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Int. J. Environ. Sci. Technol.

(2017) 14:777–784
DOI 10.1007/s13762-016-1181-2

ORIGINAL PAPER

Towards finding an efficient sorbent for antimony: comparative


investigations on antimony removal properties of potential
antimony sorbents
P. A. Nishad1 • A. Bhaskarapillai1 • S. Velmurugan1

Received: 8 July 2015 / Revised: 5 April 2016 / Accepted: 9 November 2016 / Published online: 28 November 2016
Ó Islamic Azad University (IAU) 2016

Abstract Removal of antimony, classified as a pollutant of Keywords Antimony  Anion resin  Nano-TiO2 
priority importance, is a challenge due to its presence in Chitosan  Sorption  Antimony speciation
various forms in solution and the low concentration in
which it is to be removed. In this study, sorption profile and
the sorption mechanisms associated with the removal of Introduction
antimony in its two oxidation states (?3 and ?5) have been
investigated in detail through batch studies involving tita- The need for better antimony-removing materials is
nia sorbents, strong base anion resin, a chelating resin, and necessitated in view of the concerns in general drinking
a biosorbent. Significant sorption-associated change in water treatment processes and in treating industrial efflu-
solution pH was observed with all the sorbents, which ents. Antimony, an emerging contaminant with proven
revealed the nature of respective sorption equilibrium toxicity (Amarasiriwardena and Wu 2011; Richardson
involved. The results have shown that Sb(V) is removed 2009), is being increasingly found as a toxic pollutant in
only as anionic species, while Sb(III) is removed either as the environment, and USEPA has set a maximum con-
an anionic species or as cationic species according to the taminant level of 6 lg/L antimony in drinking water. Major
functional groups present in the sorbent and the solution sources of antimony pollution in natural waters are the
conditions. Titania-based sorbents were found to be antimony mining and smelting processes, and coal burning
effective sorbents for Sb(III) and Sb(V) within a narrow pH (He et al. 2012). It is also a concern as an impurity in the
range, while anion resin was found to be superior for copper electro-refining industry (Riveros et al. 2008). A
removing Sb(V) as Sb(OH)- 6 under a wide range of solu- recent report showed that antimony could be present in
tion conditions. The suitability of the sorbents for column water stored in polyethylene terephthalate (PET) bottles as
mode of operation has also been investigated. This report is it leaches from the PET bottles(Shotyk and Krachler 2007).
a first attempt at a rational comparison of promising sor- Apart from such general aspects, antimony is of serious
bents for antimony, and the results demonstrate the com- concern in nuclear industry (Kohlmann 1998) and its
plexity involved in antimony sorption and give an removal is a pressing problem due to the non-availability of
understanding of the available options for handling the efficient sorbents for its removal during decontamination of
antimony removal problem in large-scale applications. nuclear reactors (Mittal et al. 2011). Thus, there is a clear
need for better antimony-removing materials across vari-
ous fields. The current work is part of our efforts towards
Editorial responsibility: M. Abbaspour.
finding a suitable sorbent for bridging this gap.
The complex speciation of antimony, which is driven by
& A. Bhaskarapillai the solution conditions, makes its separation cumbersome
anup@igcar.gov.in (Filella et al. 2002). Different materials and methodologies
1 such as ion exchange(Riveros et al. 2008), sorption(Anjum
Water and Steam Chemistry Division, Bhabha Atomic
Research Centre Facilities, Kalpakkam, Tamil Nadu 603102, 2012), solvent extraction (Navarro et al. 1999), coagulation
India (Kang et al. 2003; Wu et al. 2010), membrane separation

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778 Int. J. Environ. Sci. Technol. (2017) 14:777–784

