Science of the Total Environment 662 (2019) 324–331

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Science of the Total Environment

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

Highly efficient removal of ceftiofur sodium using a superior hydroxyl

group functionalized ionic liquid-modified polymer
Meng Cheng a,b, Xiaodi Zhang a, Yueyue Shi a, Dongyang Shi a, Guifen Zhu a,⁎, Jing Fan a,⁎
a
School of Environment, Henan Key Laboratory for Environmental Pollution Control, Key Laboratory for Yellow River and Huai River Water Environment and Pollution Control, Ministry of Edu-
cation, Henan Normal University, Xinxiang, Henan 453007, PR China
b
School of Environmental and Municipal Engineering, North China University of Water Resources and Electric Power, Zhengzhou, Henan 450046, PR China

H I G H L I G H T S G R A P H I C A L A B S T R A C T

• A superior hydroxyl-functionalized
ionic liquid based polymer adsorbent
was designed.
• The adsorbent exhibited an ultrahigh
adsorption capacity of 1260.5 mg/g for
CFS.
• High removal efficiencies in a wide CFS
concentrations range
(0.005–1000 mg/L) were observed.
• Adsorption performance for CFS was far
beyond several commercially available
adsorbents.
• The adsorbent possessed strong anti-
interference capability and excellent
recyclability.

a r t i c l e i n f o a b s t r a c t

Article history: The occurrence of cephalosporin antibiotics in water resources has caused increasing concerns about their poten-
Received 18 November 2018 tial effects on ecosystem and human health. However, reports on the efficient removal of these antibiotics are
Received in revised form 20 January 2019 limited. In this work, a superior hydroxyl-functionalized ionic liquid based polymer (PS-[Hemim][Cl]) was pre-
Accepted 21 January 2019
pared for highly efficient removal of ceftiofur sodium (CFS) antibiotic from aqueous solutions, and the effect of
Available online 21 January 2019
various factors on the adsorption was investigated. It was found that the PS-[Hemim][Cl] exhibited a super-
Editor: Shuzhen Zhang high adsorption capacity of 1260.5 mg/g for CFS within 60 min and kept high removal efficiency in a wide
range of antibiotic concentrations from 5 ppb level to 1000 mg/L. Even the concentration of common inorganic
Keywords: ions was 1000 times higher than that of CFS, the adsorption efficiency remained above 93%. At the same time,
Functionalized ionic liquid the PS-[Hemim][Cl] showed excellent adsorption performance for the antibiotics with similar structure to CFS.
Polymer support Compared with commercially available adsorbents, the adsorption capacity of PS-[Hemim][Cl] for CFS was
Efficient adsorption 4–468 times higher under the same experimental conditions. The application of PS-[Hemim][Cl] to real wastewa-
Ceftiofur sodium ter containing different concentrations of CFS was investigated and promising results were reported. Addition-
Cephalosporin antibiotics
ally, preliminary mechanism studies suggested that electrostatic attraction, hydrogen bond and ion exchange
synergistically contributed to the highly efficient adsorption of CFS.
© 2019 Elsevier B.V. All rights reserved.

1. Introduction

⁎ Corresponding authors. Nowadays, antibiotics are becoming irreplaceable in treating various

E-mail addresses: gfzhu617@163.com (G. Zhu), fanjing@htu.cn (J. Fan). diseases for human and veterinary (Drawz and Bonomo, 2010; Yu et al.,

