cm-1 and 450 cm-1 could be
due to the superposition of the characteristic stretching bands of aluminum oxide. The bands
observed between 1100 cm-1 and 500 cm-1 could be characteristic vibrations of aluminum oxide.
FTIR spectrum of As(III) loaded MBOP is shown in (Fig. S2d). The predominant peaks due to -
OH and -NH stretching vibrations of hydroxyl and amine groups sharpen and shifted to 3640cm-1
and 3063cm-1 indicating interaction of arsenic at hydroxyl and amine sight through hydrogen
bonding. FTIR peaks corresponding of Fe-OH structural vibration and stretching bands of
aluminium oxide becomes broad and overlapped due to arsenic adsorption. The surface
morphology of MBOP before and after As(III) adsorption was studied by SEM (Fig. S2e and f)
analysis and observed porous in nature which implies that the adsorbent may have reasonable
high surface area and adsorption capacity. The large pores are developed by the elimination of
chitosan template during calcination step of synthesis. Pore size of MBOP is much larger than
the radius of arsenite (0.58Ao) which may facilitate dispersion of arsenite in the inner layer of
granular MBOP. It was found that after adsorption of arsenic, the surface morphology of MBOP
not changed much, suggesting physical adsorption of arsenic occurred. From the XRD, SEM and
FTIR analysis of MBOP, it is observed that no variation in the core structural properties of
MBOP before and after the adsorption of As(III), which reveals that the MBOP retains its
stability.
The physical properties like BET surface area, average pore size etc., given in Table 1.
The chemical composition of MBOP was analyzed by Wave length Dispersive X-Ray
Fluorescence Spectrophotometer (WDXRFS) and the percentage of Fe, Al, O, Ca, P, Mg, Mn
10
and S are shown in Table 1. The special feature of MBOP is that it has super paramagnetic
property. The saturation magnetization value (18.78 emu/g) achieved with MBOP was sufficient
for magnetic separation (Table 1; Fig. 2) which is more than the saturation value of 16.3 emu/g
for magnetic separation with a conventional magnet [30]. Hence MBOP can be easily isolated
from solution by application of external magnetic bar. MBOP is attracted by the magnet before
adsorption of As(III) in dry condition and after adsorption of As(III) in water as shown in Fig.2.
This further confirms that MBOP has magnetic nature after adsorption of As(III) in wet
condition. In the XPS spectra, Fe 2p electron binding energies are shown in Fig.3. The spectra
indicates the presence of carbon, oxygen, iron and alumina on the surface of MBOP as indicated
by the peaks corresponding to the binding energies at 288.2eV (C1s), 530eV (O1s), 724.5eV (Fe
2 p1/2) and 710.4eV (Fe 2p3/2), 74.2eV (Al 2p) (Fig.3 a-d). It is indicated that the relative intensity
of the Fe 2p1/2 and Fe 2p3/2 peak positions (724.5eV and 710.4eV) and the shape are the
characteristic presence of Fe(III). These observations confirm the presence of Fe2O3 phase of
iron and Al2O3 phase of aluminium and some organic/carbonaceous chitosan residue in MBOP.
3.2.1. Column study on fresh MBOP at flow rate of 2.0 ml/min. and 5.0 ml/min.
To investigate the influence of flow rate chosen at 2.0 ml/min. and 5.0 ml/min., MBOP
was used in continuous flow in column of 1.0 cm diameter and 18.0 cm media height. The
schematic diagram of experimental column study is shown in Fig. 1. Comparison of empty bed
contact time (EBCT), breakthrough time and breakthrough capacity of MBOP were conducted at
flow rates of 2.0 ml/min. & 5.0 ml/min. and is shown in Table 2. EBCT is a significant
parameter which determines the residence time when the solution is in contact with the adsorbent
and the removal efficiency is strongly depends on the contact time between the adsorbate
(arsenic) and the adsorbent coated with iron hydroxide [31]. From experiments, at flow rate of
11
5.0 ml/min. and 2.0 ml/min., it was observed that EBCT was 3.0 min. and 7.1 min.; breakthrough
time was 26.15 h and 72 h; volume of water treated was 7.845 liters and 8.64 liters and
breakthrough capacity was 0.436 mg/g and 0.477 mg/g respectively. Due to decrease of flow
rate, increase in EBCT, breakthrough time, volume of water treated and breakthrough capacity
were observed and the percentages were 136.66, 175.33, 10.20 and 9.40 respectively (Table 2).
