water research 43 (2009) 24192430

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Performance of activated carbon and bentonite for

adsorption of amoxicillin from wastewater:
Mechanisms, isotherms and kinetics
Eric Kristia Putraa, Ramon Pranowoa, Jaka Sunarsob,
Nani Indraswatia, Suryadi Ismadjia,*
a

Department of Chemical Engineering, Widya Mandala Surabaya Catholic University, Kalijudan 37, Surabaya 60114, Indonesia
Division of Chemical Engineering, The University of Queensland, Brisbane, Qld 4072, Australia

article info

abstract

Article history:

Amoxicillins traces within pharmaceutical effluents have toxic impact toward the algae

Received 8 December 2008

and other lower organisms within food web. Adsorption, as an efficient process to remove

Received in revised form

contaminants from water was chosen; in particular with bentonite and activated carbon

20 February 2009

as adsorbents. The study was carried out at several pH values. Langmuir and Freundlich

Accepted 27 February 2009

models were then employed to correlate the equilibria data on which both models equally

Published online 11 March 2009

well-fit the data. For kinetic data, pseudo-first and second order models are selected.
While chemisorption is the dominant adsorption mechanism on the bentonite case, both

Keywords:

physisorption and chemisorption play important roles for adsorption onto activated

Amoxicillin

carbon. Also, several possible mechanisms for these adsorption systems were elaborated

Adsorption

further.
2009 Elsevier Ltd. All rights reserved.

Activated carbon
Mechanism

1.

Introduction

Due to their importance in medical treatment, more and

more antibiotic compounds are at large employment. Yet,
their occurrence in aquatic environment is considered as an
emerging issue, which mostly come from pharmaceuticals
industry as well as veterinary and human medication uses
(Halling-Sorensen et al., 1998). About 3090% of the given
dose would remain undegradable in human or animal body,
largely excreted as active compound (Aksu and Tunc, 2005;
Alcock et al., 1999). Although pharmaceutical products, in
particular are designed to exhibit low half lives, several
antibiotics such as ampicillin, erythromycin, sulphamethoxazole, tetracycline and penicilloyl groups cannot be
removed even by a sewage treatment of which their

continual introduction to environment would pose serious

ecological risk (Richardson and Bowron, 1985). Recent studies
showed that numerous antibiotics have toxic nature toward
algae and other lower organisms which can bring about
indirect effect in long terms toward ecological sustainability
(Halling-Sorensen, 2000; Holten Lutzhoft et al., 1999; Pan
et al., 2008).
Amoxicillin is a broad-spectrum b-lactam antibiotic that
belongs to penicillin class organism used as veterinary
medicine for treatment of bacterial infections encountered in
gastro-intestinal and systemic infections (Baere and Backer;
Dousa and Hosmanova, 2005). It is also commonly employed
for human prescription medicine (against infections caused
by bacteria) and as therapeutic agents due to its broad
spectrum against bacteria (Aksu and Tunc, 2005). Amoxicillin

* Corresponding author. Tel.: 62313891264; fax: 62313891267.

E-mail address: suryadiismadji@yahoo.com (S. Ismadji).
0043-1354/$ see front matter 2009 Elsevier Ltd. All rights reserved.
doi:10.1016/j.watres.2009.02.039