(Kang et al. 2000; Saito et al. 2004) have been studied for samples by Graver Technologies USA and Evonik Indus-
antimony removal. Of these, sorption/ion exchange tries AG, Hanau, Germany, respectively. Nano-TiO2 (spe-
removal is more suitable for industrial applications, espe- cial grade) was obtained from Travancore Titanium
cially in nuclear industry. Anion resins, by their very nat- Products Limited, India. Chitosan (medium molecular
ure, can be a viable sorbent for the anionic species of weight) was obtained from Sigma-Aldrich. AmberliteÒ
antimony. Titanium dioxide is known to be an effective IRC-718, a chelating resin containing iminodiacetic acid
sorbent capable of sorbing both cations and anions based functional groups, was obtained from HiMedia Laborato-
on the solution pH(Pena et al. 2006; Yang and Lee 2005) ries Limited, India.
and is thus a promising sorbent for the anionic species of
antimony. High sorption capacity associated with titania, Other chemicals
especially in its nano-form, further makes this an attractive
sorbent. Potassium hexahydroxo antimonate (KSb(OH)6) was
We have studied the antimony sorption properties of obtained from Sigma-Aldrich. Potassium antimony(III)
three commercially available titania-based sorbent materi- tartrate (K2Sb2(C4H2O6)2) was obtained from SD Fine
als, and a strong base anion resin Tulsion A33. Further, in Chem Ltd., India. All the chemicals were used as supplied
order to understand the speciation during sorption, two without further purification. Sample solutions were pre-
different types of sorbent materials namely Amberlite IRC- pared in double-distilled water.
718 (chelant) and chitosan (sorption through electrostatic
interactions) have also been evaluated. This report is a first Antimony removal studies
attempt at a rational comparison of potential antimony
sorbents. The paucity of literature in this area (antimony Antimony uptake studies of the materials were carried out
sorption) and its increasing need found in nuclear industry, in both batch mode and column mode. Sb(V) and Sb(III)
and in general water analysis, makes this a timely inves- solutions were prepared from KSb(OH)6 and potassium
tigation. Apart from comparative sorption studies, the antimony(III) tartrate, respectively. The solution pH was
report also explores the nature of sorption of antimony in adjusted with dil. NaOH/HCl solutions. Solution pH mea-
its two oxidation states by these sorbents, which belong to surements were done using a glass electrode.
three different classes in terms of sorbent composition and The batch sorption studies were done by equilibrating
nature of binding. 5 ml of 1 mM solution of Sb(V) or Sb(III) with 25 mg of
This study was carried out at Water and Steam Chem- the sorbent for 24 h. Antimony concentration in the
istry Division, Chemistry Group, BARC, IGCAR Campus supernatant was measured after equilibration. For column
situated in Kalpakkam, a coastal town near Chennai, India studies, about 5 L of the Sb(V) solution, de-aerated and pH
during December 2014 to June 2015. adjusted with LiOH was passed through a glass column
filled with the resin, 10 mL (wet volume) in case of anion
resin and 10 g (dry weight) in case of RADEXÒ Sb-1000,
Materials and methods with a flow rate of 10 mL/min in once-through mode. The
solution was passed through the column using a peristaltic
Sorbent materials pump. Sb(V) concentration and pH of the effluent collected
at the outlet of the column were monitored with time.
RADEXÒ Sb-1000 is a granular titanium dioxide-based Antimony concentrations were measured using an
commercial antimony sorbent. Its specific surface area was Inductively Coupled Plasma-Atomic Emission Spectrom-
estimated (BET) to be 193.3 m2/g. The Raman spectra eter (ICP-AES, Ultima2 Horiba Jovin Yvon, France; anti-
showed it to be of TiO2 anatase phase. Nano-TiO2 (special mony detection limit: 30 ppb). Antimony uptake capacity,
grade) used was of anatase phase (80–88%) with 10–18% qt (mol/g) of the sorbent on equilibration to time t, was
moisture content, and specific surface (BET) area of calculated as
146 m2/g (Nishad et al. 2014). AEROXIDEÒ TiO2 P 25 is
V
a hydrophilic fumed titanium dioxide with typical average qt ¼ ðCi  Ct Þ ð1Þ
primary particle size of 21 nm and specific surface area W
(BET) of 50 ± 15 m2/g. The nuclear-grade anion resin where Ci and Ct are the initial and equilibrium liquid-phase
(TULSIONÒ A-33) used has polystyrene copolymer as the antimony concentrations (mol/L), V is the volume (L) of
matrix and quaternary ammonium functional groups, and the solution equilibrated or passed through the column, and
the moisture content was 60%. The anion (–OH form) resin W is the weight (g) of the sorbent used. All the sorption
was obtained from Thermax, India. RADEXÒ Sb-1000 and experiments have been carried out in triplicate, and the
AEROXIDEÒ TiO2 P 25 were kindly provided as free mean capacity values were calculated.

