Ecotoxicology and Environmental Safety 138 (2017) 139–145

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Ecotoxicology and Environmental Safety

journal homepage: www.elsevier.com/locate/ecoenv

Adsorption of ciprofloxacin and norfloxacin from aqueous solution onto MARK

granular activated carbon in fixed bed column
⁎
Teeba M. Darweesh, Muthanna J. Ahmed
Department of Chemical Engineering, University of Baghdad, Baghdad, Iraq

A R T I C L E I N F O A B S T R A C T

Keywords: Carbonization of Phoenix dactylifera L stones followed by microwave K2CO3 activation was adopted for
Activated carbon preparation of granular activated carbon (KAC). High yield and favorable pore characteristics in terms of
Potassium carbonate surface area and pore volume were reported for KAC as follows: 44%, 852 m2/g, and 0.671 cm3/g, respectively.
Biomass The application of KAC as adsorbent for attraction of ciprofloxacin (CIP) and norfloxacin (NOR) was investigated
Adsorption
using fixed bed systems. The effect of flow rate (0.5–1.5 ml/min), bed height (15–25 cm), and initial drug
Antibiotics
concentration (75–225 mg/l) on the behavior of breakthrough curves was explained. The fixed bed analysis
showed the better correlation of breakthrough data by both Thomas and Yoon-Nelson models. Inlet drug
concentration was of greatest effect on breakthrough data compared to other fixed bed variables. Experimental
and calculated breakthrough data were obtained for CIP and NOR adsorption on KAC, thus being important for
design of fixed bed column.

1. Introduction
Pharmaceutical compounds have been recognized as a hazardous
class of organic pollutants due to their extensive use and long term
effects towards aquatic environment (Ashfaq et al., 2016). Antibiotics
constitute a group of pharmaceuticals that is widely used to treat
several infectious diseases in both human and animals (Moussavi et al.,
2013). About 30–90% of the given antibiotic dose can remain un-
degradable in the human or animal body, and is largely excreted as an
active compound (Pouretedal and Sadegh, 2014). Ciprofloxacin and
norfloxacin antibiotics are belonging to the Fluoroquinolones (FQs)
family. These antibiotics are heavily used in medical and veterinary
practice (Van Doorslaer et al., 2014). The presence of FQs residues in
effluents from households, hospitals, and pharmaceutical industries is a
major cause of acute and chronic toxicity, as well as the emergence of
resistant bacteria (Prutthiwanasan et al., 2016). Consequently, removal
of FQs residues from the environment is a crucial issue.
Many techniques have been used for treatment of FQs-rich effluents
such as electrochemical oxidation (Zhu et al., 2016), biodegradation
(Cˇvancˇarová et al., 2015), photodegradation (Sturini et al., 2015),
catalytic degradation (Feng et al., 2016), micro-extraction
(Ebrahimpour et al., 2012), oxidation (catalytic degradation) (Guo
et al., 2016), and adsorption (Ferreira et al., 2016). Of these processes,
it has been demonstrated that adsorption is a simple, effective, and
economical method to remove low concentration FQ pollutants from
waters (Tan et al., 2013). Adsorption is the widely used method for
removal of a broad range of FQs pollutants due to its simple design,
easy operation, and relatively simple regeneration. It has been detected
that activated carbon is the efficient adsorbent for removal of FQs as
compared to zeolite (Maraschi et al., 2014), clay (Sturini et al., 2016),
silica (Liang et al., 2016), and carbon nanotube (Yu et al., 2016),
because of its large surface area, micro-porous nature, and high
adsorption capacity (Ahmed and Theydan, 2014).
Adsorption of FQs represented by ciprofloxacin and norfloxacin on
activated carbons has been explained in many studies using batch
operation (Sun et al., 2016, 2014; Wang et al., 2015; Peng et al., 2015;
Liu et al., 2011, 2013; Yu et al., 2016). However, fixed bed adsorption
of these FQs compounds on activated carbons has not been addressed
by researchers. The data obtained during batch adsorption is not
sufficient to provide accurate scale-up data required in the design of
adsorption columns. Therefore, adsorption of many pharmaceutical
groups like cephalosporin (Nazari et al., 2016), quinolones (Patiño
et al., 2016; Sotelo et al., 2013), non-steroidal anti-inflammatory
(Álvarez-Torrellas et al., 2016; Katsigiannis et al., 2015; Torrellas
et al., 2015; Sotelo et al., 2014, 2012a; Dubey et al., 2014), tetra-
cyclines (Álvarez-Torrellas et al., 2016), β-lactam (Yaghmaeian et al.,
2014; Burkerta et al., 2011), sulfonamide (Zuo et al., 2016), analgesic
drug (García-Mateos et al., 2015), and β-blocker (Sancho et al., 2012;
Sotelo et al., 2012b, 2012c) has been studied by column adsorption
systems, in which breakthrough curves are determined, and that is