2420

water research 43 (2009) 24192430

has also been known to be hardly degradable, remains as

active compound within urine and feces (Andreozzi et al.,
2005; Jara et al., 2007). In addition, amoxicillin also accumulates through industrial route, where the concentration is
usually much more higher than that originated from public
excretion (Aksu and Tunc, 2005). Their existence on the
environment can be associated to some potential problems
in the future. For example, Pan et al. (Pan et al., 2008)
recently reported the toxic effects of this compound toward
algae Synechocystis sp., mainly by inhibiting its photosynthesis mechanism. And also, while accumulated within
single organism, i.e. pathogenic bacteria; amoxicillin would
increase its resistance, leading to higher dosage needed or
even its incapability to treat conventional diseases (Aksu and
Tunc, 2005).
Removal of amoxicillin residue from the environment is
therefore considered important and serves as an attractive
case study. Although amoxicillins removal involves high
cost, the pharmaceutical industry in particular must treat
their wastewater properly prior to environment discharge.
Several methods are available for this purpose such as
ozonation (Andreozzi et al., 2005; Baciogliu and Otker,
2003), membrane (RO-UF) filtration (Li et al., 2004) and
adsorption process (Adriano et al., 2005; Aksu and Tunc,
2005; Dutta et al., 1997a; Saleh et al., 1984). Adsorption is
considered very effective to remove contaminants within
water or wastewater even at very low concentration (less
than 1 mg/L). Depending on the adsorbent type, this
method is simple and applicable for common substances
with low operation cost in comparison to other techniques.
Till present time, only small amount of reports focusing on
antibiotics removal from wastewater using alternative
adsorbents are available to be referred upon (Adriano et al.,
2005; Gao and Pedersen, 2005; Saleh et al., 1984; Zhang and
Huang, 2007).
Activated carbon has been widely used to remove organic
contaminants from water and wastewater in industrial scale
application. It has high adsorption capacity as well as
removal efficiency for certain organic substances. In some
application, the removal efficiency can reach 100%. In real
application, the adsorption processes using activated carbon
are carried out in column mode. However, the major drawback for wastewater treatment utilization comes from
economic consideration; the commercially available activated carbons are expensive, rendering its infeasibility for
large scale operation. Therefore, alternative adsorbent which
is inexpensive and comes in abundant amount naturally is of
interest. Bentonite, an absorbent aluminium phyllosilicate,
generally impure clay consisting mostly of montmorillonite
fulfills such criteria. This material which is largely available
in some parts of Indonesia at very low cost has been
employed as adsorbent on some industrial application such
as vegetable oil refinery. To that end, bentonite as alternative
adsorbent can be exploited to adsorb amoxicillin from
synthetic wastewater, justifying this study. The performance
of bentonite is also compared with that of commercially
available granular activated carbon NORIT ROW 0.8 SUPRA to
justify bentonites potential application as adsorbents.
Several proposed mechanism for adsorption will also be
discussed.

2.

Materials and methods

2.1.

Materials

Amoxicillin was obtained as trihydrate from P.T. Coronet

Crown, Sidoarjo, East Java, Indonesia and used without any
further treatment. Activated carbon type was granular activated carbon NORIT ROW 0.8 SUPRA (NORIT Netherland)
while bentonite was acquired from a bentonite mining site
located on Pacitan, East Java, Indonesia. Prior to application as
adsorbents, both bentonite and activated carbon were ground
to obtain the particle size of 60/80 mesh. The elemental
analysis of bentonite (pristine and after adsorption) was
conducted by atomic absorption spectrophotometer AAS
SHIMADZU AA6200 flame emission spectrophotometer of
which the result is summarized in Table 1.

2.2.
Determination of physical characteristics of
adsorbent
Surface area and pore characteristics of adsorbents (activated
carbon and bentonite) were determined by nitrogen adsorption at normal boiling point of nitrogen using Quadrasorb SI.
Prior to nitrogen sorption measurements, the adsorbents
were degassed at vacuum condition at temperature of 150  C
for 24 h. Nitrogen sorption isotherms were measured over
a relative pressure (P/P0) range of approximately 105 to 0.998.
The BET (BrunauerEmmettTeller) surface area was
measured by means of standard BET equation applied in the
relative pressure range of 0.060.3. The pore size distribution
of the carbons was ascertained using density functional
theory (DFT) software available within instrument using
medium regularization.
The surface morphology of these adsorbent were analysed
using JEOL JSM-6400F FESEM (Field Emission Scanning Electron Microscopy). The samples were put onto a conductive
carbon tape above the metal stub and coated with a thin layer
of platinum for charge dissipation during FESEM imaging. The
sputter coater (Eiko IB-5 Sputter coater) was operated in an
argon atmosphere using a current of 6 mA for 3 min. The
coated samples together with the stub were then transferred
to the SEM specimen chamber and observed at an accelerating
voltage of 5 kV, spot size of 8, aperture of 4 and 15 mm working
distance.

Table 1 Elemental analysis of bentonite using AAS.

No.