This trend may be due to the availability of more adsorption sites to capture arsenic ions around
or within MBOP, which results the more diffusion of solute into the pores of adsorbent. An
increase flow rate reduces the volume of water treated until breakthrough and this is due to the
decrease in the residence time of the As(III) ions within the bed or this may be because of
reduced contact time, which causes a weak distribution of the liquid inside the column that in
turn leads to a lower diffusivity of the solute into MBOP indicating that adsorption of As(III)
may be slightly depends on diffusion. It is also reported that at higher flow velocities, the film
surrounded by adsorbent particle breaks thus reducing the adhesion of adsorbate to the adsorbent
particle [12]. MBOP at 2.0 ml/min. flow rate has higher breakthrough time and breakthrough
capacity by a factor of 2.75 and 1.1 than 5.0 ml/min flow rate respectively. The shape of the
and bed height. Steep slopes of breakthrough curves in column exhibiting high film transfer
coefficients and high internal diffusion [12]. At 5.0 ml/min. flow rate, the breakthrough time
curve is very steep compared to 2.0 ml/min. flow rate indicating high film transfer coefficient
and high internal diffusion coefficient (Fig.4). Hence the time required to reach breakthrough
time at 5.0 ml/min. flow rate is less than 2.0 ml/min. flow rate. As per IS 1172-1993, drinking
water requirement is 5.0 liter/capita/day and it was observed that at 5.0 ml/min flow rate, the
volume of water treated by single column was 7.845 liters in 26.15 h (Table 2) which is more
than 5.0 liters/capita/day and hence in this study, all the experiments were conducted at 5.0
12
ml/min. flow rate. The saturation time and saturation capacity of MBOP was found to be 515 h
and 4.67 mg/g respectively at flow rate of 5.0 ml/min. (Table 3). Compared with other
adsorbents reported in literature [13 and references there in], MBOP showed higher
breakthrough capacity of 0.436 mg/g and 0.477 mg/g at a flow rate of 5.0 ml/min. and 2.0
ml/min. respectively.
Due to regeneration, the replacement of new adsorbent and disposal problem can be
reduced considerably. Economic viability of any adsorbent depends on its regeneration and reuse
for many cycles of operation. Once the adsorbent exhausted, then adsorbate which is adsorbed
must be recovered and then regenerated. Selection of regeneration solution is depending upon the
arsenic adsorption mechanism and the nature of adsorbent. During the first cycle of regeneration
study, 1% of 1N NaOH was passed through the exhausted MBOB column for 1h at the rate of
5.0 ml/min. in upflow condition and then the column was washed with double distilled water
with a flow rate of 5.0 ml/min. till the effluent pH comes to neutral. The regenerated adsorbent
was then reused for adsorption of As(III) in the column. The nature of curves for fresh and
regenerated MBOP is shown in Fig.5. The regenerated MBOP at 5.0 ml/min. flow rate showed,
breakthrough time, saturated time, breakthrough capacity and saturation capacity of 21 h, 314 h
(13.08 days), 0.318 mg/g and 2.05 mg/g respectively (Table 3). When compared with fresh
MBOP, it was observed that fresh MBOP has higher breakthrough time and breakthrough
capacity than regenerated MBOP by a factor of 1.25 and 1.37 respectively (Table 3). Thus the
percentage decrease in EBCT, breakthrough time, saturation time, breakthrough capacity and
saturation capacity of regenerated MBOP were 6.66, 19.69, 39.03, 27.21 and 56.10 respectively
(Table 3) indicating that few adsorption sites were still occupied by As(III) ions even after
regeneration of MBOP.