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Int. J. Environ. Sci. Technol. (2017) 14:777–784 779

Results and discussion Sorption by the titania sorbents

Batch sorption studies with the sorbents There are number of reports on the removal of various
metal ions as their cationic and anionic species by titania,
Most sorbents exhibit a pH-dependent sorption as the in particular the arsenic ions (Kaur and Gupta 2009; Guan
solution pH influences the nature of surface charge over the et al. 2012). In the case of arsenic species, formation of
sorbent and the speciation of the sorbate in solution (Li negatively charged inner-sphere surface complexes during
et al. 2012; Padala et al. 2011). The effect of pH on the the sorption, for both As(V) & As(III), was suggested
sorption of antimony [as Sb(V) or Sb(III)] over various (Pena et al. 2006). Similar reaction was proposed for
sorbents was studied in this regard. Sorption results, sorption of antimony over SiO2/TiO2 binary oxide surface.
including the respective equilibrium pH values attained on The surface hydroxylation and the resultant surface
sorption, are tabulated in Table 1 (Sb(V)) and Table 2 charge on the titania in aqueous solutions change with the
(Sb(III)). The results demonstrate the influence of initial solution pH (Eq. 2). Thus, the solution pH determines the
pH on antimony removal efficiency by the sorbents. The predominant surface charge, and hence the sorption prop-
change in solution pH during sorption and the uptake erties, of the TiO2.
capacity of the sorbent gives an insight into the possible TiðIVÞOHþ
2

TiðIVÞOH
TiðIVÞO
sorption mechanism. ! ð2Þ
Increasing pH

Sorption by the anion resin The titania-based sorbents; RADEXÒ Sb-1000,


AEROXIDEÒ TiO2 P 25 and nano-titania (special grade)
In the case of strong base anion resin TULSIONÒ A-33, showed good pick up of antimony. Both RADEXÒ Sb-
which contains quaternary ammonium functional groups 1000 and AEROXIDEÒ TiO2 P25 exhibited similar
with (OH)- as the counter (exchangeable) ions, the decreasing trend in sorption with increasing equilibrium
Sb(V) uptake capacity decreases with increase in solution pH. This is explainable by the fact that the surface charge
pH (Table 1). of TiO2 becomes more negative at higher pH and thus
The results show that there is concomitant increase in making it less preferred by the anionic species of the
the pH [pH(Eqbm) [ pH (Initial) except when pH (ini- antimony present in the solution. Nano-titania (special
tial) = 11)] with sorption, which shows that the ion grade), however, showed almost complete removal of
exchange equilibrium involves exchange of surface Sb(V) at all the (initial) pH conditions studied (Table 1),
hydroxyl ions with the anionic species of antimony pre- which is explained by the almost identical (acidic) equi-
sent in the solution. When the initial pH was 11, there librium pH achieved irrespective of the initial pH. The
was reduction in the pH indicating higher pick up of acidic equilibrium pH ensures positive surface charge
excess hydroxyl ions present in the solution than the enabling sorption of the anionic species of antimony from
amount of hydroxyl ions released in exchange on sorption the solution. The acidic equilibrium pH (irrespective of the
of antimony species. High solution pH, due to excess initial pH) perhaps is due to the very high capacity of the
hydroxyl ion concentration in the solution, shifts the special grade nano-TiO2, which enables higher abstraction
equilibrium towards retention of antimony species in the of hydroxyl ions from the solution leading to reduced
solution leading to reduced pick up from more alkaline equilibrium pH (Table 1).
solutions.