1
2
3
4
5
6
7
8

Parameter

Al
Si
Fe
Ca
Mg
K
Na
Mn

Concentration (%)
Pristine

After adsorption

39.12
47.89
3.44
0.15
0.45
0.24
0.47
0.03

38.92
48.05
3.26
0.09
0.38
0.22
0.41
0.04

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water research 43 (2009) 24192430

2.4.
Determination of surface functional groups of
activated carbon
The surface functional groups on activated carbon were
determined using Boehms titration (Boehm, 1994) and FTIR
spectrophotometer. The FTIR measurements were carried out
using Shimadzu 8400S. On the other hand, Boehms titration
was conducted by adding 0.5 g of activated carbon into several
flasks; each containing 50 mL of 0.05 N NaHCO3, Na2CO3, and
NaOH solutions for acidity analysis as well as 50 mL of 0.05 N
HCl solution for basicity analysis. After 24 h, 10 mL of each of
NaHCO3, Na2CO3 and NaOH solutions which have been filtered
from its mixture with carbon is titrated with 0.05 N HCl solution previously standardized with Na2B4O7 solution. For
basicity test, HCl solution from earlier filtration is titrated with
0.05 N NaOH solution previously standardized with H2C2O4
solution.

2.5.
Adsorption isotherm of synthetic amoxicillin
solution
Synthetic amoxicillin solution with initial concentration of
300 mg/L was added into a series of erlenmeyer flasks for
adsorption experiments. This quite high concentration value
was chosen to represent the condition of wastewater from
Indonesian pharmaceutical companies. As the solvent, double
distilled water were used. The pH of solution was adjusted to
three different pH values (i.e. pHsoln 2, pHsoln pHpzc of the
adsorbents and pHsoln 7) by addition of 0.1 M HCl or 0.1 M
NaOH solution. Afterwards, adsorbents (0.11.5 g) were added
to a series of erlenmeyer flasks each of which contains of
50 mL of amoxicillin solution. Then, the flasks were transferred to temperature controlled shaking water bath. The
temperature of water bath was maintained at 30  C. The flask
was shaked at 200 rpm until the equilibrium was reached.
Preliminary experiments pointed out that the adsorption
equilibrium time for bentonite was 8 h while that for activated
carbon was 35 min. After equilibrium was reached, the solutions were later centrifuged at 2500 rpm for 10 min to separate
the adsorbent. The concentration of amoxicillin in supernatants were analysed using GENESYS 10V spectrophotometer
at wave length of 230 nm and pH values of 2, 3.85, 4.91, and 7.

2.6.

Adsorption kinetics of synthetic amoxicillin solution

To begin with, 250 mL of synthetic amoxicillin solution was

poured into erlenmeyer flasks and the solution pH was

3.

Result and discussion

3.1.

Physical characteristics of adsorbent

Nitrogen sorption isotherms for bentonite and activated

carbon are depicted in Fig. 1. Fig. 1 reveals different structures
for bentonite and activated carbon. Mesoporous structure in
bentonite is indicated by the presence of hysteresis between
adsorption and desorption isotherm at relative pressures
above 0.4 (Lillo-Rodenas et al., 2005). In contrast, activated
carbon is mainly consist of micropores as displayed by rapid
adsorption of nitrogen at low relative pressure (Citraningrum
et al., 2007). The BET surface area of bentonite and activated
carbon was determined based on the nitrogen sorption

200
Bentonite Adsorption
Desorption
150

Vads (cm3/g)

The determination of pHpzc of adsorbents was carried out by

pH titration procedures (Orfao et al., 2006). 50 cm3 of NaCl
0.01 M solution was poured into several erlenmeyer flasks.
The pH of solution within each flask was adjusted to a value
between 2 and 9 by addition of HCl 0.1 M or NaOH 0.1 M
solution. Then, 0.15 g of adsorbent was added to the flasks and
the final pH was measured after 48 h. The pHpzc is defined as
the point where the curve pHfinal vs pHinitial crosses the line
pHfinal pHinitial.

adjusted to three different pH values (i.e. pHsoln 2,

pHsoln pHpzc and pHsoln 7) by adding 0.1 M HCl solution or
0.1 M NaOH solution. Then 3.5 g of each adsorbent was added
onto the flasks and transferred to shaking water bath and
shaked until equilibrium was reached. After each certain time
interval, a known amount of solution was taken from the
mixtures and analysed to obtain its amoxicillins concentration using GENESYS 10V spectrophotometer.

100

50

0
0.0

0.2

0.4

0.6

0.8

1.0

P/Po

b 400
300

Vads (cm3/g)

2.3.
Determination of point of zero charge (pHpzc) of
adsorbent

200

100
Activated Carbon Adsorption
Desorption
0
0.0

0.2

0.4

0.6

0.8

P/Po
Fig. 1 Nitrogen sorption isotherm for (a) bentonite and
(b) activated carbon.