13
3.2.3. Arsenic removal by commercial activated alumina and activated carbon
To compare the MBOP with the commercial activated alumina and commercial activated
carbon, column experiments for activated alumina and activated carbon were conducted at the
flow rate of 5.0 ml/min. The surface area (m2/g), total pore volume (cm3/g) and average pore
diameter (Ao) of bare alumina was 189.12, 0.4691 and 98.33 respectively. Pore diameter of bare
activated alumina is more than the diameter of arsenite (0.58 Ao) which helps to insert arsenite
into activated alumina. Column study upto breakthrough capacity on commercial activated
alumina and commercial activated carbon is shown in Fig.6. In commercial activated alumina
column study, EBCT, breakthrough time, breakthrough capacity and saturation capacity were
found to be 2.42 min., 5.0 h, 0.126 mg/g and 0.35 mg/g respectively whereas on commercial
activated carbon column study the results were observed as 2.98 min., 3.75 h, 0.109 mg/g and
0.29 mg/g respectively (Table 4). The saturation time on activated alumina and activated carbon
3.2.4. Comparison of fresh MBOP with commercial activated alumina and activated carbon
From the Table 4, it is observed that at 5.0 ml/min. flow rate, percentage increase in
EBCT, breakthrough time, breakthrough capacity and saturation capacity of fresh MBOP were
23.97, 423, 246 and 1234 respectively when compared with commercial activated alumina.
Similarly on commercial activated carbon were also found to be higher by 0.67%, 596%, 300%
and 1510% respectively. Breakthrough capacity of fresh MBOP was observed much higher by a
factor of 3.46 and 4.0 compared to commercial activated alumina and commercial activated
carbon respectively. These observations reveals that MBOP had significant enhancement of
adsorption capacity for As(III) removal than commercial activated alumina and commercial
14
From Logit method (Fig.7), the values of K and N on fresh MBOP were found to be
0.2076 (L/mg h) and 1015 (mg/L) respectively. These K and N values might be used for the
design of adsorption column. After regeneration of MBOP with 1N NaOH, the value of K and N
were obtained as 0.2032 (L/mg h) and 756 (mg/L) respectively. This shows that the adsorption
capacity coefficient (N) was reduced by 25.51% due to regeneration of first cycle, which is
nearly same as the percentage decrease of 27.21 for the regenerated MBOP (Table 3).
To understand the effect of using MBOP to remove As(III) from drinking water, water
quality parameters of effluent after column adsorption were determined. From Table 5, it is
observed that pH of the treated water remained within permissible limit and was closed to the pH
of the water before treatment, suggesting that no post treatment is required. After treatment,
As(III) concentration was less than permissible limit of 10 g/L [11]. It is also observed that the
conductivity was reduced significantly from 306 S/cm to 214 S/cm, indicating that there is
significant removal of dissolved solids. Aluminum (Al3+) concentration was below the
permissible limit of BIS 10500-2012, indicating that the MBOP can be used for treatment of
As(III) in groundwater. All the parameters are within in the prescribed standard limit [11].
From the TCLP test as per the procedure mentioned in the supplementary material S1, it
is observed that the maximum As(III) concentration in leachate was 0.0167 mg/L, 0.0186 mg/L
and 0.0722 mg/L for the mix of cement: fine aggregates: arsenic loaded MBOP solid waste
ratios of 01:02:01, 01:02:05 and 01:02:10 respectively (Fig.8). The leachates from all the mix
proportions showed much less than 1.0 mg/L as per the limit [32]. Hence the above said mixed
15
4.2. Semi dynamic test
Semi dynamic test was carried out on exhausted As(III) loaded MBOP before disposal.
From Fig.9, it is observed that the maximum concentration of As(III) in leachate was 0.813
mg/L, 0.915 mg/L and 0.989 mg/L for the mix proportion of 01:02:01, 01:02:05 and 01:02:10
after 72 h, 72 h and 96 h respectively which is less than the permissible limit of 5.0 mg/L [32-
35]. This shows that all mix proportions are safe for disposal in landfill.