Table 1 Batch sorption studies using Sb(V) solutions (25 mg sorbent equilibrated for 24 h with 5 mL of 1 mM Sb(V) solution)
Sorbent Initial pH: 3.00 Initial pH: 6.49 Initial pH: 11.10
Capacity (lmol/g)a pHEqbm Capacity (lmol/g) pHEqbm Capacity (lmol/g) pHEqbm
Ò
TULSION A-33 133.1 ± 2.3 (71%) 7.74 108.8 ± 0.7 (57%) 8.17 34.7 ± 1.0 (19%) 9.19
RADEXÒ Sb-1000 188.5 ± 0.1 (98%) 6.80 144.6 ± 1.4 (75%) 8.84 77.4 ± 3.5 (42%) 10.43
Nano-TiO2 (special grade) 202.1 ± 0.1 (100%) 2.33 185.5 ± 0.3 (100%) 2.64 178.6 ± 0.9 (100%) 2.62
AEROXIDEÒ TiO2 P 25 182.0 ± 0.5 (94%) 3.10 84.9 ± 2.0 (44%) 7.65 36.7 ± 0.1 (19%) 10.75
Chitosan 118.4 ± 1.1 (59%) 5.93 BDL 7.36 BDL 10.78
AmberliteÒ IRC-718 BDL 4.02 BDL 5.92 BDL 6.27
a
Percentage of antimony removed is given in the parenthesis

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780 Int. J. Environ. Sci. Technol. (2017) 14:777–784

Table 2 Batch sorption studies Sorbent Initial pH: 3.07 Initial pH: 6.92
using Sb(III) solutions: 25 mg
a
sorbent equilibrated for 24 h Capacity (lmol/g) pHEqbm Capacity (lmol/g)a pHEqbm
with 5 mL of 1 mM Sb(III)
solution) TULSIONÒ A-33b 179.9 ± 0.5 (97%) 7.80 164.6 ± 0.5 (97%) 8.98
RADEXÒ Sb-1000 193.3 ± 0.1 (100%) 6.54 175.2 ± 0. 2 (99%) 7.84
Nano-TiO2 (special grade) 187.7 ± 0.6 (100%) 2.42 173.2 ± 0.6 (99%) 2.67
AEROXIDEÒ TiO2 P 25 153.1 ± 0.7 (85.8%) 3.20 116.7 ± 0.5 (96.3%) 6.11
Chitosan 93.8 ± 0.6 (52%) 6.27 BDL 7.50
AmberliteÒ IRC-718 34.6 ± 0.2 (18%) 4.34 60.2 ± 0.1 (34%) 5.67
a
Percentage of antimony removed from the solution is given in the parenthesis
b
Sb(III) precipitated as white powder over the resin surface [See text (‘‘Sorption by the anion resin’’
section)]

Our results show that there is an optimum pH for the is normally in the range of 6.3–6.7 (Navarro et al. 2003))
anionic species Sb(OH)- 6 to be sorbed over the titania and thus bind anions/negatively charged metal complexes
surfaces through electrostatic interactions. Moderately as shown in Eq. (4). At pH greater than the pKa, it can
acidic or neutral pH is needed for Sb(V) sorption. Almost complex with the cations as shown in Eq. (5).
similar [as with Sb(V)] sorption capacity and sorption-as- Hþ