1.0

2422

water research 43 (2009) 24192430

3.3.

0.008

dv(r) (cc//g)

0.006

0.004

0.002

0.000
20

40

60

80

pore width ()

0,20
0,18

dv(r) (cc//g)

0,16
0,14
0,12
0,10
0,08
0,06
0,04
0,02
0,00
20

40

60

80

pore width ()
Fig. 2 DFT result for (a) bentonite and (b) activated carbon.

isotherms of which their values are 91.627 m2/g and

1092.951 m2/g, respectively.
The pore size distribution of both adsorbents was analysed
using DFT method, as displayed in Fig. 2. Bentonites pores are
mainly mesopores with average pore width between 20 and
. Activated carbon, on the other hand has microporous
80 A
). The surface morphology of both
structure (pore size < 20 A
adsorbents was also characterized using SEM images (Fig. 3)
that shows clearly their heterogeneity structures.

3.2.

Point of zero charges (pHpzc)

The point of zero charges of adsorbents (pHpzc) is a point

where an adsorbent have zero potential charge on its surface.
The presence of H or OH ions in solutions may change the
potential surface charges of adsorbents. If the pH of solution is
above its pHpzc the surface functional groups on adsorbents
will be protonated by the excess H ions; on the contrary if it is
below its pHpzc, the surface functional groups will be deprotonated by the OH ions presence in the solution (Kubilay
et al., 2007). The plot to determine the point of zero charges for
bentonite and activated carbon is depicted in Fig. 4. The point
of zero charge of bentonite and activated carbon is 3.85 and
4.91, respectively.

Surface functional groups of adsorbent

Surface functional groups within activated carbon give

significant contribution toward its adsorption ability,
primarily through providing selectivity to attract cation onto
carbon surface (Valix et al., 2006). These functional groups are
consisted mainly by acidic and basic groups which affect the
surface charges and adsorption properties of activated carbon.
Adsorption on activated carbon therefore not only relies upon
its pore structure as the change of surface charges is also
a crucial factor affecting the adsorption capacity.
From Boehms titration, several surface functional groups
existence can be verified, which is lactone, carboxyl and
phenolic groups. The result of Boehms titrations is given in
Table 2. Significant difference exists on the amount of its
acidic and basic functional groups, confirming previous
observation on pHpzc of activated carbon which exists within
acidic range.
FTIR spectra can reveal the surface functional groups on
activated carbons surface qualitatively based on the characteristic absorbed energy for each bonds in certain groups
(Bruice, 2004), although some particular peaks overlap might
exist.
Surface functional groups in bentonite are depicted in
Fig. 5. Its spectral evaluation is also summarized in Table 3.
The presence of Si and Al as oxygen functional groups within
AlOH and SiOH can be confirmed from Table 2 (Bajpai and
Sachdeva, 2002; Kubilay et al., 2007).
FTIR spectra of activated carbon were also determined by
FTIR spectra as shown in Fig. 5. The presence of C]O peaks
around 1685 cm1 can be identified, originated from bonding
in carboxylic, lactone and another basic oxygen functional
groups, i.e. chromene and pyrone structures. Peaks around
1025 cm1 come from CO bonding while the very broad
peaks in wavenumber 35503200 cm1 are recognized to be
OH functional groups for caboxyl and phenol. The presence
of phenol is confirmed by the presence of peak around 1578
and 1610 cm1 which was the absorption energy of benzene
rings.

3.4.

Adsorption studies

In general, the exact mechanism involved within liquid

phase adsorption is more complicated than that for the gas
phase adsorption. In liquid phase adsorption, many factors
affect the adsorption such as temperature, affinity of adsorbate to solvent, solution pH, adsorbent concentration, etc. In
adsorption of amoxicillin, the most important factor within
the adsorption process is the solution pH as it can alter the
charge of amoxicillin molecule. In most cases, amoxicillin
has a positive charge when the solution pH lies below its
isoelectric point which then shifts into negative charge as the
solution pH rises above its isoelectric point (Adriano et al.,
2005). This phenomenon occurs due to the ionization of its
functional groups, identified as carboxyl (pKa 2.68), amine
(pKa 7.49) and phenolic hydroxyl (pKa 9.63) (Goddard
et al., 1996).
The equilibria isotherm data for adsorption of amoxicillin
onto bentonite and activated carbon were fitted by Langmuir

water research 43 (2009) 24192430

2423

Fig. 3 SEM pictures of (a), (b), (c) and (d) bentonite; (e), (f) and (g) activated carbon.