⁎
Corresponding author.
E-mail address: muthanna.ja@gmail.com (M.J. Ahmed).

http://dx.doi.org/10.1016/j.ecoenv.2016.12.032
Received 8 November 2016; Received in revised form 16 December 2016; Accepted 27 December 2016
0147-6513/ © 2016 Elsevier Inc. All rights reserved.
T.M. Darweesh, M.J. Ahmed
useful for determination of the operating life span of the fixed
adsorbent bed.
The present study is the first case where sorptive removal of FQs in
terms of ciprofloxacin and norfloxacin has been investigated at various
operational conditions in fixed bed column reactor using date stones
derived active carbon as an adsorbent. Date stones have been utilized as
precursors due to their renewability, availability and favorable ligno-
cellulosic composition including 42% cellulose, 18% hemicellulose, and
11% lignin (Ahmed and Theydan, 2012). Moreover, several adsorption
models, such as the Bohart–Adams model, the Thomas model, and the
Yoon–Nelson model have been applied for analysis of experimental
breakthrough curve data with the aid of nonlinear regression analyses
in order to get the suitable model with least error for measuring the
adsorptive capacity of the adsorbent.
2. Materials and methods
2.1. Materials
Date stones (DS) were isolated from date fruits, frequently washed
with tap water, and then dried in an oven at 110 °C for 24 h. After
crushing and sieving, a fraction of 1–2 mm particle size was utilized as a
precursor for preparation of activated carbon. Potassium carbonate
(Didactic Company, Espuma) of purity 99.9% was used as an activator.
Ciprofloxacin (Nanjing Huaxin Biopharm. Company Ltd. China) and
norfloxacin (Ajanta pharma limited company, India) with purities of
99.9% were used as adsorbates where Table 1 shows their character-
istics.
2.2. Preparation and characterization of KAC
Carbonization of dried DS sample to a solid char followed by its
K2CO3 chemical activation was adopted as a preparation technique for
KAC. Char was prepared by pyrolysis of 20 g dried DS sample using a
stainless steel reactor of 3 cm diameter and 15 cm length. The reactor
was designed to contain a removable upper cover with 1 mm concentric
hole for escaping of pyrolysis gases. The reactor was placed in a furnace
operated at 500 °C with a constant heating rate of 10 °C/min for 1 h
activation time. Then the char product was withdrawn and allowed to
Table 1
Characteristics and structure of ciprofloxacin and norfloxacin.
Compound Structure Formula
Ciprofloxacin C17H18FN3O3
Norfloxacin C16H18FN3O3
a
Solubility at the pH range from 7 to 5.
140
Ecotoxicology and Environmental Safety 138 (2017) 139–145
cool.
Char (2 g) was well mixed with 10 ml K2CO3 solution at 0.8 g/g
impregnation ratio for 24 h at room temperature. The impregnated
sample was dried at 110 °C in an oven (Model IH-100, England) and
then stored in a desiccator for the next treatment. The dried sample was
activated with the aid of a modified microwave oven (MM717CPJ,
China) by using a quartz glass reactor, described else-where (Ahmed
and Theydan, 2013). After activation step at 540 W radiation power
and 8 min radiation time, the activated sample was withdrawn from
microwave oven and allowed to cool. The sample was leached with
0.1 M HCl solution for 24 h at room temperature in order to remove the
residual of K2CO3 activator. Then the samples was filtered and
repeatedly washed with distilled water to remove alkalis and organic
matters, until the pH of filtrate reached 6.5–7. The product sample
(KAC) was dried at 110 °C for 24 h. The yield of activated carbon was
determined as follow:
WC
Yield (%) = x100
WS (1)
where Wc and Ws are the weights of activated carbon and dried date
stones, respectively.
The surface area, total pore volume and average pore diameter of
KAC were evaluated. Surface area was determined by the application of
BET equation to the adsorption–desorption isotherm of N2 at 77 K.
Total pore volume was evaluated by converting the adsorption volume
of N2 at relative pressure of 0.95 to equivalent liquid volume of
adsorbate. Structures of KAC and DS samples were also examined by
scanning electron microscopy SEM (VEGA3 TESCAN) and Fourier
transforms infrared spectroscopy FTIR (ABB MB3000).
2.3. Fixed bed adsorption
The breakthrough curves for adsorption of CIP and NOR on KAC in
terms of effluent to influent concentrations ratio, C/Co, versus contact
time were investigated by carrying out a set of fixed bed experiments at
a constant temperature of 30 °C. Granular KAC with a given amount
was placed in a glass column of 30 cm length and 1.0 cm internal
diameter. The upper and lower parts of column contained plastic pellets
to compact the bed and avoid dead volume and channeling. KAC was
packed on a plastic sieve placed at the bottom of column. CIP or NOR
Weight (g mol−1) Solubilitya (mg/l) γmax (nm) Ref.
331.35 150–6190 270 Li et al. (2015);
Wu et al. (2010)
319.33 400–161000 273 Yang et al. (2012)
T.M. Darweesh, M.J. Ahmed Ecotoxicology and Environmental Safety 138 (2017) 139–145

