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Apple Peels-A Versatile Biomass for Water Purification?

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 Research Article

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Apple PeelsA Versatile Biomass for Water Purification?

Ramakrishna Mallampati and Suresh Valiyaveettil*
Department of Chemistry, National University of Singapore, Singapore 117543

ABSTRACT: The presence of anions such as chromate, arsenate, and arsenite in drinking water is a major
health concern in many parts of the world due to their high toxicity. Removal of such anions from water
using low cost biomass is an efficient and affordable treatment process. Owing to the easy availability and
biodegradability, we chose to use apple peel as a substrate for our investigations. Zirconium cations were
immobilized onto the apple peel surface and used for the extraction of anions. Zirconium loaded apple peels
were used to extract anions such as phosphate, arsenate, arsenite, and chromate ions from aqueous solutions.
The presence of Zr cations on the apple peel surface was characterized using XPS. The modified adsorbent
was characterized using SEM, EDS, and FT-IR. Zr treated apple peels showed efficient adsorption toward
AsO2− (15.64 mg/g), AsO43− (15.68 mg/g), Cr2O72− (25.28 mg/g), and PO43− (20.35 mg/g) anions. The
adsorption and desorption studies revealed the adsorption mechanism involves electrostatic interactions.
Anion removal efficiency was estimated by batch adsorption studies. Adsorption kinetic parameters for all
anions at different concentrations were described using pseudo-first-order and pseudo-second-order rate
equations. Langumir and Freundlich isotherms were used to validate our adsorption data. Arsenate and
chromate anions were strongly adsorbed at the pH range from 2 to 6, while arsenite was extracted efficiently between pH 9 and
10. Overall, the Zr immobilized apple peel is an efficient adsorbent for common anionic pollutants.
KEYWORDS: anions, apple peel, adsorption, isotherms, kinetics

1. INTRODUCTION biomaterials19,28−31 were considered for the removal of anions.

Ground water contaminated with anions such as chromate These adsorbents have different adsorption capacities that
(Cr2O72−), arsenite (AsO2−), arsenate (AsO43−), and other depend on the sorbent mass, pH, contact time, and initial
anions has become one of the most serious problems concentration of the adsorbate in the solution. Adsorption of
throughout the world.1 These oxoanions are known to be anions using biomass has emerged as a viable option for
highly toxic even at low concentrations and can accumulate in developing economic and eco-friendly wastewater treatment
the human body, causing various diseases and disorders.2 These processes. Natural materials have been tested for removal of
anions are considered as toxic contaminants found in water and pollutants from water. A number of studies have shown the use
can exist as various forms in the environment. Arsenic is of bioadsorbents including biochar,32 fungal biomass,33 chicken
present as arsenite (AsO33−), and arsenate (AsO43−) salts are feathers,34 methylated yeast biomass,35 and alginate36 to
common in natural waters. In chromate anion, chromium can remove anions from aqueous solution. Many biopeels such as
exist in oxidation states from +2 to +6, but only Cr(III) and banana peel, orange peel, papaya peel, potato peel, water melon
Cr(VI) are of environmental significance.3 Long-term con- shell, and mango peel, to name a few, were exploited for the
sumption of drinking water containing arsenic and chromium extraction of different pollutants.29,30 In most cases, pollutants
led to many health problems including cardiovascular effects, such as dyes, pesticides, and cations were extracted from water.
bladder, skin cancer, and anemia among populations in Extraction of anions is much tougher than extraction of the
different parts of the world.4−8 High levels of phosphate in other pollutants. Only a few reports exist on the use of fruit
wastewater disturb the nutrient equilibrium, leading to peels for anion extraction from water. A cationic adsorbent is
enhanced growth of aquatic plants and subsequent eutrophi- needed to extract anions, and functionalization via chemical
cation of lakes and rivers.9−11 Therefore, it is important to treatment methods is used to transform biopeels as efficient
develop effective methods to remove such toxic anions from adsorbents for anion removal. Some of the surface modifcations
water.
involve immobilization of chitosan, PEI coating, and Fe or Zr
Common water treatment technologies include filtration,
cation loading. However, these modified biopeels were used for
precipitation, oxidation, coagulation, and anion exchange.12−17
These methods are efficient in removing pollutants, including the extraction of a single anion. We used Zr immobilized apple
anions from aqueous media, but produce large amounts of toxic peel to extract different anions efficiently. Metal cations such as
wastes that require further decontamination processes before La(III), Ce(IV), Fe(III), and Zr (IV) loaded orange waste were
disposal. Adsorption of anions onto an active surface has been used for the extraction of arsenic and phosphate anions. Banana
considered as an efficient alternative method for purifying
contaminated water.18,19 Different adsorbents including acti- Received: March 12, 2013
vated alumina,20 sand,21 iron and manganese oxide or Accepted: May 1, 2013
hydroxide,22−24 hydroxyapatite,25,26 activated carbon,18,27 and Published: May 1, 2013

