Available online at www.sciencedirect.

com
JOURNAL OF
ENVIRONMENTAL
SCIENCES
ISSN 1001-0742
CN 11-2629/X
Journal of Environmental Sciences 2012, 24(9) 1579–1586
www.jesc.ac.cn

Ciprofloxacin adsorption from aqueous solution onto chemically prepared

carbon from date palm leaflets
El-Said Ibrahim El-Shafey ∗, Haider Al-Lawati, Asmaa Soliman Al-Sumri

Department of Chemistry, College of Science, Sultan Qaboos University, P. O. Box 36-Al-Khodh 123, Muscat, Oman

Received 13 October 2011; revised 14 December 2011; accepted 16 December 2011

Abstract
A chemically prepared carbon was synthesized from date palm leaflets via sulphuric acid carbonization at 160°C. Adsorption of
ciprofloxacin (CIP) from aqueous solution was investigated in terms of time, pH, concentration, temperature and adsorbent status
(wet and dry). The equilibrium time was found to be 48 hr. The adsorption rate was enhanced by raising the temperature for both
adsorbents, with adsorption data fitting a pseudo second-order model well. The activation energy, E a , was found to be 17 kJ/mol,
indicating a diffusion-controlled, physical adsorption process. The maximum adsorption was found at initial pH 6. The wet adsorbent
showed faster removal with higher uptake than the dry adsorbent, with increased performance as temperature increased (25–45°C). The
equilibrium data were found to fit the Langmuir model better than the Freundlich model. The thermodynamic parameters showed that
the adsorption process is spontaneous and endothermic. The adsorption mechanism is mainly related to cation exchange and hydrogen
bonding.