solution, at required concentration, was added to a glass beaker and

pumped into the column by a dozing pump (Watson Marlow) at desired
volumetric flow rate. The effluent samples were collected at different
time intervals until the saturation state occurred where C/Co reached
unity or the concentration remains constant along the time. The
concentration of CIP or NOR in effluent stream was calculated
continually using UV–Visible Spectrophotometer at maximum wave-
lengths of 274 and 272 nm for CIP and NOR, respectively. By using
0.1 M NaOH or HCl solutions, CIP and NOR solutions were adjusted to
constant pH values of 9 and 5, respectively, being chosen according to
high adsorption of both antibiotics on KAC at these conditions. The
tested operational adsorption parameters were volumetric flow rate,
mass of adsorbent (length of the bed), and inlet antibiotic concentra-
tion.
For analysis of experimental breakthrough curves, three common
models represented by Thomas (Thomas, 1944), Adams-Bohart (Bohart
and Adams, 1920), and Yoon-Nelson (Yoon and Nelson, 1984) were
applied as follows:
C 1
Thomas model =
Co 1 + exp (kT qo M / Q − kT Co t ) (2)
C
Adams−Bohart model Co
= exp (kA Co t −kA No H /u ) (3)

C exp (kT t − kT τ )
Yoon−Nelson model =
Co 1 + exp (kT t − kT τ ) (4)
Where kT (l/min.mg) is the Thomas rate constant, qo (mg/g) is the
adsorption capacity, M (mg) is the amount of adsorbent in the column,
Q (ml/min) is the volumetric flow rate, kA (l/min.mg) is the Adams-
Bohart constant, No (mg/l) is the saturation concentration, H (cm) is the
bed height of the column, u (cm/min) is the superficial velocity, kY
Fig. 1. SEM images of (a) DS and (b) KAC.
(min−1) is Yoon-Nelson rate constant, and τ (min) is the time required
for 50% adsorbate breakthrough.
directly affects the porous characteristics of ACs, and their performance
The correlation of these models for breakthrough curve data was
for specific industrial applications. Similar trends were observed by
validated by sum squares error (SSE) and correlation coefficient (R2) as
Deng et al. (2010) for preparation of ACs from cotton stalks by
follows:
microwave assisted KOH and K2CO3 activations. The percentages of
n
micropores area were reported as 72.6% and 38.10% for AC-KOH and
SSE = ∑ (qe, exp−qe , cal )2
i =1 (5) AC-K2CO3, respectively. The results could be related to the fact that the
volume of K2CO3 molecule is twice that of KOH molecule, leading to
n
∑i =1 (qe, exp−qe , cal )2 deep interaction between KOH and raw cotton stalk.
R 2 = 1− n n
∑i =1 (qe , exp)2 −[(∑i =1 qe, exp) / n]
2 The SEM image of raw DS and KAC are viewed in Fig. 1. It can be
(6)
found that the surface of raw precursor is dense, rough, non-planar, and