© 2013 American Chemical Society 4443 dx.doi.org/10.1021/am400901e | ACS Appl. Mater. Interfaces 2013, 5, 4443−4449
ACS Applied Materials & Interfaces Research Article

peel was reported for the extraction of chromate anion.29 the Dual-view Optima 5300 DV ICP-OES system; for arsenic(III, V),
Lemon peel was used for the removal of anionic dyes.30 and chromium(VI), the ion-exchange chromatography was employed,
Advantages of biomembranes include low cost, nontoxic, using the 818 IC Pump, 820 Separation Center, 830 Interface, 833
easy processing, and presence of abundant functional groups. Liquid handling Unit, and 732 Detector and 813 Compact auto
sampler for phosphate. Surface elements of the peels were identified
However, these biomembranes with surface functional groups using X-ray photoelectron spectroscopy (XPS) with a spatial
such as −COOH and −OH can remove cationic pollutants resolution of 30 μm (Kratos XPS system, Axis His, 165 Ultra,
more effectively than anion.37 Therefore, adsorption based on Shimadzu, Japan). The C 1s signal of an adventitious carbon was used
ligand substitution with metal loaded adsorbents is gaining as reference to compensate for charging effect at a binding energy
more attention. It is shown that loaded metal cations with high (BE) of 284.8 eV. The XPS results were collected in binding energy
positive charges can bind oxoanionic species such as arsenate, form, and data were analyzed using a nonlinear least-squares curve
arsenite,9,38 and phosphate ions.10,11 Removal of arsenic and fitting program (XPSPEAK41 Software). The peak’s full-width-at-half-
chromium anions by using zirconium salt treated adsorbents maximum (fwhm) was fixed during the fitting.
was reported,39 because zirconium in its hydrated form can 2.3. Effect of Initial Adsorbate Concentration and Time.
Apple peel (0.1 g) treated with Zr salt was added to solutions (10 mL)
generate tetranuclear ions as well as octanuclear species which of different concentrations of pollutants. All adsorption experiments
have hydroxyl ions and water molecules to take part in ligand were done at 30 °C using an orbital shaker at 200 rpm. Singapore is a
exchange with phosphate and arsenic species. Moreover, tropical country with a day time temperature of 30 °C, and we have
hydrated zirconium cations are resistant to attack by alkali carried out extractions at this temperature to assess the performance of
acids, oxidants, and reductants.40 Apple peels are available adsorbents. In our previous studies,37 an increase in temperature led to
worldwide as biowaste from food processing industries and decrease in adsorption efficiency. The residual concentration of
offer abundant functional groups which can be exploited for pollutants were analyzed after predetermined intervals of time until the
water treatment. Apples contain a large concentration of system reached equilibrium. The pollutant adsorbed at equilibrium qe
(mg/g) was calculated by using the following equation.31
flavonoids of the procyanidins, catechin, epicatechin, chloro-
genic acid, phloridzin, and the quercetin conjugates.41,42 These qe = (C0 − Ce)V /M (1)
functional groups from these compounds are expected to bind
Zr(IV) strongly on the membrane surface. Here we discuss the where C0 and Ce (mg/L) are concentration of pollutant at initial stage
and equilibrium conditions, V (L) is volume of the pollutant solution,
development of an efficient adsorbent using a readily easily and M (g) is mass of the adsorbent used. The initial concentrations of
available apple peel immobilized with Zr(IV) ions on the anionic solution used were 5, 10, 20, 40, 70, 100, and 200 mg/L, and
surface for the extraction of multiple anions from aqueous the experiments were carried out for 24 h.
media. 2.4. Kinetic and Isotherm Studies. Samples consisting of a
portion (0.1 g) of the adsorbent material (apple peel) and various
2. MATERIALS AND METHODS initial pollutant concentrations 5−200 mg/L were poured into the
conical flask and agitated using an orbital shaker at 200 rpm at 30 °C.
