Accepted Manuscript

Title: Removal of arsenic (III) from water by magnetic binary

oxide particles (MBOP): Experimental studies on fixed bed
column

Author: Rajesh M. Dhoble Pratap Reddy Maddigapu Sadhana

S. Rayalu A.G. Bhole Ashwinkumar S. Dhoble Shubham R.
Dhoble

PII: S0304-3894(16)30897-4
DOI: http://dx.doi.org/doi:10.1016/j.jhazmat.2016.09.075
Reference: HAZMAT 18081

To appear in: Journal of Hazardous Materials

Received date: 19-7-2016

Revised date: 29-9-2016
Accepted date: 30-9-2016

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

The filtrate of column study maintained drinking water quality parameters

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

safe for the disposal.

Keyword: MBOP, Arsenic, Column study, Logit model, TCLP

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

producing dermatosis at 0.2 mg/L [6].

The main objective for setting regulation of arsenic is to reduce the level as close to zero

as possible, taking into consideration of occurrence, human exposure, toxicology, availability

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

arsenic is reduced from 50 to 10 g/L [11].

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

safe disposal of arsenic loaded adsorbent in nature.

2. Materials and Methods

2.1. Reagents

Reagents and chemicals used for the study were given separately in supplementary

material S1.

2.2. Synthesis of MBOP

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.

84.78 g of aluminium nitrate (Al(NO3)3.9H2O) was dissolved in 100 mL of distilled water in a

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.

2.3. Characterization of MBOP prepared by template method using chitosan

Characterisation techniques used for MBOP prepared by template method using chitosan

was given in supplementary material S1.

2.4. Fixed bed column study

Experiments were conducted in continuous-flow system to evaluate empty bed contact

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

were used at a flow rate of 5.0 ml/min.

2.5. Logit method

The fixed bed column was designed by Logit method [20, 21]. In this method the curve is

plotted between ln [Co/(Co-C)] verses t. The Logit equation can be written as

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

to experimental data of fresh MBOP and regenerated MBOP.

2.6. Solidification and stabilization of arsenic waste

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

conducted to know the safe disposal of arsenic loaded adsorbent in nature.

2.6.1. Toxicity characteristic leaching procedure (TCLP) test

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

suitable for disposal in a hazardous waste landfill.

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.

2.6.2. Semi dynamic test

Semi-dynamic leach tests are generally used to determine the leachability of

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

duration of 2 h, 7 h, 24 h, 48 h, 72 h, 96 h, 120 h, 456 h, 1128 h and 2160 h (90days) as per

ANSI/ANS 16.1 standard [28].

3. Results and discussion

3.1. Characterization of MBOP

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. Fixed bed column study

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

breakthrough curve is affected by fluid viscosity, concentration of solute in feed, pH of adsorbate

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.

3.2.2. Regeneration study

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

was found to be 55.45 h and 36.56 h respectively.

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

activated carbon in water.

3.2.5. Logit method

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).

3.2.6. Effluent water quality parameter

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].

4. Solidification and stabilization of arsenic waste

4.1. Toxicity characteristic leaching procedure (TCLP) test

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

proportions of combination are safe for disposal in secured landfill.

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

be non-hazardous mode of disposal consideration. Concentration of As(III) in leachates from all

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

We thank Director of CSIR- National Environmental Research Institute (NEERI) Nagpur

for providing research facilities. Dr. M.P. Reddy thanks CSIR, New Delhi in granting the Pool

Scientist award.

References:

[1] C.T. Kamala, K.S. Chu, N.S. Chary, P.K. Pandey, S.L. Ramesh, A.R.K. Sastry, K.C.

Sekhar, Removal of arsenic(III) from aqueous solutions using fresh and immobilized plant

biomass, Water Res. 39 (2005) 2815-2826.

[2] M.J. DeMarco, A.K. SenGupta, J.E. Gerrenleaf, Arsenic removal using a

polymeric/inorganic hybrid sorbent, Water Res. 37 (2003) 164-176.

[3] B. Manna, U.C Ghose, Adsorption of arsenic from aqueous solution on synthetic hydrous

stannic oxide, J. Hazard. Mater. 147 (2007) 522-531.

[4] P.C. Hutchinson, K.M. Meena, Lead, mercury, cadmium and arsenic in the environment,

Scope 31, John Wiley & Sons, New York, 1987.

17
[5] S. Kundu, S.S. Kavalakatt, S.K. Ghose, S.K. Mandal, T. Pal, Removal of arsenic using

hardened paste Portland cement batch adsorption and column study, Water Res. 38 (2004)

3780-3790.

[6] A.K. Chakraborti, K.C. Saha, Arsenical dermatosis from tube well water in West Bengal,

Indian J. of Med. Res. 85 (3) (1987) 326-334.