Key words: ciprofloxacin; carbon; adsorption; palm leaflets

DOI: 10.1016/S1001-0742(11)60949-2

Introduction (Bhandari et al., 2008; Golet et al., 2002). In addition,

Ciprofloxacin (CIP) is an antibiotic that is globally used for
the treatment of several bacterial infections in humans and
animals. Significant sources of wastewater drug contami-
nation include drug manufacturers and hospitals (Bhandari
et al., 2008). In addition, the incomplete metabolization
of the drug in humans and improper disposal of unused
or expired drugs through the sink contribute to wastew-
ater CIP contamination. In wastewater treatment plants,
CIP and other antibiotics are only partially eliminated
and residual amounts can reach the aquatic ecosystem.
CIP has been found in wastewater and surface water at
concentrations typically < 1 μg/L (Bhandari et al., 2008;
Carmosini and Lee, 2009). Higher concentrations were
reported in effluents from hospitals (up to 150 μg/L) and
drug production facilities (31 mg/L) (Hartmann et al.,
1999; Martins et al., 2008). CIP can be adsorbed by sewage
sludge with concentrations up to 2.42 mg/kg (Golet et al.,
2002). It can accumulate in soils when CIP-contaminated
sludge is utilized as fertilizer (Golet et al., 2003). CIP
was also found to accumulate in plants such as lettuce,
cucumber and common barley when cultivated in CIP-
spiked soil (Lillenberg et al., 2010).
The presence of CIP in wastewater and surface water,
even at low concentrations, is considered an environmental
hazard as it can develop antibiotic resistance in bacteria
* Corresponding author. E-mail: dr el shafey2004@yahoo.co.uk
because it is toxic to some microorganisms, CIP can
cause disturbances to the biological balance in the aquatic
ecosystem. In the literature, several studies have been
conducted for the removal of CIP from water including
photodegradation (Belden et al., 2007), photo-Fenton oxi-
dation (Sun et al., 2009), ozonation (De Witte et al., 2010),
and adsorption on activated charcoal and talc (Ibezim et
al., 1999), dissolved organic carbon (Carmosini and Lee,
2009), montmorillonite (Wang et al., 2010, 2011), surface-
modified carbon materials (Carabineiro et al., 2011a) and
goethite (Zhang and Huang, 2007).
Date palm (Phoenix dactylifera L.) is an important com-
mercial crop in the Middle East, particularly in Oman and
the Gulf states (Al-Yahyai and Al-Khanjari, 2008) where
180,000 and 3 million tons of palm leaflets are produced
annually, respectively. Burning in the field is a common
practice that poses environmental problems. The objective
of this research was to prepare a carbonaceous adsorbent
from date palm leaflets using sulphuric acid carbonization,
and to investigate its capability for the adsorption of CIP
from aqueous solution in terms of kinetics and equilibrium.
1 Materials and methods
1.1 Materials
All the chemicals used were of analytical grade. Pure
ciprofloxacin HCl·H2 O, CIP, was supplied by the National
1580 Journal of Environmental Sciences 2012, 24(9) 1579–1586 / El-Said Ibrahim El-Shafey et al.
Pharmaceutical Industries Company, Muscat, Oman. Palm
leaflets were collected from a local farm in Muscat and
were washed with distilled water to remove dirt, dust and
surface impurities. The cleaned leaflets were put in plastic
trays and left to dry at room temperature. A stock CIP
solution, 500 mg/L, was prepared by dissolving 0.5 g of
CIP in 1000 mL deionized water. Other concentrations
were prepared by suitable dilution with deionized water.
1.2 Preparation of the carbon adsorbent
Clean dry palm leaflets were cut into small pieces and
were chemically carbonized via sulphuric acid treatment
as follows: 40 g of clean dry palm leaflets was mixed
with 12 mol/L sulphuric acid (100 mL). The mixture was
heated to (160 ± 2)°C and was kept in that temperature
range for 25 min for complete carbonization. The resulting
black mixture was allowed to cool to room temperature and
the spent sulphuric acid was filtered off using a Buchner
funnel under vacuum. The produced wet carbon was
stored under 1 mol/L sulphuric acid solution to avoid any
possible bacterial growth. Before use, the wet adsorbent
was washed in a Gooch crucible (G2) with distilled water
to remove residual acid until the wash water did not show
a change in methyl orange color. The sample was then
left under suction for 30 min to remove water among
the particles. The wet carbonaceous product was then
used for adsorption experiments and 1 g sample was used
for moisture content determination. Moisture content was
determined in each experiment using the wet adsorbent and
was found to be 76%. For experiments with dry adsorbent,
the acid-free wet carbon was dried at 120°C to constant
weight. The dry carbon was transferred to a desiccator
to cool and then used in the adsorption experiments. The
yield of the carbon produced was 96%.
1.3 Adsorption experiments
For the kinetic experiments, samples of 0.4 g of the dry
carbon (or its equivalent mass of wet carbon) were mixed
with CIP (200 mL, 100 mg/L) at initial pH 6. At different
time intervals, an aliquot of supernatant was withdrawn for
analysis. Batch experiments were carried out by mixing 0.1
g of the adsorbent with 50 mL of CIP solution of the de-
sired concentration, pH and temperature in a shaking water
bath (100 r/min) until equilibrium was reached. The effect
of pH on CIP adsorption was studied for a concentration
of 200 mg/L at different pH values (2.0–11.5). Before the
addition of the pre-weighed adsorbent to the CIP solution,
the solution pH was adjusted by adding 0.1 mol/L NaOH
or 0.1 mol/L H2 SO4 . Equilibrium isotherm studies were
carried out at initial pH 6 for different CIP concentra-
tions (50–300 mg/L) at different temperatures (25–45°C).
After the equilibrium time was reached, an aliquot of
the supernatant was analyzed spectrophotometrically using
a UV-Visible spectrophotometer (Varian/Cary/50 Conc.,
Varian Incorporation, The Netherlands) at a wavelength
(λ) of 273 nm (Wang et al., 2010). All experiments were
carried out at least twice.
Vol. 24
1.4 Physicochemical characterization
Physico-chemical tests were carried out using the dry
carbon. The surface area was measured using an Autosorb-
1(Quantachrome Instruments, USA) via nitrogen adsorp-
tion at 77 K. Scanning electron microscope (SEM) analysis
was carried out using a Geol JSM 840-A scanning electron
microscope (Jeol, Japan). X-ray powder diffraction was
carried out to reveal information about the crystallographic
structure of the carbon. A Philips PW 1830 generator with
a Philips PW 1050 powder goniometer (Philips, USA) was
used and the diffraction patterns were determined using
copper Kα radiation with a Ni filter. FT-IR spectroscopy
was also employed using a FT-IR spectrometer (Spectrun
BX, Berkin Elmer, Germany) in the wavelength range
of 4000–800 cm−1 with background subtraction. Surface
functional groups were also determined using Boehm titra-
tions (Boehm, 1996; El-Shafey, 2007). The point of zero
charge (PZC) of the carbon was determined by following
procedure (Lu et al., 2009): 0.1 g of the dry carbon was
placed in a 25 mL Erlenmeyer flask to which 20 mL of
CO2 -free water was added. The flask was sealed with a
cap and left with occasional agitation for 48 hr at room
temperature. The pH of the filtrate was then measured and
this value is the point of zero charge. This method has
been used satisfactorily by Moreno-Castilla et al. (2000)
and Leyva-Ramos et al. (2005).
2 Results and discussion
2.1 Characterization of chemically carbonized adsor-
bent
Cellulose, hemicelluloses and lignin are the main con-
stituents of the agricultural waste of date palm leaflets.
Concentrated sulphuric acid acts as an extremely strong
dehydrating agent, carbonizing the cellulose and hemicel-
luloses via the removal of water. In addition, it acts as
a strong oxidizing agent because of its affinity to lose
an atom of oxygen to form sulphurous acid, that readily
decomposes to sulfur dioxide and water (Parker, 1997).
Cellulose is susceptible to oxidizing agents due to the
presence of three hydroxyl groups in each anhydroglucose
unit (Nikitin, 1996). Lignin is more readily oxidized than
cellulose and other wood polysaccharides (Nikitin, 1996).
Under the applied preparation conditions, carbonization
(via dehydration) with partial oxidation took place to the
cellulose and hemicelluloses, however, for lignin, partial
oxidation and fragmentation took place (Cox et al., 1999).
The scanning electron microscope image in Fig. 1 shows
that the carbonaceous adsorbent still maintains the plant’s
fibrous texture. The X-ray diffraction pattern showed no
observable peaks, indicating the amorphous structure of
the adsorbent (data not shown).
The FT-IR spectrum of the produced carbon (Fig. 2)
shows the presence of hydroxyl, carboxyl and other
carbon-oxygen species as assigned in Table 1. Simi-
lar functional groups were identified on the surface of
chemically-carbonized carbon from flax shive via sul-
phuric acid treatment (Cox et al., 1999). Surface acidic
No. 9 Ciprofloxacin adsorption from aqueous solution onto chemically prepared carbon from date palm leaflets 1581

for a carbonaceous adsorbent prepared from flax shive

via sulphuric acid carbonization. The ash content was
determined to be 11.5%.
2.2 Effect of pH
Adsorbed CIP was calculated from the decrease in CIP
concentration in solution by considering the adsorption
volume and amount of the adsorbent (Eq. (1)).