and Freundlich models. Langmuir model was the most widely

used isotherm equation, which has the form
qe q0

KL Ce
1 KL Ce

these parameters, based on Langmuirs dimensionless

constant, RL, adsorption performance also can be classified as
(Kubilay et al., 2007)

(1)

where q0 (mg/g) is the maximum adsorption capacity and KL

(L/mg) is the Langmuir isotherms constant. In addition to

 Unfavourable, if RL > 1
 Linear, if RL 1
 Favourable, RL < 1

2424

water research 43 (2009) 24192430

a 120
8
110
100

%T

pHfinal

90

4
80
2

70

00

37

40

50
35
00
32
50
30
00
27
50
25
00
22
50
20
00
17
50
15
00
12
50
10
00
75
0

60
0

Wavenumber (cm-1)

pHinitial

65

8
60
55

%T

pHfinal

50
45
40

2
35

Equation (2) can be used to determining Langmuirs dimensionless constant as follows

1
1 KL CO

(2)

Freundlich model, on the other hand is defined as

qe Kf Ce1=n

0
75

50
15
00
12
50
10
00

00

17

50

20

00

22

50

25

00

where Kf is Freundlich constant and n was the parameter of

heterogeneity of adsorption process. Higher n value suggests
the non-linearity of the data while n value above 10 indicates
that the adsorption process was irreversible (Do, 1998).
As-fitted Langmuir and Freundlich parameters for
adsorption of amoxicillin onto bentonite are given in Table 4.
Fig. 6(a) depicts its adsorption isotherms. In Fig. 6(a), symbols
represent the experimental data while solid lines represent
the model as-fitted by Langmuir or Freundlich equations.

(3)

Table 2 Surface chemistry analysis of activated carbon

using Boehms titration.
Amount of surface functional groups, meq/gr AC
Acidic

101.06

27

Fig. 5 FTIR spectra for (a) bentonite and (b) activated

carbon.

 Irreversible, RL 0

Carboxyl

50

Wavenumber (cm-1)

Fig. 4 Determination of point of zero charge for (a)

bentonite and (b) activated carbon.

RL

30

00

pHinitial

32

35

00

37

40

50

30

Basic

Lactone

Phenol

244.62

2.06

Total
347.74

87.91

Table 3 FTIR identification of bentonite spectra.

Assignment
Al(Mg)OH
HOH bending
SiOSi stretching
OH bending bounded 2 Al3
OH bending bounded Fe3 and Al3
SiO stretching of silica and quartz

Wavenumber (cm1)
3631
1643
1111
927
892
807

2425

water research 43 (2009) 24192430

Table 4 Parameters of adsorption equilbria isotherms.

Adsorbent

pH

Bentonite

2.31
3.85
7.01

Activated carbon

2.15
4.98
7.04

Langmuir

Freundlich

qmax (mg/g)

KL (L/mg)

RL

1/n

Kf (mg/g) (L/mg) (1/n)

R2

53.9315
49.9968
47.3715

0.0074
0.0060
0.0050

0.9886
0.9766
0.9899

0.2995
0.3453
0.3876

0.5616
0.5840
0.6077

1.6261
1.2129
0.9275

0.9655
0.9537
0.9658

0.0196
0.0382
0.0256

0.9948
0.9853
0.9816

0.1390
0.0765
0.1100

0.6468
0.6693
0.6183

7.1170
12.2835
9.4347

0.9936
0.9905
0.9949

186.934
221.868
189.551

As seen in Fig. 6(a), Langmuir model can represent the

equilibria data reasonably well. The pH value of 2.31 came out
as the best of three chosen pH value for adsorption of amoxicillin onto bentonite as indicated in Fig. 6(a) and also Langmuir parameter q0 and Freundlich parameter Kf as

summarized in Table 4. On the basis of Langmuirs dimensionless constant; RL, the adsorption of amoxicillin onto
bentonite is favourable as also indicated in Table 4. The nonlinearity and heterogeneity of adsorption can also be identified from the value of Freundlich parameter, n. These features

Qe (mg/g)

30

20

10
pH 2,31
pH 3,85
pH 7,01

0
0

50

100

150

200

250

Ce (mg/L)

b
120

Qe (mg/g)

100

80

60

40

20

pH 2,15
pH 4,98
pH 7,04

0
0

20

40

60

Ce (mg/L)
Fig. 6 Equilibria adsorption isotherms for (a) bentonite and (b) activated carbon by Langmuir model and Freundlich model
(inset).