Apples were bought from the local supermarket, and the outer layer The time required to reach equilibrium was maintained as determined
was carefully peeled off and cut into small pieces of around 0.04 cm2 in in equilibrium studies. The equilibrium adsorptions of anions were
size. Raw peels were saponified with NaOH to cleave ester bonds and studied using Langmuir33 and Freundlich36 isotherm models. The rate
generate more hydoxyl groups. Deionized water washings were given of adsorption of different anionic pollutants on apple peels was
to remove excess base. Washed peels were then sonicated in 2- measured by studying pseudo-first-order and pseudo-second-order
proponol to extract leachable organics. The resulting adsorbent was kinetics of adsorption.
washed with water and dried. Stock solutions of arsenite (AsO2−), 2.5. Effect of Solution pH. The solution pH effect on pollutant
arsenate (AsO43−), chromate (Cr2O72−), and phosphate (PO43−) removal was studied by varying the pH from 2 to 12 using 0.01 N HCl
anions were prepared by dissolving stoichiometric amounts of or 0.01 N NaOH. The initial concentration used was 100 mg/L for all
NaAsO2, Na 2HAsO4·7H2O, K 2Cr 2O 7, and Na3 PO4·12H2 O in anions. Other parameters such as adsorbent dosage, agitation speed,
deionized water, respectively. Aqueous solutions of HCl (0.1 mol/L) and solution temperature remained constant. The percentage removal
and NaOH (0.1 mol/L) were used for pH adjustments. All chemicals of pollutant was calculated as31
and reagents used were AR grade and purchased from Sigma Aldrich.
2.1. Immobilization of Apple Peel. Zr(IV) (0.1 M) solution was ⎛ C − Cf ⎞
removal % = ⎜ i ⎟100
prepared by dissolving ZrO2Cl·8H2O (3.22 g) in deionized water (100 ⎝ Ci ⎠ (2)
mL). Dried apple peel (5 g) was added to Zr solution (100 mL, 0.1
M), and it was left for 6 h at room temperature at neutral pH. The Zr- where Ci and Cf (mg/L) are initial and final concentration of
loaded apple peel was then washed with copious amounts of water to pollutants in the water.
remove excess ions from the surface. The peel was dried and used for 2.6. Desorption Studies. Samples were prepared by adding
characterizations and adsorption studies. This study was focused on pollutant adsorbed apple peel (0.1g) to solution (10 mL) of double
the water treatment using Zr immobilized apple peels. distilled water. The solutions were equilibrated for different time
2.2. Characterization of Peels. Surface structures of the peel periods and stirred constantly. Desorption studies were conducted at
were captured using field emission scanning electron microscopy different pH values, and samples were analyzed at different time
(JEOL JSM-6701F). Dried apple peels were coated with platinum intervals. The concentrations of anionic pollutants were measured with
metal before SEM analysis to make the surface conductive. Energy ICP-OES and ion chromatography. Each experiment was repeated
dispersive X-ray spectroscopy (EDS) was done in conjunction with under identical conditions to check reproducibility.
SEM to investigate the chemical composition of the apple peel. The IR
spectra were recorded in the range of 4000−400 cm−1 using a Bruker 3. RESULTS AND DISCUSSION
ALPHA FT-IR spectrophotometer with a resolution of 4.0 cm−1.
The chemical constituents of apple peels were well studied.41
Specimens were first mixed with KBr powder and then grounded in an
agate mortar. The mixture was pressed at 10 tons for 5 min to form a Apples mainly contain flavonoids of the procyanidins, catechin,
100 mg disk using a KBr press model MP-15. Twenty scans were used epicatechin, chlorogenic acid, phloridzin, and the quercetin
for each spectrum. The concentrations of pollutants of experimental conjugates. The FT-IR spectra of apple peel in the range of
and control samples were analyzed using inductively coupled plasma 4000−400 cm−1 is shown in Figure 1. The broad band in the
optical emission spectroscopy (ICP-OES), which was carried out using range of 3760−3204 cm−1 corresponds to the O−H bond
4444 dx.doi.org/10.1021/am400901e | ACS Appl. Mater. Interfaces 2013, 5, 4443−4449
ACS Applied Materials & Interfaces Research Article