(C0 − Ce )V
qe = (1)
m
where, qe (mg/g) is the amount of CIP (mg) adsorbed onto
a unit mass of the carbon (g) on dry basis at equilibrium;
C 0 (mg/L) and C e (mg/L) are the concentrations of CIP in
Fig. 1 SEM image of the chemically carbonized adsorbent. the initial solution and at equilibrium; m (g) is the amount
of adsorbent used on dry basis and V (L) is the volume of
functional groups were determined by Boehm titra- CIP solution.
tions, where NaHCO3 neutralizes carboxylic, Na2 CO3 The CIP acid dissociation constants pK a1 and pK a2 are
neutralizes carboxylic and lactonic, and NaOH neutral- 6.1 and 8.7 respectively (Gu and Karthikeyan, 2005) as
izes carboxylic, lactonic and phenolic functional groups presented in Fig. 3. At pH < 6.1, CIP molecules mainly
(Boehm, 1996). The number of milliequivalents (meq) exist as cations (CIP+ ) because of the protonation of the
calculated based on the titrations for the surface carboxyl,
lactone and phenol groups were 2.6, 1.5 and 0.82 meq/g, O O
pKa1 6.1
respectively. The carbon pHpzc (Lu et al., 2009) was found
F
to be 3.4. HO
The surface area measured via nitrogen adsorption at 77
K using the BET model was 24.4 m2 /g. The monolayer
N N
capacity and the BET constant were found to be 5.61
cm3 /g and 149 respectively. Such a low surface area NH
can be possibly related to the presence of carbon-oxygen
functional groups that occupy a large fraction of the pKa2 8.7
adsorbent surface (Youssef et al., 1995). A low surface Fig. 3 Molecular structure of ciprofloxacin.
area of 19 m2 /g was also found by Cox et al. (1999)
60
46 pKa1 = 6.1 pKa2 = 8.7
44 55
42
CIP sorbed (mg/g)

40 50
Transmittance (%)

38
36 45
34
32 40
30
28 35 Wet
26 Dry
24 30
0 2 8 4 10 6 12 14
22
Initial pH
4000 3600 3200 2800 2400 20001800 1600 1400 1200 1000 800
Wavenumber (cm-1) Fig. 4 Adsorption of CIP at different initial pH values and 25°C on wet
and dry carbons. Initial concentration 200 mg/L, volume of CIP solution
Fig. 2 FT-IR spectrum of the carbonaceous adsorbent. 50 mL, shaking speed 100 r/min.

Table 1 FT-IR band positions and suggested assignment for the functional groups on the surface of the carbonaceous adsorbent

Band position (cm−1 ) Band assignment Reference

3410 O–H stretching vibrations (H-bonded) Zawadzki, 1980

2920, 2855 C–H stretching vibrations in CH2 George and McIntyre, 1987
1700 –C=O stretching vibrations (lactone and carboxylic acids) George and McIntyre, 1987
1613 –COO− asymmetric and symmetric stretching (carboxylate) Gómez-Serrano et al., 1994; van der Mass, 1969
or skeletal C=C aromatic vibrations
1300–900 stretching C–O vibrations in hydroxyl groups and ether type structures Gmez-Serrano et al., 1994
1582 Journal of Environmental Sciences 2012, 24(9) 1579–1586 / El-Said Ibrahim El-Shafey et al. Vol. 24