5. Conclusion
In the present study, removal of As(III) from groundwater was achieved using MBOP
which is cost effective and can be developed with the help of locally available materials. The
most significant feature of MBOP is that it has magnetic property before and after adsorption of
As(III) and is easy to separate from the effluent using magnet. The breakthrough time of MBOP
at a flow rate of 2.0 ml/min. and 5.0 ml/min. was observed to be 72 h and 26.15 h respectively.
The percent increase of breakthrough capacity was observed 9.4 as the flow rate decreased from
5.0 ml/min. to 2.0 ml/min. Fresh MBOP has higher breakthrough time and capacity than
regenerated MBOP by a factor of 1.25 and 1.37 respectively. In Logit method, the values of K
(adsorption rate constant) and N (adsorption capacity coefficient) were obtained as 0.2076 (L/mg
h) and 1015 (mg/L) for 5.0 ml/min. flow rate. These K and N values might be used for the design
of adsorption column. Breakthrough capacity of fresh MBOP was higher by a factor of 3.46 and
4.0 than the commercial activated alumina and commercial activated carbon respectively;
indicating MBOP is much better adsorbent. The effluent water quality parameters after
adsorption was within the permissible limit of drinking water standards BIS 10500-2012;
indicating that the MBOP can be used for treatment of As(III) from groundwater.
TCLP and semi dynamic tests were performed on stabilized MBOP which are proving to
16
the mix proportions (01:02:01, 01:02:05 and 01:02:10 for cement: fine aggregates: arsenic
loaded waste) showed much less than 1.0 mg/L as per the limit hence safe for disposal. In semi
dynamic test, the As(III) concentration in leachates were less than the permissible limit (5.0
mg/L) for all mix proportions hence it is safe for disposal in secured landfill.
Acknowledgement
for providing research facilities. Dr. M.P. Reddy thanks CSIR, New Delhi in granting the Pool
Scientist award.
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20
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21
List of figures
Fig. 2. VSM Magnetization curve of MBOP (insight MBOP attracted by magnet: (a) Before
adsorption (dry condition) (b) After adsorption (in water)).
Fig. 5. Column study on fresh MBOP and regenerated MBOP with 1% of 1N NaOH.
Fig. 6. Column study on commercial activated alumina and commercial activated carbon upto
breakthrough capacity.
22
List of tables
23
Table 1
Physical property, chemical composition and magnetic property of MBOP.
Table 2
Comparison of EBCT, breakthrough time and breakthrough capacity of MBOP at flow rate of
2.0 ml/min. & 5.0 ml/min.
Flow rate EBCT Break Vol. of Breakthrough Percentage Percentage Percentage Percentage
(ml/min.) (min.) through water capacity, increase of increase of increase of increase of
time treated qe (mg/g) EBCT breakthroug volume of breakthrough
(L) (decreasing h time treated capacity
(h)
flow rate (decreasing water (decreasing
from flow rate (decreasing flow rate from
5.0ml/min. from flow rate 5.0ml/min. to
to 5.0ml/min. from 2.0ml/min.)
2.0ml/min.) to 5.0ml/min.
2.0ml/min.) to
2.0ml/min.)
24
Table 3
Comparison of fresh MBOP and regenerated MBOP with 1% of 1NNaOH at flow rate of
5.0 ml/min.
Condition Flow rate EBCT Breakthrough Saturated Breakthrough Saturation
(ml/min.) (min.) time (h) time (h) capacity, capacity,
qb (mg/g) qs (mg/g)
Percentage -- 6.66 -- -- -- --
decrease of
EBCT after
regeneration
Percentage -- -- 19.69 -- --
decrease of
breakthrough --
time after
regeneration
Percentage -- -- -- 39.03 --
decrease of
saturation time ---
after
regeneration
Percentage -- -- -- -- 27.21
decrease of
breakthrough --
capacity after
regeneration
Percentage -- -- -- -- -- 56.10
decrease of
saturation
capacity after
regeneration
25
Table 4
Comparison of breakthrough and saturation capacity of commercial activated carbon, commercial
activated alumina with fresh MBOP.