sociated change in pH were observed for Sb(III) as well R  NHþ


3 $ R  NH2 ð3Þ

(Table 2), indicating their sorption as anionic species. On R  NHþ x ðx1Þ
3 þ MLn $ ½ðR  NH3 ÞðMLn Þ ð4Þ
equilibration with Sb(V) solution of initial pH 6.5, RADEX
showed 75% sorption and the equilibrium pH attained was R  NH2 þ Mxþ $ ½ðR  NH2 ÞðMÞðxþÞ ð5Þ
8.8. While in the case of equilibration with Sb(III) of initial
Chitosan showed 60% sorption of Sb(V) [used as
pH 6.9, complete pick up and an equilibrium pH of 7.8
Sb(OH)- 6 ] at initial pH of 3.0 (Table 1). The solution pH
were observed. This shows a moderately preferential
increased during equilibration as a result of the protonation
sorption of Sb(III), perhaps due to its presence as com-
of the amine groups (Eq. 4). The equilibrium pH was 5.9
plexed tartrate anions in the solution (Zeng et al. 2001).
(Table 1), which was less than the amine pKa (*6.5),
Such preferential sorption [over Sb(V)] of Sb(III) as
which shows that the majority of the amine groups were
complexed anions has been reported in the literature
protonated and that the sorption was predominantly elec-
(Nishad et al. 2014). The effect of pH on the Sb(III)
trostatic involving anionic species of Sb(V). At higher pH
sorption over titania could not be investigated at alkaline
conditions, as the amine groups would be present in
conditions due to its hydrolysis at higher pH conditions.
deprotonated (neutral) form, there was no sorption of
The batch sorption results obtained indicate that anti-
Sb(V) as it would be predominantly present as anionic
mony is sorbed as anionic species. We have investigated
species in the alkaline solution. The uptake of Sb(III)
further on this aspect through sorption studies with two
(Table 2) at (equilibrium) pH 5.9 was found to be close to
distinct types of sorbents namely chitosan, which is capable
50% while there was no sorption at higher pH conditions,
of sorption through electrostatic attraction, and Amberlite
confirming the uptake to be as anionic species (antimony
IRC 718 which sorbs through chelation of cations These
tartrate complex).
studies revealed interesting observations.
AmberliteÒ IRC-718, which is a chelating resin with
iminodiacetic acid as the chelating functional group, did
Sorption by chitosan and Amberlite IRC 718 not pick up Sb(V) at any of the pH conditions studied
(Table 1), while it showed noticeable uptake of antimony
The biosorbent chitosan (Muzzarelli 2011) has amino and from Sb(III) tartrate solution. The Sb(III) uptake increased
hydroxyl groups as the binding functionalities. The sorp- with increase in pH (Table 2), which is typical of binding
tion occurs through electrostatic attraction as well as through carboxylic acid groups. The results indicate that
complexation. The extent to which each mode operates the iminodiacetic acid groups in the Amberlite had bound
depends on speciation in the solution state and that of the the antimony as cations through the deprotonated car-
chitosan functional groups (Guibal 2004). Both these are in boxylic groups (Bhaskarapillai et al. 2009), and that the
turn affected predominantly by the solution pH. The amino groups were able to force the equilibrium towards cationic
functional groups, for example, can bind both cations and species in case of Sb(III). This is in line with the marked
anions according to the solution conditions. The –NH2 tendency of Sb(III) to form complexes with multidentate
group is protonated (Eq. 3) at pH lower than its pKa (which carboxylic ligands (Tella and Pokrovski 2009). However,

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Int. J. Environ. Sci. Technol. (2017) 14:777–784 781

such complexation was not seen to be feasible in case of hydrolysis (vide supra). The effect of pH and antimony
Sb(V) as indicated by the absence of its sorption by concentration in the inlet solution on the breakthrough
AmberliteÒ IRC-718. This is perhaps due to the high sta- volume was studied. The results obtained will be useful in
bility of the Sb(OH)-6 anions. choosing the most suitable sorbent for large-scale
The results indicate that Sb(V) was removed as anionic applications.
species, while Sb(III) was removed either as an anionic
species or as cationic species according to the functional Effect of solution pH and Sb concentration
groups present in the sorbent and the solution conditions. on the Sb(V) removal/column breakthrough volume

Suitability of the sorbents for column mode To know the effect of pH on the Sb(V) pickup and on the
of operation breakthrough volume, Sb(V) solutions of varying pH
conditions were passed through the column. The influent
The utility of any sorbent for a large-scale application antimony concentration was 1.1 ppm. Sb(V) concentration
requires the sorbent to be suitable for column mode of and pH of the effluent solutions collected at the outlet of
operation. Amberlite, though the best suited for column the column were monitored with time. Ratio of the effluent
operations, has shown poor sorption capacities. Chitosan antimony concentration to the influent antimony concen-
showed noticeable sorption capacities, but its physical tration was calculated and plotted (Fig. 1).
format is not suitable for column operation. Out of the three TULSIONÒ A-33 showed a strong dependence of
titania materials studied, Nano-TiO2 (special grade) showed influent solution pH on the Sb(V) removal over the resin
the best sorption characteristics across all the pH conditions (Fig. 1a). At pH below 10.0, anion resin showed excellent
studied. However, its current available physical format was sorption profile. Breakthrough occurred earlier in case of
found to be not suitable for column application. Further solutions with pH higher than 10.0, which indicates com-
modifications are required to be able to use it in column petition for the anion exchange sites by the excess hydroxyl
mode. Aeroxide performed poorly, when the initial pH was ions. RADEXÒ Sb-1000 also showed strong dependence of
basic or closer to neutral. RADEXÒ Sb-1000, whose sorp- Sb(V) sorption on pH (Fig. 1b). There was gradual increase
tion characteristics were slightly inferior to that of Nano- in the effluent antimony concentration with time at pH 7.4,
TiO2 special grade, but much superior to Aeroxide, was while the increase was sharper in the higher pH conditions,
found to be having flow characteristics suitable for column indicating reduced sorption at alkaline conditions. Under
mode of operation. Thus, RADEX was chosen among the alkaline conditions, the sorption was not efficient in both
investigated TiO2 materials for column studies. Its perfor- the resins, though the anion resin could perform better till
mance under column operation was compared to that of the pH 10. In the case of RADEX, the sorption was reduced
strong base anion resin, as the latter is a predominant choice even under slightly alkaline conditions, and sorption satu-
for large-scale applications. The column studies were ration was not attained within the studied eluent volume
restricted to Sb(V) as Sb(III) is seen to be prone to indicating a relatively slower kinetics.