CH and >CO stretch, respectively. The absorptions in the

ranges of 1600−1585 cm−1 and 1500−1400 cm−1 are
accountable to stretching of CC bond in the aromatic
rings. The peaks due to the angular deformation in the plane of
the CH bonds of the aromatic rings (1300−1000 cm−1),
axial bending of CO bond in phenols (1260−1000 cm−1),
and axial bending of CO bond in COOH (1320−1210
cm−1) were visible in the spectrum. IR analysis of functional
groups present in apple peel matches with reported literature
values.41 IR spectra of adsorbent were recorded before and after
adsorption of different anions, and significant differences were
not observed.
The SEM images of apple peel before and after chemical
Figure 1. FT-IR spectrum of raw apple peel after washing with treatment are shown in Figure 2. Apple peel has a fibrous
aqueous NaOH solution. structure with a fiber diameter in the range of 9−25 μm with Zr
nanoparticles bonded on the surface. EDS analysis (Figure 2)
stretch of alcohols (usually between 3700 and 3200 cm−1) and indicated carbon, oxygen, and sulfur atoms on the untreated
O−H bond vibration of carboxylic acids (3400 and 2400 cm−1). peel surface and significant amounts of Zr on the treated
The sharp peak at 2918 cm−1 and 1732 cm−1 corresponds to surface. Figure 3a shows the XPS profile of Zr treated apple

Figure 2. FESEM micrographs (a, b) and EDS (i, ii) analysis of apple peel surface before (a, i) and after (b, ii) Zr treatment. Insets in (a) and (b)
show the magnified surface image.

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ACS Applied Materials & Interfaces Research Article