amine group in the piperazine moiety (Wang et al., 2010).
At pH > 8.7, CIP molecules exist as anions (CIP− ) due to
the loss of a proton from the carboxylic group. In the pH
range 6.1–8.7, the pH values are higher than pK a1 of the
carboxylic group, thus deprotonating the carboxylic group
to the negatively charged carboxylate. However, the amine
group stays protonated and positively charged as this pH
range is still lower than pK a2 of the amine group. Ac-
cordingly, in the above mentioned pH range, zwitterionic
species of CIP molecules dominate in the aqueous solution.
Zwitterion formation of CIP molecules in the range of
pH between pK a1 and pK a2 has been emphasized in other
studies (Drakopoulos and Ioannou, 1997; Carmosini and
Lee, 2009; Wu et al., 2010, Carabineiro et al., 2011b; Wang
et al., 2010, 2011).
As shown in Fig. 4, CIP adsorption was low at pH below
3 and increased with the rise in initial pH, showing a max-
imum adsorption around pH 6, with better performance
for the wet adsorbent than for the dry. Adsorption started
to decrease at pH higher than 6; however, a significant
decrease was shown beyond pH 8.7. Thus, pH 6 was
selected as the optimum pH for the kinetic and equilibrium
studies. At pH < 3.4 (pHpzc of the carbon), the carbon
surface stays protonated (such as –COOH), however, at pH
> 3.4, the carbon surface becomes negatively charged. At
pH  3, adsorption was low between the protonated surface
and the CIP cations. However, in the pH range 3.4–6.0,
electrostatic interaction is maximized between the nega-
tively charged surface and the CIP cations. In the pH range
6.1–8.7, electrostatic interaction is believed to take place
between the positively charged amine group in the CIP
zwitterion and negatively charged carbon-oxygen groups
on the adsorbent surface. However, a degree of repulsion
between negatively charged carboxylate in the CIP zwit-
terion and the negatively charged surface probably takes
2.3 Kinetics of ciprofloxacin adsorption
Based on the results of the pH experiments, initial pH
6 was chosen for the studies of adsorption kinetics and
equilibrium. Equilibrium was reached within 48 hr. As
temperature increased, CIP adsorption appeared to be
faster, with higher performance for the wet carbon than for
the dry (Fig. 5).
CIP uptake in the initial stages of adsorption, qt , varied
almost linearly with the square root of time, t0.5 . This
indicates that the initial rate of adsorption is controlled by
intraparticle diffusion, based on Eq. (2), where kd is the
rate constant for pore diffusion (Weber and Morris, 1963)
and qt (mg/g) is the amount of adsorbed CIP at time t.
qt = kd × t0.5 (2)
The calculated values of kd (Table 2) appear higher
for the wet carbon than for the dry. The drying pro-
cess narrowed the adsorbent pores due to shrinkage and
compaction, causing less diffusion of CIP into the dry
adsorbent. An increase in kd values was observed with
rising temperature, as adsorbent swelling is expected with
higher temperatures, giving wider pores and, consequently,
more diffusion of CIP molecules.
Pseudo first- and second-order kinetic models (Eq. (3)
and (4), respectively), were tested for the adsorption kinet-
ic data (Zhang et al., 2011).
k1 t
log(qe − qt ) = log qe − (3)
2.303
60
50
Ciprofloxacin sorbed (mg/g)

place, leading to a slight decrease in CIP sorption. Beyond

pH 8.7, both the carbon and CIP stay negatively charged 40
in solution and this leads to a further decreased uptake.
Similar results were found by Wang et al. (2010) for the ad- 30
sorption of CIP onto montmorillonite. As shown in Fig. 4,
adsorption still appears significant below pH 3 and above 20
pH 8.7, and this is due to the presence of hydrogen bonding
Wet, 25°C Dry, 25°C
between the CIP molecules and carbon-oxygen functional 10 Wet, 35°C Dry, 35°C
groups on the carbon surface. Electrostatic interactions and Wet, 45°C Dry, 45°C
hydrogen bonding were reported as adsorption forces for 00 10
30 40 20 50 60
CIP adsorption on functionalized silicates (Punyapalakul Time (hr)
and Sitthisorn, 2010) and montmorillonite (Wang et al., Fig. 5 Adsorption of CIP on the wet and dry carbons as a function of
2010). time at different temperatures. Initial pH 6, volume of solution 200 mL,
shaking speed 100 r/min, initial concentration 100 mg/L.

Table 2 Pseudo first-order and second-order rate constants of the kinetics of CIP sorption at different temperatures

Adsorbent Temp. (°C) Diffusion Pseudo first-order model Pseudo second-order model
model (kd ) k1 (hr) qe (mg/g) R2 k2 (g/(mg·hr)) h (mg/(g·hr)) qe (mg/g) R2
Wet 25 16.02 0.0875 24.6 0.9750 0.0121 24.1 44.6 0.9975
35 17.96 0.0940 21.84 0.9674 0.0153 35.1 47.8 0.9992
45 21.71 0.1094 21.632 0.9606 0.0187 52.9 53.2 0.9997
Dry 25 12.64 0.0654 14.6 0.9115 0.0110 7.05 25.3 0.9976
35 13.73 0.0702 16.3 0.9591 0.0134 11.6 29.4 0.9986
45 18.52 0.1073 18.3 0.9938 0.0167 18.0 32.8 0.9994
k1 : rate const of pseudo first-order model; k2 : rate const of pseudo second-order model, h: initial adsorption rate.
No. 9 Ciprofloxacin adsorption from aqueous solution onto chemically prepared carbon from date palm leaflets 1583

1/T (hr-1)
0.0031 0.00315 0.0032 0.00325 0.0033 0.00335 0.0034
t 1 t -3.9
= + (4)
qt k2 q2e qe -4.0
y = -2067.7x + 2.527
where, k1 and k2 are the rate constants for the pseudo -4.1 R2 = 0.999
first-and second-order models, respectively. The initial
adsorption rate, h = k2 qe 2 . -4.2