2426

water research 43 (2009) 24192430

are quite consistent with the nature of amoxicillin and

bentonite.
The protonation for both amoxicillin and bentonite functional groups at low pH enhances the adsorption capacity of
bentonite. As previously mentioned, adsorption of amoxicillin
onto adsorbent in aqueous solution is strongly influenced by
the solution pH so that several possible adsorption mechanisms of amoxicillin onto bentonite can be proposed.
The first mechanism is cation-exchange mechanism. In
principle, low valence cations in bentonite structure were
exchanged by protonated functional groups within amoxicillin which have positive charge. The positive charge of

Table 5 Results of AAS analysis for amoxicillin

containing solution before and after adsorption using
bentonite.
No.

Parameters

1.
2.
3.
4.
5.
6.

Concentration (mg/L)
Before

After




1.81
1.60


23.47
15.5
6.51
8.24
2.90
49.35

Al
Mg
Fe
Na
K
Ca

H
N

N
NH2

H2O

Al

O
O

HO

H
N

N
O

NH2 O

+HO

Al

HO

AlH

H
N

NH2
O

HO

OH
O

H
N

Al
NH2

N
O
OH
O

OH

O
Al

O-

repulsion

-O

N
N
H
NH2
S

Fig. 7 Schematic diagram for (a) mechanism of protonated aluminol in bentonite and deprotonated carbonyl in amoxicillin,
(b) mechanism of unprotonated aluminol in bentonite and unprotonated amoxicillin molecule and (c) repulsion mechanism
between deprotonated aluminol groups in bentonite and deprotonated carboxyl groups in amoxicillin.

2427

water research 43 (2009) 24192430

^COOH / ^COO H

(above pH value of 2.68)

%T

The amine groups was also protonated as follows

(Andreozzi et al., 2005)

^NH2 H / ^NH
3
ions in solution)
Before adsorption
After adsorption
4000

3500

3000

2500

2000

1500

1000

Wavenumber (cm-1)
Fig. 8 FTIR spectra of bentonite after adsorption process.

amoxicillin was due to the protonation of amoxicillin carboxyl

and amine groups by the presence of free H ions in the
solution. For carboxyl groups, the protonation take place as
follows (Andreozzi et al., 2005)

^Coo H / ^COOH (below pH value of 2.68 without free

H ions in solution)

(below pH value of 7.49 with free H

On the other hand, the phenol groups on amoxicillin will

not be protonated or deprotonated in the pH range studied.
The exchange between protonated carboxyl and amine groups
in the amoxicillin and low valence cations in bentonite
structure such as Al3, Mg2, Fe3, Na, Ka, and Ca2 during
adsorption process is indicated by the presence of these
cations in solution after adsorption completes. AAS were
employed to confirm their existence of which the results are
given in Tables 1 and 5.
The second possible mechanism is the interactions
between protonated aluminol and silanol groups in bentonite
and negatively charged oxygen atoms of carboxyl groups.
Silica and alumina functional groups on bentonite surface
may be protonated as the solution pH lies below its pHpzc,
again due to the presence of free H ion in the solution. The
protonation and deprotonation of silica can be described as
(Kubilay et al., 2007)

Fig. 9 Reaction between carbonyl groups on activated carbon and amine functional groups on amoxicillin.