Figure 4. Variation of adsorption capacity of Zr treated apple peel

Figure 3. XPS profile (a) and expanded region for Zr peaks (b) of toward different anions with change in time (a) and pH (b).
treated apple peel surface.
species depending on pH of the solution The dominant species
in the acidic pH range are H2AsO4−, HCrO4−, H2PO4−, and
peel. The spectrum indicates the presence of carbon (281 eV, HAsO42− ions which can be adsorbed on the gel by substituting
1s), nitrogen (396 eV, 1s), oxygen (528 eV, 1s), and Zr (179 hydroxyl ions from the coordination sphere of the loaded
eV, 3d) on the surface of the apple peel. The peaks Zr(IV).43 Maximum adsorption of AsO2− was observed at a
corresponding to the binding energies at 179 and 182 eV in weakly alkaline environment from pH 9 to 10, and pH 10 was
Figure 3b clearly indicates that Zr is bonded to the apple peel selected for further batch-mode adsorption experiments. This
surface and exists in (+) 4 oxidation state. This high positive implies that monoanionic (H2AsO3−) species are adsorbed by
charge of the Zr immobilized surface is responsible for the substituting hydroxyl ions or water molecules.43 At high pH,
binding of anions.43 adsorbates exist as oxoanions and no precipitation was
3.1. Effects of Initial Pollutant Concentration and observed. The decrease in arsenic adsorption at higher pH
Contact Time. The adsorption rate for different pollutants at can be attributed to the competition between the hydroxyl ions
303 K is shown in Figure 4a. The amount of pollutant adsorbed and arsenic species for adsorption sites. We selected the Zr
(mg/g) increased with increase in time and reached cation for immobilization on the surface due to its stability in
equilibrium. The adsorption of chromate (Cr2O72−) is higher different pH environments. During the experiments at different
than arsenate (AsO43−) and arsenite (AsO2−) which may be pH, Zr ions were not released from the coated peels into the
due to weak interactions of arsenate anions with the aqueous solution.
adsorbent.29−31 The adsorption experiments were carried out 3.3. Isotherm Studies. 3.3.1. Langmuir Isotherm. The
for 24 h to evaluate equilibrium adsorption capacity (qe mg/g) Langmuir isotherm which has been commonly used for
of each anionic pollutant. All anions reach equilibrium within 6 describing adsorption processes can be used to explain the
h which indicates faster adsorption. Chromate ions showed adsorption of pollutants on apple peel. The basic assumption of
highest qe (25 mg/g) followed by phosphate (18 mg/g) and the Langmuir theory is that adsorption takes place at specific
arsenic (14 mg/g) ions. The results indicate that the Zr treated sites within the adsorbent.33−35 The data obtained from the
apple peel binds anionic pollutants efficiently, owing to the high adsorption experiment for different pollutants were analyzed
positive charge of Zr cations on the surface.43 using the isotherm equation. The saturation monolayer can be
3.2. Effect of pH. The effect of pH on the adsorption of expressed by the equation.35
anions onto the Zr loaded apple peel is shown in Figure 4b,
which shows that the adsorption of Cr2O72−, AsO43−, and 1 1 1
= +
PO43− reaches maximum at acidic pH but AsO2− shows higher qe qm KqmCe (3)
adsorption at pH 10. On the basis of the data, pH 10 for AsO2−
and pH 2 for other anions were selected for further batch-mode KqmCe
adsorption experiments. Release of Zr cations from the peel to qe =
1 + qmCe (4)
the aqueous medium during adsorption studies was tested by
analyzing Zr content in the adsorbate solution. Elemental A plot of 1/qe versus 1/Ce results in a linear graphical relation
analysis showed no detectable concentration of Zr in the indicating the applicability of the Langmuir model for different
solution. Arsenic and chromium can exist as different anionic anions is shown in Figure 5a. The Langmuir constants are
4446 dx.doi.org/10.1021/am400901e | ACS Appl. Mater. Interfaces 2013, 5, 4443−4449
ACS Applied Materials & Interfaces Research Article