lnk2
The linear plots of log(qe -qt ) versus t for the pseu- -4.3
do first-order model present low correlation values (R2 ), y = -1985.7x + 2.1487
showing a poor fit for the model; however, the linear -4.4 R2 = 0.998
plots of t/qt versus t for the pseudo second-order model -4.5 Wet
show better fitting with high R2 values (Table 2). This Dry
indicates that the adsorption of CIP conforms well with a -4.6
pseudo second-order kinetic reaction, which agrees with Fig. 6 Plots of lnk2 against 1/T for the adsorption of CIP at different
chemisorption as the rate-limiting mechanism through temperatures on wet and dry carbons.
sharing or exchange of electrons between adsorbent and
adsorbate (Ho, 2006). Both of the rate constants k2 (Fig. 7). The experimental isotherm data conform well
(g/(mg·hr)), and the initial adsorption rate, h (mg/(g·hr)), to the Langmuir equation (Zhang et al., 2011), Eq. (6),
were higher for the wet adsorbent than for the dry (Table 2) showing high correlation values of R2 . However, a poor fit
and this, again, could be related to the shrinkage and with low correlation values was found for the application
compaction of the adsorbent as a result of drying, giving of the Freundlich equation (Zhang et al., 2011), Eq. (7), to
narrower pores for the diffusion of CIP molecules (El- the equilibrium adsorption data, Table 3.
Shafey, 2007). The pseudo first-order kinetic model gave
a poor fit and a trend of results cannot be established. Ce 1 Ce
The Arrhenius equation (Eq. (5)) was applied to calcu- = + (6)
qe b×q q
late the activation energy (E a ) for the adsorption processes.
As a result of the good fitting of the kinetic data to the where, q (mg/g) and b (l/mg) are the Langmuir constants
model, the rate constant of the pseudo second-order model, related to maximum adsorption capacity and the relative
k2 , was selected for E a calculation. energy of adsorption, respectively.

k2 = Ae−Ea /RT (5) 1

where, E a (kJ/mol) is the activation energy of CIP adsorp-
tion. A is the pre-exponential factor (frequency factor),
R is the gas constant (8.314 J/(mol·K)) and T (K) is the
solution temperature. From the linear relationship between
the logk2 and 1/T (Fig. 6), E a was calculated and found
to be 17.2 and 16.5 kJ/mol for the wet and dry adsor-
bents, respectively. Low E a values (< 42 kJ/mol) indicate
diffusion-controlled processes, while higher E a values (>
42 kJ/mol) indicate chemically-controlled processes (Liu
and Huang, 2003). Accordingly, the rate-limiting process
for CIP adsorption is evidently physical.
2.4 Adsorption capacity and temperature effect
The adsorption of CIP showed an ‘L-type’ adsorption
isotherm for both wet and dry adsorbents. As temperature
rose, adsorption increased with an advantage for the wet
adsorbent over the one that has been previously dried
Table 3 Isotherm parameters for CIP sorption onto wet and dry adsorbents at different temperatures
log qe = log Ce + log K (7)
n
where, 1/n and K (L1/n mg1−1/n g−1 ) are constants which
are considered to be the relative indicators of adsorption
intensity and adsorption capacity, respectively.
The 1.15 and 1.2 fold increases of CIP adsorption on
wet and dry carbons, respectively, were obtained with
temperature rise from 25 to 45°C (Table 3). This could be
a result of the carbon swelling, allowing more adsorption
active sites to become free for CIP. In a previous study,
Zhang et al. (2011) found that CIP adsorption on modified
coal ash increased with rising temperature. The adsorption
capacities of CIP from the present study were compared
with other adsorbents in previous studies (Table 4). It is
clear that the cheap carbonaceous adsorbent produced from
date palm leaflets shows a high adsorption capacity for CIP.
The isotherm shape can be used to predict if an ad-
sorption system is ‘favorable’ or ‘unfavorable’. Hall et

Adsorbent Temp. (°C) Langmuir model Freundlich model

q (mg/g) b (mg−1 ) Rs R2 1/n K R2
Wet 25 116.3 0.0664 0.048–0.23 0.9973 0.3129 25.28 0.9797
35 125.0 0.0758 0.042–0.21 0.9975 0.3281 26.67 0.9870
45 133.3 0.0997 0.032–0.17 0.9953 0.3213 31.62 0.9892
Dry 25 104.2 0.0522 0.060–0.28 0.9996 0.3362 19.10 0.9515
35 113.6 0.0601 0.053–0.25 0.9998 0.3545 20.42 0.9484
45 125.0 0.0719 0.044–0.22 0.9986 0.3748 21.97 0.9593
Rs : separation factor.
1584 Journal of Environmental Sciences 2012, 24(9) 1579–1586 / El-Said Ibrahim El-Shafey et al. Vol. 24

140 temperatures (Eq. (9)).

120
qe
100 Kc = (9)
CIP sorbed (mg/g)

Ce
80
K c (L/g) values were obtained using the method of Khan
60 and Singh (1987) by plotting ln (qe /C e ) versus qe and
40 Wet 25°C Dry 25°C
extrapolating to zero qe . The intercept of the straight
Wet 35°C Dry 45°C line with the vertical axis gives the values of Kc . As
20 Wet 45°C Dry 45°C presented in Table 5, the value of K c increases with rising
0 temperature, indicating an endothermic nature for CIP
0 40 20 60 80 100 120
adsorption. The Gibbs free energy change of the adsorption
Equilibrium Ce concentration (mg/L)
process is related to K c as shown in Eq. (10) (Uslu and Inci,
Fig. 7 Adsorption of CIP on wet and dry carbons at initial pH 6 at
different temperatures. 2009).