Where, n is the number of data points, qexp and qcal (mg/g) are the there are agglomerations on it (Fig. 1a). On the other hand, the
experimental and calculated adsorption capacities, respectively. microwave activation verified a well improvement and uniform surface,
and making a pore structure with thin boundary (Fig. 1b). The surface
3. Results and discussions of KAC has some cavities that liberated from the evaporation of the
impregnated K2CO3, leaving the space previously occupied by reagent.
3.1. Characterization of DS and KAC The cavities gave channels for the molecules of the adsorbate to pass
through the micropores and mesopores of carbon particle (Saucier
High yield of 44% was calculated from Eq. (1) for KAC prepared by et al., 2015).
carbonization of date stones followed by K2CO3 chemical activation.
Foo and Hameed (2012) also observed the favorable property of K2CO3 3.2. Continuous adsorption kinetics
in producing AC with high yield compared to other acidic and basic
activators. The most important characteristics of adsorbents are the 3.2.1. Effect of volumetric flow rate
surface area, total pore volume, and average pore diameter. The surface The behaviors of breakthrough curves for CIP and NOR adsorption
area, pore volume, and average pore diameter of KAC are 852 m2/g, onto KAC at volumetric flow rates of 0.5, 1.0, and 1.5 ml/min are
0.671 cm3/g, and 3.150 nm, respectively. High surface area adsorbent investigated at inlet drug concentration of 150 mg/l, solution tempera-
in terms of KAC has been obtained from raw DS with surface area of ture of 30 °C, and bed length of 25 cm (Fig. 2a and b). It can be
214.46 m2/g. The average pore diameter of 3.150 nm indicates that observed that at volumetric flow rates of 0.5 and 1.5 ml/min, the
prepared KAC is in the mesopores region according to the IUPAC breakthrough times at C/Cₒ=0.05 are reported as 37 and 32 min, and
classification. The mesoporosity of AC is a favorable structural property 23 and 20 min for CIP and NOR, respectively. This can be related to low
for utilization which involves large molecules. Foo and Hameed (2011) interaction between adsorbates and adsorbent at high flow rates which
obtained AC from date stones by microwave KOH activation with accelerates breakthrough and saturation (Han et al., 2009). Also, the
surface area, pore volume, and average pore diameter of 856 m2/g, early breakthrough of NOR compared to CIP is due to relatively low
0.468 cm3/g, and 2.182 nm, respectively. The structure of AC was near adsorption of weak NOR adsorbate with respect to strong CIP. For both
from micropores region, this can be related to activator type which adsorbates, at high volumetric flow rate, the breakthrough curve is