Adsorbent Flow EBCT Break Break Saturation Percentage Percentage Percentage Percentage
rate (min.) through through capacity, increase of increase of increase of increase of
(ml/ time (h) capacity, qS EBCT break break saturation
min.) qe (mg/g) of fresh through through capacity of
(mg g-1) MBOP time capacity of fresh
compared of fresh fresh MBOP MBOP
with MBOP compared compared
compared with with
with
Commercial 5.0 2.42 5.0 0.126 0.35 23.97 423 246 1234
activated
alumina
Commercial 5.0 2.98 3.75 0.109 0.29 0.67 596 300 1510
activated
carbon
Table 5
Physico-chemical properties of field water before and after treatment by MBOP.
Parameter Unit Before treatment After treatment Desirable limits as per Indian
Drinking Water Standard
( BIS :10500-2012)*
pH - 7.23 6.89 6.5-8.5
Colour - colourless colourless colourless
Odour - odourless odourless Unobjectionable
Alkalinity mg/L 129 118 200
Total hardness CaCO3 109 102 200
Conductivity S/cm 306 214 --
Chloride mg/L 154 29 250
Sulphate mg/L 21 17 200
Nitrate mg/L 1.514 1.213 45
TDS mg/L 397 149 500
2+
Ca mg/L 42 36 75
2+
Mg mg/L 18.2 13.56 30
Fe3+ mg/L 0.216 0.241 0.3
As(III) g/l 992.6 9.81 10
Aluminium mg/L <0.002 <0.002 <0.003
26
*Bureau of Indian standard specifications for drinking water (IS:10500-2012) second Revision.
27
Fig. 1. Schematic diagram of MBOP column study for the removal of As(III) from water
Fig. 2. VSM Magnetization curve of MBOP (insight MBOP attracted by magnet (a). Before
adsorption (dry condition) (b) After adsorption (in water)).
1
(a) (b)
(c) (d)
2
0.012
Flow rate : 5.0 ml/min
0.01 Flow rate : 2.0 ml/min
0.008
Ct/Co
0.006
0.004
0.002
0
0 5 10 15 20 25 30 35 40 45 50 55 60 65 70 75 80
Time (h)
Fig. 4. Column study on fresh MBOP upto breakthrough time at flow rate of 2.0 & 5.0ml/min.
1.2
Fresh MBOP at 5.0 ml/min
1 Regenerated MBOP with 1%NaOH
0.8
Ct/Co
0.6
0.4
0.2
0
0 50 100 150 200 250 300 350 400 450 500 550
Time (h)
Fig. 5. Column study on fresh MBOP and regenerated MBOP with 1% of 1N NaOH.
3
0.016
Commercial activated alumina
0.014 Commercial activated carbon
0.012
0.01
Ct/Co
0.008
0.006
0.004
0.002
0
0 1 2 3 4 5 6
Time (h)
Fig. 6. Column study on commercial activated alumina and commercial activated carbon upto
breakthrough capacity.
Regenerated MBOP
-1 Fresh MBOP
-2 y = 0.2032x - 7.3355
R = 0.8675
Ln Ct/( Co- Ct)
-3
-4
-5
y = 0.2066x - 9.9955
-6 R = 0.9231
-7
0 2 4 6 8 10 12 14 16 18 20 22 24 26 28 30
Time (h)
4
0.08
0.0722
Concentration of As(III) in leachate 0.07
0.06
0.05
(mg/L)
0.04
0.03
0.0186
0.02 0.0167
0.01
0
1:02:01 1:02:05 1:02:10
Cement: Sand : Waste material (MBOP)
1.2
01:2:01 mix proportion
As(III) conecntration in Leachate
0.6
0.4
0.2
Time in days