ΔG0 = −RT lnKc (10)

al. (1966) pointed out that the essential characteristics of
the Langmuir isotherm can be expressed in terms of a The changes in enthalpy (ΔH 0 ) and entropy (ΔS 0 )
dimensionless constant, Rs , as presented in Eq. (8). for CIP adsorption were calculated from the slope and
1 intercept of the plot of lnK c against 1/T according to the
Rs = (8) van’t Hoff equation (Uslu and Inci, 2009), Eq. (11).
1 + bC0
where, Rs is the separation factor or equilibrium parameter, ΔS 0 ΔH 0
lnKc = − (11)
which is a direct function of the Langmuir constant b. R RT
The values of Rs indicate the shape of the isotherm: Rs > Plotting lnK c versus 1/T for the wet and dry adsorbents
1 (unfavorable), Rs = 1 (linear), 1 > Rs > 0 (favorable) shows straight lines (Fig. 8). From their slope and inter-
and Rs = 0 (irreversible) (Hall et al., 1966). As shown in cept, ΔH 0 and ΔS0 were determined. The negative values
Table 3, Rs values are in the range of 0.032–0.23 for the of ΔG0 (Table 5) indicate a favorite and spontaneous
wet adsorbent, and 0.044–0.28 for the dry, thus, indicating process (Li et al., 2011).
‘favorable adsorption’ and strong binding between the CIP The positive values of ΔH 0 show that CIP adsorption is
and the adsorbent. endothermic on both adsorbents. As ΔH 0 values are below
R2 values appear more satisfactory for the Langmuir 40 kJ/mol (Table 5), it can be concluded that the nature of
isotherm than for the Freundlich isotherm (Table 3). As the adsorption process is physical (Chern and Wu, 2001),
the Langmuir adsorption isotherm is based on monolayer either cation exchange or hydrogen bonding (Li et al.,
coverage of the adsorbate onto the active sites of the
adsorbent surface (Nadeem et al., 2006), CIP sorption onto Table 5 Thermodynamic parameters of CIP adsorption on wet and dry
the investigated carbon (wet and dry) seems to generate adsorbents
monolayer formation. Adsorbent Temp. Kc ΔG0 ΔH 0 ΔS 0
(K) (L/g) (kJ/mol) (kJ/mol) (kJ/mol)
2.5 Thermodynamic calculations
Wet 298 1.71 –1.33 11.68 43.63
Thermodynamic parameters were calculated from the 308 1.95 –1.71
variation of the equilibrium constant, K c , at different 318 2.31 –2.21
Dry 298 1.33 –0.71 13.10 46.4
Table 4 Maximum adsorption capacities of CIP on different adsorbents 308 1.57 –1.15
318 1.86 –1.64
Adsorbent Maximum Reference
adsorption
(mg/g) 1.2

Kaolinite 6.3 Li et al., 2011 1.0

Kaolinite 7.95 Mackay and Seremet, 2008 y = -1576.5x + 5.5748
Rectorite 135 Wang et al., 2011 0.8
R2 = 0.9983
Illite 33 Wang et al., 2011
lnKc