[7] WHO Guidelines for Drinking Water Quality. 2nd Edition Vol. 1 Recommendations.

http://www.who.int/water_sanitation_health/dwq/2edvol1c.pdf?ua=1, 1993 (accessed

05.09.16)

[8] H. Romero-Schmidt, A. Naranjo-Pulido, L. Mndez- Rodrguez, B. Acosta-Vargas, A.

Ortega-Rubio, Environmental health risks by arsenic consumption in water wells in the

Cape region, Mexico, in: C.A.Brebbia, D. Fajzieva, (Eds.), WIT Press, Southhampton, UK,

2001, pp. 131138.

[9] L.S. Yadav, B.K. Mishra, A. Kumar, K.K. Paul Arsenic removal using bagasse fly ash-iron

coated and sponge iron char, J. Environ. Chem. Eng. 2 (3) (2014) 1467-1473.

[10] J. Maa, M.K. Sengupta, D. Yuan, P.K. Dasgupta, Speciation and detection of arsenic in

aqueous samples: A review of recent progress in non-atomic spectrometric methods, Anal.

Chim. Acta 831 (2014) 123.

[11] Bureau of Indian Standards-BIS10500-report: Indian standard Drinking water specification.

2nd revision. http://cgwb.gov.in/Documents/WQ-standards.pdf, 2012 (accessed 05.09.16)

[12] T.S. Singh, K.K. Pant, Experimental and modeling studies on fixed bed adsorption of

As(III) ions from aqueous solution, Sep. Purif. Technol. 48 (2006) 288-296.

18
[13] P. Roy, N.K. Mondal, K. Das, Modeling of the adsorptive removal of arsenic: A statistical

approach, J. Environ. Chem. Eng. 2 (2014) 585597.

[14] N.M. Mubarak, J.N. Sahu, E.C. Abdullah, N.S. Jayakumar, Plam oil empty fruit bunch

based magnetic biochar composite comparison for synthesis by microwave-assisted and

conventional heating, J. Anal. Appl. Pyrolysis (2016),

http://dx.doi.org/10.1016/j.jaap.2016.06.026.

[15] M.N. Noraini, E.C. Abdullah, R. Othman, N.M. Mubarak, Single-route synthesis of

magnetic biochar from sugarcane bagasse by microwave-assisted pyrolysis, Mater. lett.

(2016), http://dx.doi.org/10.1016/j.matlet.2016.08.064.

[16] N.M. Mubarak, A. Kundu, J.N. Sahu, E.C. Abdullah, N.S. Jayakumar, Synthesis of palm

oil empty fruit bunch magnetic pyrolytic char impregnating with FeCl 3 by microwave

heating technique, Biomass bioenergy 61 (2014) 265-275.

[17] K.R. Thines, E.C. Abdullah, M. Ruthiraan, N.M. Mubarak, M. Tripathi, A new route of

magnetic biochar based polyaniline composites for supercapacitor electrode materials, J.

Anal. Appl. Pyrolysis (2016), http://dx.doi.org/10.1016/j.jaap.2016.08.004

[18] A. Kundu, B.S. Gupta, M.A. Hashim, J.N. Sahu, M. Mubarak, G. Redzwan, Optimisation

of the process variables in production of activated carbon by microwave heating, RSC

advances 5 (2015) 3589935908.

[19] R.M. Dhoble, S. Lunge, A.G. Bhole, S. Rayalu, Magnetic binary oxide particles (MBOP): a

promising adsorbent for removal of As(III) in water, Water Res. 45 (2011) 47694781.

[20] S.K. Maji, A. Pal, T. Pal, Arsenic removal from real-life groundwater by adsorption on

laterite soil, J. Hazard. Mater. 151 (2008) 811-820.

19
[21] P.B. Bhatkar, A.K. Gupta, S. Ayoob, S. Kundu, Investigation on arsenic (V) removal by

modified calcined bauxite, Colloids and surf., A 281 (2006) 237-245.

[22] J.K. Shaw, S.B. Fathordoobadi, J. Zelinski, W.P. Ela, A.E. Sez, Stabilization of arsenic-

bearing solid residuals in polymeric matrices, J. Hazard. Mater. 152 (3) (2008) 1115-1121.

[23] W.H. Choi, S.R. Lee, J.Y. Park, Cement based solidification/stabilization of arsenic-

contaminated mine tailings, Waste Manage. 29 (5) (2009) 1766-1771.

[24] J. Kumpiene, A. Lagerkvist, C. Maurice, Stabilization of As, Cr, Cu, Pb and Zn in soil

using amendments-a review, Waste Manage. 28 (1) (2008) 215-225.

[25] K.S.B. Kameswari, A.G. Bhole, R. Paramasivam, Evaluation of solidification/stabilization

(S/S) process for the disposal of arsenic-bearing sludges in landfill sites, Environ. Eng. Sci.

18 (3) (2001) 167-176.

[26] C. Sullivan, M. Tyrer, C.R. Cheeseman, N.J.D. Graham, Disposal of water treatment

wastes containing arsenic - a review, Sci. Total Environ. 408 (8) (2010) 1770-1778.