141
T.M. Darweesh, M.J. Ahmed
Fig. 2. CIP breakthrough curves at various (a) flow rate (b) bed height (c) inlet
concentration.
shifted toward the origin and become steeper and rapidly reached
saturation. Fig. 2a also shows that at time of 35 min the values of C/Co
for CIP at 0.5 ml/min is six times lower than its value at 1.5 ml/min. As
the flow rate drops, the adsorbate has sufficient time to diffuse through
pores and produces a higher adsorption capacity. Also, high flow rate
reduces the thickness of liquid film around adsorbent particles leading
to low mass transfer resistance and high rate of mass transfer (Liao
et al., 2013). The same observations were reported by Nazari et al.
(2016) for aqueous phase adsorption of cephalexin on AC from walnut
shells by ZnCl2 chemical activation.
3.2.2. Effect of bed height
The breakthrough curves of CIP and NOR adsorption on KAC at
different bed lengths (15–25 cm) and constant conditions of 150 mg/l
inlet concentration, 30 °C solution temperature, and 1.5 ml/min flow
rate are presented in Figs. 2b and 3b. The data shows that, as the bed
height raises, the required time for achieving breakthrough point
increases and breakthrough curves are shifted away from the origin.
Furthermore, for short fixed-bed the effluent to influent concentration
ratio (C/Co) increases more rapidly than for a long bed. For example,
for bed heights of 15 and 25 cm the breakthrough concentration C/
Co=0.05 for CIP are achieved at contact times of 17 and 22 min,
respectively. On the other hand, at contact time of 35 min the values of
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Ecotoxicology and Environmental Safety 138 (2017) 139–145
Fig. 3. NOR breakthrough curves at various (a) flow rate (b) bed height (c) inlet
concentration.
C/Co are 0.42 and 0.24 at bed highest of 15 and 25 cm, respectively.
The increase in bed height means utilization of more adsorbent weight
which leads to an enhancement in the adsorption sites and an increase
in required contact time to achieve complete saturation (Baral et al.,
2009). Furthermore, the adsorbate has enough time to diffuse over
pores of adsorbent and consequently the total adsorbed amount and
removal efficiency of CIP antibiotic increase with increasing of bed
height (Reynel-Avila et al., 2015). However, the ratio of CIP molecules
to the available adsorption sites is low, and therefore, the amount
adsorbed per unit mass of adsorbent or adsorption capacity is decreases
(Chen et al., 2012). The above observations for effect of bed height or
adsorbent weight on breakthrough curves were also obtained by Dong
et al. (2016) for fixed-bed adsorption of levofloxacin on graphene
oxide.
3.2.3. Effect of initial concentration
The influence of inlet drug concentration (75–250 mg/l) on the
breakthrough curves is shown in Figs. 2c and 3c at adsorption
conditions of solution temperature of 30 °C, length of bed of 25 cm,
and flow rate of 1.5 ml/min. The results show that at higher inlet
concentration, the breakthrough curves are shifted towards the origin.
This behavior may be related to enhancement of driving force for mass
transfer across the liquid film along with acceleration of adsorption rate
T.M. Darweesh, M.J. Ahmed Ecotoxicology and Environmental Safety 138 (2017) 139–145

Table 2
Conditions and parameters of breakthrough curve models for CIP-KAC system.

Conditions Thomas Adams-Bohart Yoon-Nelson

Co Q H qo kT 104 SSE R2 kA 104 No SSE R2 kY τ SSE R2

150 0.5 25 2.094 4.58 0.095 0.941 2.06 358.8 0.252 0.844 0.0618 65.31 0.095 0.941
150 1.0 25 1.677 4.60 0.091 0.953 1.74 697.2 0.327 0.829 0.0619 57.13 0.091 0.953
150 1.5 25 1.328 4.36 0.098 0.949 1.51 1037 0.369 0.809 0.0654 51.57 0.098 0.949
150 1.5 15 1.587 4.65 0.125 0.939 1.23 1675 0.511 0.750 0.0697 41.58 0.125 0.939
150 1.5 20 1.482 4.45 0.131 0.935 1.33 1279 0.469 0.767 0.0667 45.64 0.131 0.935
150 1.5 25 1.328 4.36 0.098 0.949 1.51 1038 0.369 0.809 0.0654 51.57 0.098 0.949
75 1.5 25 0.856 8.87 0.106 0.932 4.11 544.9 0.253 0.836 0.0645 66.55 0.106 0.932
150 1.5 25 1.328 4.36 0.098 0.949 1.51 1038 0.369 0.809 0.0654 51.57 0.098 0.949
225 1.5 25 1.514 3.69 0.037 0.984 0.85 1423 0.475 0.797 0.0832 39.11 0.037 0.984

Co (mg/l), Q (ml/min), H (cm), qo (mg/g), kT (l/min.mg), kA (l/min.mg), No (mg/l), kY (min−1), τ (min).