water research 43 (2009) 24192430

^SiOH OH / ^SiO H2O

Furthermore, the aluminol groups on bentonite surface
when
were also protonated in the form of AlOH
2
pHsoln < pHpzc or in the form of AlO when pHsoln > pHpzc due
to deprotonation mechanism (Bajpai and Sachdeva, 2002). The
schematic diagram for this mechanism is given in Fig. 7(a).
During the process, not all available aluminol and silanol
groups were protonated, therefore interactions between
unprotonated aluminol and silanol groups in bentonite and
unprotonated amoxicillin molecule also take place. The
mechanism of these interactions can be seen in Fig. 7(b).
Since bentonite having negative charge on its surface due
to its isomorphous substitution of Al3 for Si4 in tetrahedral
layer and Mg2 for Al3 in octahedral sheet, it can attract
amoxicillin molecule which has positive charge from
protonation of amine groups.
FTIR spectra of bentonite after adsorption process confirm
the presence of functional groups of amoxicillin on bentonites surface as shown in Fig. 8. The attached amoxicillin
structure on bentonite was verified by peaks at 2341 cm1,
characteristic of C]O strained rings vibrations for b-lactams.
Cations with high valences, e.g. Si, were more difficult to be
released, as evidenced by the remaining existence of some
peaks on 1111 cm1 for SiO stretching and on 1055 cm1 for
SiOSi stretching.
At pH of 7.01, the presence of AlO due to deprotonation of
aluminol groups on bentonite provides a repulsive force to the
negatively charged amoxicillin molecule. The negative charge
of amoxicillin comes from deprotonation of carboxyl groups
of which the proposed mechanism for these repulsions is
given in Fig. 7(c).
Equilibria isotherms data for adsorption of amoxicillin
onto activated carbon is presented in Fig. 6(b). These
isotherms were also fitted by Langmuir and Freundlich
models. The fitted parameters of both equations obtained by
non-linear regression method are summarized in Table 4.
At pHpzc, activated carbon gave the highest removal
performance. At pHpzc of activated carbon (4.91), amoxicillin
exists in its neutral form (the pH range where amoxicillin
exists in neutral form is 36) (Lavniewski et al., 1998). Similar
observations were also noted by other researchers (Dutta
et al., 1997a,b, 1999).
At pHpzc of adsorbent (pKa1 < pHsoln < pKa2, pKa3), amine
functional groups in amoxicillin present in the form of NH
3
and carboxyl functional groups can be found in the form of
COO. At this condition, the electrostatic force would
enhance the adsorption capacity since activated carbon
contains positive and negatively charged functional groups at
the same time which attracts the positive and negatively
charged functional groups on amoxicillin.
Another possible mechanism, also worth to be mentioned
is the reaction between amine functional groups on amoxicillin with carbonyl functional groups on activated carbon.
C]O in carbonyl groups would be suppressed by the NH2
groups to become C]N while H2O is being released to the
solution. The mechanism is provided in Fig. 9.

3.5.

Adsorption kinetics

The kinetics for adsorption of amoxicillin onto bentonite and

activated carbon were also examined. Pseudo-first and second
order models were employed to correlate the kinetics data.
The pseudo-first order model has the form as follow


dqt
k1 qe  qt
dt

(4)

The integration of Equation (4) with the boundary conditions

as follow: t 0 / t and qt 0 / qt, gives the result:


1
qt qe 1  k t
e1

(5)

While the pseudo-second order model has the following form:

2
dqt
k2 qe  qt
dt

(6)

The integration of Equation (6) with the same boundary

conditions as those of Equation (4) gives

k2 q2e t
1 k2 qe t


qt

(7)

Adsorption kinetics data on bentonite along with the correlated model using the first and second order model were
shown in Fig. 10(a). The parameters for pseudo-first and

20

15

Qt (mg/g)

^SiOH H / ^SiOH
2

10

pH 2.15
pH 3.85
pH 7.01

0
0

100

200

300

400

t (minutes)

25
20

Qt (mg/g)

2428

15
10
pH 2,23
pH 4,98
pH 7,05

5
0
0

10

20

30

40

t (menit)
Fig. 10 Adsorption kinetics for (a) bentonite and
(b) activated carbon fitted by pseudo-first and second order
model (inset).

2429

water research 43 (2009) 24192430

Table 6 Parameter of adsorption kinetics.

Adsorbent

pH

qe (exp) (mg/g)

Pseudo-first- order

Pseudo-second-order

k1 (min )

qe (mg/g)

k2,10 (g/mg) (min1)

qe (mg/g)