[27] H.M.A. Mahzuz, R. Alam, M. Alam, N.R. Basak, M.S. Islam, Use of arsenic contaminated

sludge in making ornamental bricks, Int. J. Environ. Sci. Tech. 6 (2) (2009) 291-298.

[28] T.S. Singh, K.K. Pant, Solidification/stabilization of arsenic containing solid wastes using

Portland cement, fly ash and polymeric materials, J. Hazard. Mater. B 131 (2006) 2936.

[29] S.M. Maliyekkala, L. Philip, T. Pradeep, As(III) removal from drinking water using

manganese oxide-coated-alumina: Performance evaluation and mechanistic details of

surface binding, Chem. Eng. J. 153 (2009) 101107.

20
[30] Z.Y. Ma, Y.P. Guan, H.Z. Liu, Synthesis and characterization of micron-sized

monodisperse supermagnetic polymer particles with amino groups, J. Polym. Sci. Pol.

Chem. 43 (2005) 3433-3439.

[31] I.A. Katsoyiannis, A.I. Zouboulis, Removal of arsenic from contaminated water sources by

sorption onto iron-oxide-coated polymeric materials, Water Res. 36 (2002) 5141-5155.

[32] B. Sengupta, D.B. Boralkar, T. Chatterjee, Identification/characterisation of hazardous

wastes, in: B. Sengupta, S.P. Chakrabarthi, N.K. Varma, J.C. Babu (Eds.), Management of

hazardous wastes: Guideline for proper functioning and upkeep of disposal sites, NISCIR-

CSIR, New Delhi, 2005, pp. 2-6.

[33] Hazardous Waste (Management, Handling & Transboundary Movement) Rules, CPCB,

New Delhi, India. http://www.cpcb.nic.in/divisionsofheadoffice/hwmd/mhtrules2008.pdf,

2008 (accessed 05.09.16).

[34] T.M. Clancy, F.K. Hayes, L. Raskin, Arsenic waste management: A critical review of

testing and disposal of arsenic-bearing solid wastes generated during arsenic removal from

drinking water, Environ. Sci. Technol. 47 (2013) 1079 -1081.

[35] U.S. Environmental Protection Agency, Hazardous waste test methods/SW-846 test

method 1311: Toxicity characteristic leaching procedure.

https://www.epa.gov/sites/production/files/2015-12/documents/1311.pdf, 1992 (accessed

05.09.16).

21
 List of figures

Figure Figure caption

number
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)).

Fig. 3. XPS spectrum of a) Carbon 1s b) Oxygen 1s

c) Fe2O3 - Fe 2p3/2 & 2p1/2 d) Al2O3 - Al 2p
Fig. 4. Column study on fresh MBOP upto breakthrough time at flow rate of 2.0 & 5.0ml/min.

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.

Fig. 7. Linearized form of Logit model.

Fig. 8. TCLP on exhausted MBOP.

Fig. 9. Semi dynamic test for leaching of As(III) on exhausted MBOP.

22
 List of tables

Table Table caption

number
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.
Table 3 Comparison of fresh MBOP and regenerated MBOP with 1% of 1N NaOH at flow
rate of 5.0 ml/min.
Table 4 Comparison of breakthrough and saturation capacity of commercial activated
carbon, commercial activated alumina with fresh MBOP.
Table 5 Physico-chemical properties of field water before and after treatment by MBOP.

23
Table 1
Physical property, chemical composition and magnetic property of MBOP.

Physical property (MBOP)

BET surface area (m2/g) 123.28
Average pore size (Ao) 61.59
Total pore volume (cm3/g) 0.1732
Average diameter of particle (micron) 230.87
Chemical Composition (%)
Fe 42.6
O 34.21
Al 16.69
Ca 0.65
P 0.18
Mg 0.16
Mn 0.07
S 0.02
Magnetic property of MBOP
Saturation magnetization value (emu/g) 18.78

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.)

5.0 3.0 26.15 7.845 0.436 136.66 175.33 10.20 9.40

2.0 7.1 72.0 8.64 0.477

EBCT= Empty bed contact time

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)

Fresh MBOP 5.0 3.0 26.15 515 0.436 4.67

Regenerated 5.0 2.8 21.0 314 0.318 2.05

MBOP

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

Fresh MBOP 5.0 3.0 26.15 0.436 4.67 -- -- -- --

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)

Fig. 3. XPS spectrum of a) Carbon 1s b) Oxygen 1s

c) Fe2O3 - Fe 2p3/2 & 2p1/2 d) Al2O3 - Al 2p

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)

Fig. 7. Linearized form of Logit model.

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)

Fig. 8. TCLP on exhausted MBOP.

1.2
01:2:01 mix proportion
As(III) conecntration in Leachate

1 01:02:05 mix proportion

01:02:10 mix proportion
0.8
(mg/L)

0.6

0.4

0.2

Time in days

Fig. 9. Semi dynamic test for leaching of As(III) on exhausted MBOP.