Fig. 1 Effect of influent solution pH (pH adjusted with LiOH) on breakthrough: a 10 ml TULSION A-33 resin with a flow rate of 10 mL/min
(1.1 ppm of Sb), b 10 g of RADEX Sb-1000 with a flow rate of 10 mL/min (1.1 ppm of Sb)

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782 Int. J. Environ. Sci. Technol. (2017) 14:777–784

Fig. 2 Effect of influent Sb(V) concentration on column performance: a 10 mL TULSIONÒ A-33 resin, b 10 g RADEXÒ Sb-1000 (Flow rate
was 10 mL/min in once-through mode; LiOH was used for pH adjustment)

In order to understand the effect of influent Sb(V) con- suited to remove antimony present at low levels from
centration on the breakthrough, Sb(V) solutions of different complex matrices. Amberlite was able to sorb Sb(III), but
concentrations were passed through the sorbent columns. not Sb(V). Antimony is generally present in higher oxi-
The influent solution pH was adjusted to 10.4 in case of the dation state [?5, mostly as Sb(OH)- 6 ] in environmental
strong base anion resin, and close to 9.4 in case of samples, while Sb(III) is present only in trace levels (Liu
RADEXÒ Sb-1000. Ratio of the effluent antimony con- et al. 2010). Hence, Amberlite may not be suitable for
centration to the influent antimony concentration was cal- antimony removal from most environmental samples.
culated and plotted in Fig. 2. The plots clearly show that Chitosan did not show any binding. These results are in
the sorption profile is predominantly affected by pH rather tune with their sorption behaviour at high concentrations of
than the concentration. antimony (vide supra). Surprisingly, anion resin was found
to be incapable of removing antimony at low levels from
tap water samples. This can be attributed to the interference
Evaluation of the Sorbents’ ability to remove from other anionic impurities (such as carbonates) present
antimony from a typical tap water sample in the water sample.

The ability of the chosen sorbents to remove antimony


from real-life sample was examined using tap water sample Conclusion
spiked with antimony (to ppb levels) as test sample. Results
obtained on equilibrating the test sample (10 ml) with This study dealt with a real-life chemistry problem involving
various sorbents (10 mg) are shown in Table 3, which an element of environmental concern that is devoid of a
demonstrate that the titania-based sorbents are the most viable solution, namely removal of antimony from aqueous

Table 3 Batch sorption studies Sorbents 205.5 ppb Sb(V), pH: 8.06 223.8 ppb Sb(III), pH: 7.57
with a typical water sample
spiked with Sb(V) Antimony removala Antimony removala
Capacity (lg/g) pHEqbm Capacity (lg/g) pHEqbm
Ò
RADEX Sb-1000 176.3 ± 9.4 (91.7%) 7.91 194.8 ± 11.5 (90.5%) 7.59
Nano-TiO2 185.8 ± 5.8 (97.1%) 3.86 202.8 ± 13.1 (97.4%) 3.75
AEROXIDEÒ TiO2 P 25 187.7 ± 9.5 (96.7%) 7.66 211.9 ± 4.1 (98.9%) 7.42
TULSIONÒ A-33 3.4 ± 0.6 (1.7%) 8.81 BDL 7.93
AmberliteÒ IRC-718 BDL 4.40 93.6 ± 8.2 (42.8%) 4.70
Chitosan BDL 8.01 BDL 7.56
a
Percentage of antimony removed from the solution is given in the parenthesis

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Int. J. Environ. Sci. Technol. (2017) 14:777–784 783

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