Table 3
Conditions and parameters of breakthrough curve models for NOR-KAC system.

Conditions Thomas Adams-Bohart Yoon-Nelson

Co Q H qo kT 104 SSE R2 kA 104 No SSE R2 kY τ SSE R2

150 0.5 25 1.992 4.62 0.082 0.951 2.02 1073 0.243 0.854 0.0634 64.19 0.082 0.951
150 1.0 25 1.589 4.64 0.081 0.958 1.69 1043 0.328 0.832 0.0638 55.52 0.081 0.958
150 1.5 25 1.271 4.45 0.090 0.954 1.46 1025 0.385 0.806 0.0667 49.41 0.090 0.954
150 1.5 15 1.526 4.67 0.092 0.955 1.19 1648 0.474 0.767 0.0701 39.45 0.092 0.955
150 1.5 20 1.419 4.65 0.102 0.951 1.30 1258 0.464 0.775 0.0697 43.63 0.102 0.951
150 1.5 25 1.271 4.45 0.090 0.954 1.46 1025 0.385 0.806 0.0667 49.41 0.090 0.954
75 1.5 25 0.813 8.47 0.104 0.936 3.75 542.1 0.272 0.832 0.0635 63.19 0.104 0.936
150 1.5 25 1.271 4.45 0.090 0.954 1.46 1025 0.385 0.806 0.0667 49.41 0.090 0.954
225 1.5 25 1.447 3.93 0.029 0.988 0.83 1405 0.509 0.790 0.0884 37.45 0.029 0.988

Co (mg/l), Q (ml/min), H (cm), qo (mg/g), kT (l/min.mg), kA (l/min.mg), No (mg/l), kY (min−1), τ (min).

which leads to an early saturation of the fixed-bed (Gupta and Babu,

2009). For example for inlet NOR concentration of 75, 150, and
225 mg/l, the values of C/Co at contact time of 35 min are reported
as 0.06, 0.15, and 0.27, respectively. These results for inlet concentra-
tion effect on breakthrough curves are in agreement with those
proposed by Sotelo et al. (2013) for fixed-bed adsorption of flumequine
antibiotic on commercial AC. It can be deduced that the fixed bed
adsorption conditions affect C/Co ratio for both drugs according to the
order: inlet concentration > volumetric flow rate > fixed-bed height.

3.3. Modeling of breakthrough curves

Successful design and operation of a fixed-bed column system

requires the prediction of the breakthrough curve for the effluent
(Jang and Lee, 2016). Therefore, the experimental breakthrough data
for CIP and NOR adsorption on KAC are analyzed using the, Thomas,
Adams–Bohart, and Yoon–Nelson models to determine the dynamic
behaviors in the fixed-bed column. The analysis results with constants
of three models, Eqs. (2)–(3), are obtained by a non-linear regression
using Statistica 10 program with the aid of Guasi-Newton method
(Tables 2, 3). The results show that Adams-Bohart kinetic model is of
low R2 values (0.750–0.84) for CIP and (0.767–0.854) for NOR.
Moreover, high deviation between the experimental and calculated
C/Co can be seen from the values of SSE (0.252–0.511) and (0.243–
0.509). This reflects poor Adams-Bohart correlation for experimental
data. On the other hand, better correlations for breakthrough data are
obtained by both Thomas and Yoon-Nelson models with high R2
(0.932–0.984) and (0.936–0.988), and low SSE (0.037–0.131) and Fig. 4. Experimental and predicted breakthrough curves for CIP and NOR.
(0.029–0.104) for CIP and NOR at studied fixed-bed conditions. The
best fitting by Thomas and Yoon–Nelson models confirm the Langmuir by these models is presented in Fig. 4 at conditions of 225 mg/l inlet
type isotherm, second-order kinetics, and that the rate of decrease in concentration, 1.5 ml/min flow rate, and 25 cm bed height. The
adsorption is proportional to the breakthrough for CIP or NOR decrease in adsorption capacities of both drugs with increasing flow
adsorption on KAC (Katsigiannis et al., 2015; Mondal et al., 2016). rate and bed height, and its increasing with inlet concentration can be
The well prediction of breakthrough data for CIP and NOR adsorption confirmed from the reported values of qo (mg/g) for Thomas model.