Montmorillonite 395 Wang et al., 2011 0.6

Montmorillonite 330 Wang et al., 2010
Geothite (Syn-FeOOH) 49.8 Zhang and Huang, 2007 0.4
Geothite (Ald-FeOOH) 33.1 Zhang and Huang, 2007 y = -1405.4x + 5.2474
Modified coal fly ash 1.55 Zhang et al., 2011 Wet R2 = 0.9914
0.2
Aluminous oxide 13.6 Gu and Karthikeyan, 2005 Dry
Oxidized xerogel 60 Carabineiro et al., 2011a 0
Chemically prepared 133.3 This study 0.0031 0.00315 0.0032 0.00325 0.0033 0.00335 0.0034
carbon (wet) 1/T (K-1)
Chemically prepared 125.0 This study
Fig. 8 Plots of lnK c against 1/T for the adsorption of CIP at different
carbon (dry)
temperatures.
No. 9 Ciprofloxacin adsorption from aqueous solution onto chemically prepared carbon from date palm leaflets
2011). The positive value of ΔS 0 indicates an increase
in randomness at the solid-solution interface during the
adsorption of CIP onto the carbon adsorbents.
Similar thermodynamic results were found for CIP
adsorption onto modified coal fly ash (Zhang et al., 2011),
showing negative ΔG0 in the range of –5.4 to –2.8 kJ/mol,
positive ΔH 0 (14.9–28.6 kJ/mol) and positive ΔS 0 (55.3–
107 J/mol).
2.6 Desorption studies
Ciprofloxacin desorption was investigated using 0.5 mol/L
HCl at room temperature. For a sorbent sample (0.5 g)
loaded with CIP at 100 mg/g, desorption reached 83% at
such acidic conditions. The protons replace CIP cations on
the ion exchange sites. The undesorbed fraction of CIP
under such acidic conditions is probably related to other
sorption forces between CIP molecules and the carbon
surface, such as hydrogen and hydrophobic bonding.
3 Conclusions
Chemically-prepared carbon is cheap and efficient for
CIP adsorption. The wet carbon shows better diffusion
and more adsorption capacity than the dry carbon. CIP
adsorption shows a maximum at initial pH 6 because of
the electrostatic interaction between positively charge CIP
and negatively charged carbon. The activation energy E a
was 17 kJ/mol, indicating a diffusion-controlled physical
adsorption process. The calculated thermodynamic param-
eters showed that the adsorption process of CIP is physical,
spontaneous and endothermic, and the adsorption mecha-
nism is mainly related to cation exchange and hydrogen
bonding.
Acknowledgment
The authors would like to thank the National Pharma-
ceutical Industries Company, Muscat, for supplying CIP
samples.
References
Al-Yahyai R, Al-Khanjari S, 2008. Biodiversity of date palm
in the sultanate of Oman. African Journal of Agricultural
Research, 3(6): 389–395.
Belden J B, Maul J D, Lydy M J, 2007. Partitioning and
photodegradation of ciprofloxacin in aqueous systems in
the presence of organic matter. Chemosphere, 66(8): 1390–
1395.
Bhandari A, Close L I, Kim W, Hunter R P, Koch D E, Surampalli
R Y, 2008. Occurrence of ciprofloxacin, sulfamethoxazole,
and azithromycin in municipal wastewater treatment plants.
Practice Periodical of Hazardous, Toxic, and Radioactive
Waste Management, 12(4): 275–281.
Boehm H P, 1996. Chemical identification of surface groups.
Advances in Catalysis, 16: 179–274.
Carabineiro S A C, Thavorn-Amornsri T, Pereira M F R,
Figueiredo J L, 2011a. Adsorption of ciprofloxacin on
surface-modified carbon materials. Water Research, 45(15):
4583–4591.
1585
Carabineiro S A C, Thavorn-amornsria T, Pereiraa M F R, Serp
P, Figueiredo J L, 2011b. Comparison between activated
carbon, carbon xerogel and carbon nanotubes for the ad-
sorption of the antibiotic ciprofloxacin. Catalysis Today,
186(1): 29–34.
Carmosini N, Lee L S, 2009. Ciprofloxacin sorption by dissolved
organic carbon from reference and bio-waste materials.
Chemosphere, 77(6): 813–820.
Chern J M, Wu C Y, 2001. Desorption of dye from activated
carbon beds: effects of temperature, pH and alcohol. Water
Research, 35(17): 4159–4165.
Cox M, El-Shafey E I, Pichugin A A, Appleton Q, 1999.
Preparation and characterisation of a carbon adsorbent from
flax shive by dehydration with sulfuric acid. Journal of
Chemical Technology and Biotechnology, 74(11): 1019–
1029.
De Witte B, Van Langenhove H, Demeestere K, Saerens K, De
Wispelaere P, Dewulf J, 2010. Ciprofloxacin ozonation in
hospital wastewater treatment plant effluent: effect of pH
and H2 O2 . Chemosphere, 78(9): 1142–1147.
Drakopoulos A I, Ioannou P C, 1997. Spectrofluorimetric study
of the acid-base equilibria and complexation behavior
of the fluoroquinolone antibiotics ofloxacin, norfloxacin,
ciprofloxacin and pefloxacin in aqueous solution. Analytica
Chimica Acta, 354(10): 197–204.
El-Shafey E I, 2007. Sorption of Cd(II) and Se(IV) from aqueous
solution using modified rice husk. Journal of Hazardous
Materials B, 147(1-2): 546–555.
George W O, McIntyre P S, 1987. Infrared Spectroscopy. John
Wiley and Sons, Chichester.
Golet E M, Strehler A, Alder A C, Giger W, 2002. Determination
of fluoroquinolone antibacterial agents in sewage sludge
and sludge-treated soil using accelerated solvent extraction
followed by solid-phase extraction. Analytical Chemistry,
74(21): 5455–5462.
Golet E M, Xifra I, Siegrist H, Alder A C, Giger W, 2003.
Environmental exposure assessment of fluoroquinolone
antibacterial agents from sewage to soil. Environmental
Science & Technology, 37(15): 3243–3249.
Gómez-Serrano V, Acedo-Ramos M, López-Peinado A J,