R2

1

Bentonite

2.15
3.85
7.01

20.517
19.748
18.749

0.0092
0.0077
0.0069

19.5491
18.6361
17.9817

0.9796
0.9808
0.9853

5.2434
4.2101
3.7711

20.825
19.005
18.297

0.9937
0.9927
0.9942

Activated carbon

2.23
4.98
7.05

24.745
25.055
24.894

0.1954
0.2993
0.2331

23.9001
24.2975
24.2060

0.9836
0.9880
0.9856

0.0108
0.0214
0.0144

26.0374
26.7083
26.6975

0.9971
0.9980
0.9970

second order models obtained by non-linear regression were

summarized in Table 6.
The pseudo-second order model correlates the kinetic data
quite well (R2 > 0.99) as indicated in Table 6 and Fig. 10(a). This
model assumes that chemisorption is dominant and controls
the adsorption (Ho, 2006). The values of parameter k (k1 for
pseudo-first order and k2 for pseudo-second order) suggest
that similar trends exist for both pseudo-first and second
order models as their values increase with decreasing pH
which indicates that at lower pH, the interaction between
bentonite structure and amoxicillin molecule is stronger,
resulting in faster adsorption process.
The qe values also indicate that the amount adsorbed at
equilibrium increases as the pH value decrease. Accordingly at
low pH, more functional groups were protonated in comparison to that at high pH value. Thus, more interaction between
amoxicillin and surface functional groups in the adsorbent is
to be expected, leading to enhanced adsorption capacity.
Fig. 10(b) shows the kinetic data and modelling curve for
adsorption of amoxicillin onto activated carbon. In Fig. 10(b),
the kinetic data are represented by symbols while the pseudofirst and second order models are represented by solid lines.
Table 6 summarizes the as-fitted parameters for pseudo-first
and second order models. It can be seen that both models fit the
data quite well. It is thus impelling to say that both chemisorption and physisorption mechanisms take place for this
adsorption system. Physisorption occurs as the amoxicillin
which is still below the average
molecule size is only about 13 A
), justifying amoxicillin
pore size of activated carbon (<20 A
moleculess capability to penetrate carbons interior.
The k value for both pseudo-first and second order models
for this adsorption system indicates that at pHpzc, the rate
constants are higher in comparison to those observed at other
pH. This trend confirms the hypothesis that adsorption

Table 7 Adsorption of amoxicillin from real

pharmaceutical wastewater.
Parameter

Wastewater containing
amoxicillin

Adsorbent
Bentonite Activated carbon
Amount of adsorbent (g/50 mL soln.)
1.5
1.5
Initial concentration
317 mg/L
317 mg/L
Final concentration
38 mg/L
16.9 mg/L
% Removal
88.01%
94.67%

process occurs faster at neutral form (where the positive

charge equal to the negative charge).

3.6.

Adsorption of amoxicillin in real wastewater

To verify the potential bentonite application in industry, the

adsorption performance within real wastewater that contains
amoxicillin (from P.T. Coronet Crown) is also provided in
Table 7. Activated carbon indeed shows higher removal efficiency, although not in a substantial margin (only differs by
about 6%) to that shown by bentonite, indicating bentonites
suitability as adsorbent. It must be noted, however that both
adsorbents cannot completely remove the amoxicillin due to
the sorption competition with other substances which is also
present in the wastewater.

3.7.

Conclusion

Adsorption of amoxicillin onto bentonite and activated carbon

was performed at several different pH values. Several possible
adsorption mechanisms were elaborated which include
cation exchange, verified by the presence of low valence
cation in the solution after adsorption; interactions between
protonated aluminol groups in bentonite and deprotonated
carboxyl groups in amoxicillin; interactions between unprotonated aluminol and silanol groups in bentonite and carboxyl
groups in amoxicillin as well as the attraction of positively
charged amoxicillin molecule by the negatively charged
isomorphous bentonite structure. The equilibria adsorption
isotherm data on bentonite were modeled using Langmuir
and Freundlich equations while their kinetics data were fitted
by pseudo-second order model.
In the adsorption of amoxicillin onto activated carbon,
both physisorption and chemisorption play important role,
with the highest removal capacity at pHpzc. Physisorption
occurs due to the small size of amoxicillin molecules, justifying its penetration onto microporous structure of activated
carbon. On the other hand, chemisorption also take place due
to the presence of functional groups on activated carbons
surface. The equilibria isotherms data for adsorption of
amoxicillin onto activated carbon were also modeled using
the Langmuir and Freundlich models. Both pseudo-first and
second order correlates the kinetic data on activated carbon
quite well. By looking at its amoxicillins removal efficiency on
real wastewater which is only a bit less than activated carbon,
bentonite can be looked upon as an alternative potential
adsorbent, especially in Indonesia.

2430

water research 43 (2009) 24192430

Acknowledgment
The authors would like to thank A/Prof. Joao C. Diniz da Costa
from FIMLab, Division of Chemical Engineering, the University
of Queensland, Australia for his support in terms of SEM
equipment access.

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