143
T.M. Darweesh, M.J. Ahmed Ecotoxicology and Environmental Safety 138 (2017) 139–145

Table 4
Comparison of Thomas model parameters for adsorption of antibiotics on ACs.

Antibiotic Conditions Parameters Error analysis Ref.

Co Q H qo kT

Ciprofloxacin 150 0.5 25 2.094 45.8×10−5 R2=0.941 This study

Norfloxacin 150 0.5 25 1.992 46.2×10−5 R2=0.951 This study
Flumequine 3 3 6 373.4 30.0×10−6 SE=21.98 Sotelo et al. (2013)
Amoxicillin 50 1 14 510.7 21.7×10−7 R2=0.951 Yaghmaeian et al. (2014)
Atenolol 10 2 10 187.4 55.0×10−6 R2=0.986 Sotelo et al. (2012b)
Ibuprofen 20 3 3 48.57 17.9×10−5 R2=0.991 Dubey et al. (2014)
Naproxen 20 3 3 47.67 21.6×10−5 R2=0.995 Dubey et al. (2014)
Clofibric acid 20 3 3 46.53 23.3×10−5 R2=0.992 Dubey et al. (2014)
Nalidixic acid 80 1 1 1654 60.0×10−6 R2=0.920 Patiño et al. (2016)
Ranitidine 200 2 3 10.86 16.0×10−8 R2=0.985 Mondal et al. (2016)

Co (mg/l), Q (ml/min), H (cm), qo (mg/g), kT (l/min.mg), R2 correlation coefficient, SE standard error.

High adsorption capacities were observed for CIP compared to NOR
(Tables 2, 3) which may be attributed to higher water solubility and
lower molecular weight (Table 1) of NOR relative to CIP (Sotelo et al.,
2014). Also, the decrease in breakthrough time with flow rate and inlet
concentration, and its increasing with bed height can be deduced from
the values of parameter τ for Yoon-Nelson model. The favorable
enhancement of adsorption rate or breakthrough rate with the increase
of flow rate and inlet concentration, and their reduction with the
increase of bed height can be observed from the values of rate constant
kY for Yoon-Nelson models. The successful application of Thomas and
Yoon-Nelson models was also reported for analysis of breakthrough
curves of pharmaceutical pollutants on carbonaceous adsorbents
(Nazari et al., 2016; Mondal et al., 2016). The parameters of Thomas
model for ciprofloxacin and norfloxacin on KAC have been compared
with those of other drugs on ACs as summarized in Table 4. It can be
observed that the adsorption of both adsorbates on prepared KAC has
the highest breakthrough rate constants, kT, compared to adsorption of
other antibiotics. The high rate constant besides the high adsorbent
weight or bed length leads to low adsorption of both FQs where
adsorbed amount is inversely related to rate constant and column
height.
4. Conclusions
Adsorption technology has been effectively used for removal of
ciprofloxacin and norfloxacin antibiotics from aqueous solution.
Mesoporous activated carbon from date stones by microwave K2CO3
activation was used as eco-friendly adsorbent with surface area of
852 m2/g and average pore diameter of 3.150 nm. The adsorption
behavior of both drugs on prepared carbon was illustrated using
continuous or fixed-bed system. It was shown that high volumetric
flow rate and inlet concentration and low bed height accelerated
breakthrough of adsorbates. The initial concentration of antibiotic
was of significant effect on adsorption performance compared to flow
rate and bed height. The analysis results for experimental breakthrough
data confirmed the better application of both Thomas and Yoon-Nelson
models compared to Adams-Bohart model. Accordingly, this study
provided useful informations for design of fixed bed column for
ciprofloxacin or norfloxacin-activated carbon system.
Acknowledgement
The authors are grateful to Baghdad University and chemical
engineering department for assist and support of this work.
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