3.3.2. Freundlich Isotherm. The Freundlich model is an

empirical equation based on adsorption on heterogeneous
surfaces. It is assumed that the stronger binding sites are
occupied first and the binding affinity decreases with an
increasing degree of site occupation.36,37 The isotherm is
expressed as
1
ln qe = ln K f + ln Ce
n (6)
where Kf and n are Freundlich constants related to sorption
capacity and sorption intensity of the adsorbent, respectively. Kf
can be defined as the adsorption coefficient and represents the
quantity of pollutant adsorbed onto treated apple peel for a unit
equilibrium concentration. A value for 1/n below 1 refers to a
normal Langmuir isotherm while 1/n above 1 represents a
cooperative adsorption. The 1/n value for AsO2− (0.8124),
AsO43− (0.8233), Cr2O72− (0.9475), and PO43− (0.5966)
indicates that the adsorption follows the Freundlich isotherm.
This isotherm model (Figure 5b, Table 1) also yielded good fit
with the highest R2 values for anionic pollutants, which
indicates that the adsorption of anions on apple peel surface is a
heterogeneous process. Table 1 lists the comparison of
Langmuir and Freundlich constants for various pollutants on
treated apple peel surface. It can be seen from the table that the
Langmuir model was found to fit the data significantly better,
Figure 5. Langmuir (a) and Freundlich (b) isotherms for anions
adsorption.
indicating monolayer adsorption of anions on apple peel.
3.4. Adsorption Kinetics. Kinetic models elucidating the
mechanism by which pollutants are adsorbed on adsorbent
surfaces have been proposed.38−40 Different adsorption kinetic
elucidated from the slope and intercept of straight lines for models were used to investigate the adsorption mechanism. A
different anions. The observed linear relationship is statistically pseudo-first-order eq 7 was used for data analysis;39
significant as evidenced by the R2 values (close to unity), ⎛ k ⎞
implying the applicability of isotherm for our extraction studies. log(qe − qt) = log qe − ⎜ 1 ⎟t
⎝ 2.303 ⎠ (7)
Adsorption data for Cr2O72− fits well with the Langmuir linear
equation with the best R2 value (0.999) compared with the where qe and qt indicate the amount of pollutant adsorbed
others. The Langmuir isotherm constants along with correction (mg/g) at equilibrium and in time t, respectively. k1(min−1) is
coefficients are reported in Table 1. The essential characteristic the first order rate constant applied in the present studies of
of the Langmuir isotherm can be expressed in terms of a pollutant adsorption. The plot of log(qe − qt) versus t for
dimensionless equilibrium parameter, such as the separation different pollutants (Figure 6a) gave first order rate constants k1
factor (RL) used in the following equation35 (slope) and equilibrium concentration qe (intercept). The
1 values of k1 and qe for different pollutants were calculated from
RL = the plots and are shown in Table 2. The adsorption kinetics of
1 + KCe (5)
some systems can also be explained by a pseudo-second-order
where K is the Langmuir constant and Ce is the initial reaction (Figure 6b). The pseudo-second-order equation based
concentration of the adsorbate in solution. This parameter on adsorption equilibrium capacity may be expressed in the
indicates that the isotherm will be shaped according to the form,40
following adsorption characteristics: RL > 1 is unfavorable; RL = ⎛1⎞
1 corresponds to linear; 0 < RL< 1 is favorable, and RL= 0 is t 1
= + ⎜⎜ ⎟⎟t
irreversible. The RL values for AsO2− (0.4138), AsO43− qt k 2qe 2
⎝ qe ⎠ (8)
(0.7578), Cr2O72− (0.8294), and PO43− (0.2468) indicate
that the adsorption of anionic pollutants on to treated apple where k2 is the rate constant of pseudo-second-order
peel is favorable (Table 1). adsorption and qe is the equilibrium adsorption capacity

Table 1. Langmuir and Freundlich Isotherm Model Constants and Correlation Coefficients for Adsorption of Different Anions
on Zr Immobilized Apple Peel Surface

Langmuir Freundlich
pollutant K (L/g) RL R2 KF (mg/g)(L/g)n 1/n R2
AsO2− 0.0070 0.4138 0.9973 0.2484 0.8124 0.9968
AsO43− 0.0015 0.7578 0.9976 0.3136 0.8233 0.9362
Cr2O72− 0.0010 0.8294 0.9992 0.2216 0.9475 0.9824
PO43− 0.0152 0.2468 0.9941 0.9007 0.5966 0.9141

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ACS Applied Materials & Interfaces Research Article

Figure 6. Pseudo-first-order (a) and pseudo-second-order (b) kinetics Figure 7. EDS analysis of Zr treated apple peel surface after adsorption
for the adsorption of anions onto the Zr treated apple peel. of chromate (a) and arsenate (b) anions.

(mg/g). The k2 and qe values of different pollutants can be 7, 10, and 12) at a constant temperature of 30 °C. Minimum
calculated experimentally from the slope and the intercept of t/ desorption was observed at acidic pH, but about 90% of
qt versus t plots. From Table 2, the correlation coefficients R2 pollutants were desorbed at pH 12 within 10 min (Figure 8).
for AsO2− (0.9937), AsO43− (0.9318), Cr2O72−(0.9990), and
PO43−(0.9990) indicate that the pseudo-second-order model
fits the experimental data better than the pseudo-first-order
model. The calculated correlations are closer to unity for the
second-order kinetics model and calculated equilibrium
adsorption capacities of all pollutants matched with exper-
imental values. The calculated k2 (g/mg min) and qe are listed
in Table 2.
3.5. Regeneration of Adsorbent. The adsorption of
different anions on the surface of Zr treated apple peel can be
confirmed by the energy dispersive X-ray spectroscopy (EDS)
analysis after adsorption. The adsorbent was washed with
deionized water to remove free anions after adsorption and
dried at room temperature. The peels were analyzed using EDS
(Figure 7), and the peaks corresponding to Cr and As were
seen in the spectra along with Zr, which confirms the binding of
anions on the surface of Zr treated apple peel. Mechanism of
adsorption can be further investigated by using the desorption
and regeneration process. The nature of the adsorption of Figure 8. Desorption of anions from the Zr immobilized apple peel
pollutant onto the surface of the peels involves electrostatic surface at various pH values under ambient conditions.
attractions between anions and Zr(IV) present on the surface.
Desorption of these pollutants was studied at different pH (2, 4,