Valenzula-Calahorro C, 1994. Oxidation of activated carbon
by hydrogen peroxide: study of surface functional groups
by FTIR. Fuel, 73(3): 387–395.
Gu C, Karthikeyan K G, 2005. Sorption of the antimicrobial
ciprofloxacin to aluminum and iron hydrous oxides. Envi-
ronmental Science & Technology, 39(23): 9166–9173.
Hall K R, Eagleton L C, Acrivos A, Vermeulen T, 1966. Pore-
and solid-diffusion kinetics in fixed-bed adsorption un-
der constant-pattern conditions. Industrial & Engineering
Chemistry Fundamentals, 5(2): 212–223.
Hartmann A, Golet E M, Gartiser S, Alder A C, Koller T,
Widmer R M, 1999. Primary DNA damage but not mu-
tagenicity correlates with ciprofloxacin concentrations in
German hospital wastewaters. Archives of Environmental
Contamination and Toxicology, 36(2): 115–119.
Ho Y S, 2006. Review of second-order models for adsorption
systems. Journal of Hazardous Materials B, 136(3): 681–
689.
Ibezim E C, Ofoefule S I, Ejeahalaka C N C, Orisakwe O E, 1999.
In vitro adsorption of ciprofloxacin on activated charcoal
and talc. American Journal of Therapeutics, 6(4): 199–201.
Khan A A, Singh R P, 1987. Adsorption thermodynamics of
carbofuran on Sn(IV) arsenosilicate in H+ , Na+ and Ca2+
forms. Colloids and Surfaces, 24(1): 33–42.
1586 Journal of Environmental Sciences 2012, 24(9) 1579–1586 / El-Said Ibrahim El-Shafey et al.
Leyva-Ramos R, Bernal-Jacome L A, Acosta-Rodriguez I, 2005.
Adsorption of cadmium(II) from aqueous solution on nat-
ural and oxidized corncob. Separation and Purification
Technology, 45(1): 41–49.
Li Z H, Hong H L, Liao L B, Ackley C J, Schulz L A,
MacDonald R A et al., 2011. A mechanistic study of
ciprofloxacin removal by kaolinite. Colloids and Surfaces
B: Biointerfaces, 88(1): 339–344.
Lillenberg M, Litvin S V, Nei L, Roasto M, Sepp K, 2010.
Enrofloxacin and ciprofloxacin uptake by plants from soil.
Agronomy Research, 8(1): 807–814.
Liu C, Huang P M, 2003. Kinetics of lead adsorption by iron
oxides formed under the influence of citrate. Geochimica et
Cosmochimica Acta, 67(5): 1045–1054.
Lu D D, Cao Q L, Cao X J, Luo F, 2009. Removal of Pb(II) using
the modified lawny grass: Mechanism, kinetics, equilibrium
and thermodynamic studies. Journal of Hazardous Materi-
als B, 166(1): 239–247.
Mackay A A, Seremet D E, 2008. Probe compounds to quan-
tify cation exchange and complexation interactions of
ciprofloxacin with soils. Environmental Science & Technol-
ogy, 42(22): 8270–8276.
Martins A F, Vasconcelos T G, Hariques D M, Frank C S, König
A, Kümmerer K, 2008. Concentration of ciprofloxacin in
Brazilian hospital effluent and preliminary risk assessment:
a case study. Clean-Soil, Air, Water, 36(3): 264–269.
Moreno-Castilla C, López-Ramón M V, Carrasco-Marı́n F, 2000.
Changes in surface chemistry of activated carbons by wet
oxidation. Carbon, 38(14): 1995–2001.
Nadeem M, Mahmood A, Shahid S A, Shah S S, Khalid A M,
McKay G, 2006. Sorption of lead from aqueous solution
by chemically modified carbon adsorbents. Journal of Haz-
ardous Materials B, 138(3): 604–613.
Nikitin N I, 1966. The Chemistry of Cellulose and Wood,
Translated from Russian by Schmorak J. Israel Program for
Scientific Translation, Jerusalem.
Parker S P, 1997. McGraw-Hill Encyclopedia of Science &
Technology (8th ed.). McGraw-Hill, London. vol. 7, 161.
Punyapalakul P, Sitthisorn T, 2010. Removal of ciprofloxazin
Vol. 24
and carbamazepine by adsorption on functionalized meso-
porous silicates. World Academy of Science, Engineering
and Technology, 69: 546–550.
Sun S P, Guo H Q, Ke Q, Sun J H, Shi S H, Zhang M L et al.,
2009. Degradation of antibiotic ciprofloxacin hydrochloride
by photo-fenton oxidation process. Environmental Engi-
neering Science, 26(4): 753–759.
Uslu H, Inci I, 2009. Adsorption equilibria of L-(+)-tartaric acid
onto alumina. Journal of Chemical & Engineering Data,
54(7): 1997–2001.
van der Mass J H, 1969. Basic Infrared Spectroscopy. Heyden &
Son Ltd., London.
Wang C J, Li Z H, Jiang W T, 2011. Adsorption of ciprofloxacin
on 2:1 dioctahedral clay minerals. Applied Clay Science,
53(4): 723–728.
Wang C J, Li Z H, Jiang W T, Jean J S, Chuan C C, 2010. Cation
exchange interaction between antibiotic ciprofloxacin and
montmorillonite. Journal of Hazardous Materials B, 183(1-
3): 309–314.
Weber W J Jr, Morris J C, 1963. Kinetics of adsorption on
carbon from solutions. Journal of the Sanitary Engineering
Division ASCE, 89(2): 31–60.
Wu Q F, Li Z H, Hong H L, Yin K, Tie L Y, 2010. Adsorption and
intercalation of ciprofloxacin on montmorillonite. Applied
Clay Science, 50(2): 204–211.
Youssef A M, El-Khouly A A, Ahmed A I, El-Shafey E I, 1995.
Changes in the adsorption properties of activated carbon
due to partial oxidation of the surface. Adsorption Science
& Technology, 12: 211–219.
Zawadzki J, 1980. IR spectroscopic investigations of the mech-
anism of oxidation of carbonaceous films with HNO3
solution. Carbon, 18(4): 281–285.
Zhang C L, Qiao G L, Zhao F, Wang Y, 2011. Thermodynamic
and kinetic parameters of ciprofloxacin adsorption onto
modified coal fly ash from aqueous solution. Journal of
Molecular Liquids, 163(1): 53–56.
Zhang H C, Huang C H, 2007. Adsorption and oxidation of
fluoroquinolone antibacterial agents and structurally related
amines with goethite. Chemosphere, 66(8): 1502–1512.