Table 2. Pseudo-First-Order and Pseudo-Second-Order Constants and Correlation Coefficients for Adsorption of Different
Anions on Treated Apple Peel

pseudo-first-order kinetic model Pseudo-second-order kinetic model

pollutant qe(exp) (mg/g) qe (mg/g) k1 (min−1) R2 qe (mg/g) k2 (g/mg min) R2
AsO2− 15.6400 7.6749 0.0056 0.9542 15.0648 0.0032 0.9937
AsO43− 15.6800 13.1039 0.0051 0.9451 15.3681 0.0009 0.9318
Cr2O72− 25.2860 11.6322 0.0039 0.8467 22.8676 0.0026 0.9990
PO43− 20.3540 13.4444 0.0029 0.9533 16.3425 0.0018 0.9905

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 ACS Applied Materials & Interfaces Research Article

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the medium also influence the extraction efficiency. The Zr on Air Soil Pollut. 2007, 180, 75.
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contaminants in water. It is conceivable that the use of such (27) Chen, W.; Parette, R.; Zou, J.; Cannon, F. S.; Dempsey, B. A.
biowaste is a simple, cost-effective, and efficient method for Water Res. 2007, 41, 1851.
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■ AUTHOR INFORMATION
Corresponding Author
Gil, J. A.; Mateos, L. M.; Aller, A. J. Water Res. 2007, 41, 531.
(29) Memon, J. R.; Memon, S. Q.; Bhanger, M. I.; El-Turki, A.;
Hallam, K. R.; Allen, G. C. Colloids Surf., B 2009, 70, 232.
(30) Bhatnagar, A.; Kumar, E.; Minocha, A. K.; Jeon, B. H.; Song, H.;
*E-mail: [email protected]. Seo, Y. C. Sep. Sci. Technol. 2009, 44, 316.
Notes (31) Oke, I. A.; Olarinoye, N. O.; Adewusi, S. R. A. Adsorption 2008,
The authors declare no competing financial interest. 14, 73.

■ ACKNOWLEDGMENTS
The authors thank the Environment and Water Industry
(32) Mohan, D.; Pittman, C. U., Jr. J. Hazard. Mater. 2007, 142, 1.
(33) Say, R.; Yilmaz, N.; Denizli, A. Sep. Sci. Technol. 2003, 38, 2039.
(34) Teixeira, M. C.; Ciminelli, V. S. T. Environ. Sci. Technol. 2005,
39, 895.
Programme Office (EWI) under the National Research (35) Seki, H.; Suzuki, A.; Maruyama, H. J. Colloid Interface Sci. 2005,
Foundation of Singapore (PUBPP 21100/36/2, NUS WBS 281, 261.
no. R-706-002-013-290, R-143-000-458-750, R-143-000-458- (36) Zouboulis, A. I.; Katsoyiannis, I. A. Ind. Eng. Chem. Res. 2002,
731) for the financial support for the work. Also funding and 41, 6149.
financial support from Department of Chemistry, NUS- (37) Mallampati, R.; Valiyaveettil, S. RSC Adv. 2012, 2, 9914.
Environmental Institute, and National University of Singapore (38) Ghimire, K. N.; Inoue, K.; Ohto, K.; Hayashida, T. Bioresour.
are acknowledged. Technol. 2008, 99, 32.

■
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4449 dx.doi.org/10.1021/am400901e | ACS Appl. Mater. Interfaces 2013, 5, 4443−4449

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