https://doi.org/10.1016/j.scitotenv.2019.01.223
0048-9697/© 2019 Elsevier B.V. All rights reserved.
 M. Cheng et al. / Science of the Total Environment 662 (2019) 324–331
2017), but they cannot be completely metabolized by organisms, nor ef-
fectively removed from municipal wastewater treatment (Ren et al.,
2018; C. Zhang et al., 2016). The continuous introduction of antibiotics
into the environment may bring about severe eco-toxicological effects.
For example, they may induce bacteria to generate drug resistance,
resulting in incapability of them to treat conventional diseases
even at trace concentrations (Bondarczuk and Piotrowska-Seget,
2019; Laxminarayan, 2014; Shan et al., 2018). Cephalosporins is
one of the most used antibiotics in the world, and has been fre-
quently detected in aquatic environment in many countries at the
concentrations from 0.30 ng/L to 0.03 mg/L due to its increasing
usage and consumption (Östman et al., 2019; Álvarez-Torrellas
et al., 2017; Y. Xiao et al., 2017; Hsu et al., 2018; Ribeiro et al.,
2018; Yu et al., 2016). In the family of cephalosporins, ceftiofur so-
dium (CFS) is the third-generation veterinary cephalosporin, and is
frequently discharged from animal farms and becomes a major per-
sistent organic pollutant (Pugazhenthiran et al., 2017).
Many studies have been devoted to the removal of antibiotics, but
very few have focused on CFS. Methods developed for the removal of
cephalosporins include membrane separation (Shi et al., 2012), ad-
vanced oxidation processes (Serna-Galvis et al., 2017), photocatalytic
degradation (Pugazhenthiran et al., 2014; Xiao et al., 2018), and adsorp-
tion (Ahmed and Theydan, 2012). Among these methods, membrane
fouling is still a problem that needs to be resolved, while oxidation
and degradation processes aim at degradation of cephalosporins and
thus the antibiotics cannot be recovered from effluent. Therefore, ad-
sorption is superior to the other techniques in the separation of cepha-
losporins from water with the advantages of cost-effective, high
efficiency, facile operation, design simplicity and little harmful second-
ary products (Tian et al., 2016; X. Xiao et al., 2017; X. Li et al., 2018; J.
Li et al., 2018). Adsorbents such as polymeric resins (Racovita et al.,
2016), activated carbons (Nazari et al., 2016), zeolite (Samarghandi
et al., 2015) and carbon nanotubes (Fakhri et al., 2016) have been re-
ported for the removal of cephalosporins. However, the performance
of these adsorbents seems to be unsatisfactory because most of them ex-
hibit low adsorption capacity for cephalosporins (16.1–211.78 mg/g)
and regeneration is not investigated in these studies. Therefore, the de-
sign and fabrication of more efficient, sustainable and economically at-
tractive adsorbents are still a challenge (Gu et al., 2018).
Ionic liquids (ILs) have attracted great attention due to their inter-
esting properties such as good thermal stability, excellent solvation for
many compounds and highly tunable structure (Cho et al., 2018; Dai
et al., 2017). Recently, functionalized ILs containing hydroxyl (\\OH)
and carboxyl group (\\COOH) have received much attention because
introduction of \\OH and \\COOH groups have positive effect on the
formation of hydrogen bonds with target compounds compared to the
traditional ILs (Zhang et al., 2014). However, the disadvantages such
as high cost and big difficulty to regenerate the ILs hinder their
large scale application. Then, supported ILs materials have become
an active area of research since they may offer the benefits of ILs in
solid supports. Nevertheless, no studies have been reported for the
removal of cephalosporin antibiotics from wastewater using sup-
ported ILs.
In this work, a resin supported hydroxyl group functionalized ILs ad-
sorbent PS-[Hemim][Cl] was designed and synthesized by chemical re-
action of chloromethyl polystyrene resin with 1-(2-hydroxyethyl)
imidazole. This novel adsorbent was then attempted to remove CFS
from water. Being different from the frequently used porous supports,
chloromethyl polystyrene resin has negligible adsorption toward CFS,
which would fully embody the performance of the ILs. It was found
that the PS-[Hemim][Cl] exhibited super high adsorption capacity,
quick removal rate, well environmental adaptability and excellent re-
generation ability in the removal process of CFS. In comparison with
several commercially available adsorbents, the adsorption performance
of PS-[Hemim][Cl] for CFS was much remarkable both at high and low
CFS concentrations. This study opens a new avenue for the application
325
of supported functionalized ILs in the remediation of waters contami-
nated by sodium salt of cephalosporin.
2. Experimental
2.1. Chemicals
Chloromethyl polystyrene resin (PS-CH2Cl, 4.5 mmol of Cl/g,
100–200 mesh) was obtained from Tianjin Nankai Hecheng Sci. &
Tech. Co. Ltd. (China). Prior to synthesis, PS-CH2Cl was sieved to obtain
the particles with size of 160–180 mesh. 1-(2-Hydroxyethyl) imidazole
was purchased from Shanghai Darui Fine Chemicals Co. Ltd. (China).
Ceftiofur sodium (CFS) obtained from Macklin (China) was employed
as a target organic pollutant. N-methyl-2-pyrrolidone and hydrochloric
acid were purchased from Tianjin De'en Chemical Reagents Co. Ltd.
(China) and Zhengzhou Paini Chemical Reagent Factory (China), re-
spectively. Commercially available adsorbents such as silica gel, artificial
zeolite, weak base anion exchange resin, activated aluminium oxide and
activated carbon were supplied by J&K Chem. Ltd. (Beijing, China) and
sieved to obtain the particles with size of 160–180 mesh before use.
All the other chemicals were of reagent grade and used as received.
2.2. Synthesis of polymer supported hydroxyl-functionalized ionic liquids
As shown in Scheme S1, the PS-[Hemim][Cl] was prepared by a one-
step procedure. 1 g of PS-CH2Cl was added into a round-bottom flask
containing 20 mL of N-methyl pyrrolidone, and the polymer was swell-
ing for 12 h. Next, 2.52 g of 1-(2-hydroxyethyl) imidazole was added,
and the mixture was stirred at 85 °C for 12 h and centrifuged after
cooling. Then, the obtained solid product was washed thoroughly with
deionized water and ethanol separately and dried under reduced pres-
sure for 24 h at 45 °C.
2.3. Characterization and analysis
Fourier transform infrared spectrum (FT-IR) measurements were
performed by using a Spectrum 400 F infrared spectrophotometer
(Perkin-Elmer, USA) in KBr pellet at room temperature. Thermogravi-
metric analysis (TGA) curves were obtained using a STA449C Gerätebau
thermogravimetric analyzer (NETZSCH, Germany) under nitrogen at-
mosphere. Size and morphology of the samples were observed by
field-emission scanning electron microscopy (FE-SEM) using a SU8010
microscope (Hitch, Japan). A TU-1810 ultraviolet-visible spectropho-
tometer (Persee, China) was used to determine the concentrations of
CFS left in the supernatants at the maximum wavelength of 292 nm.
2.4. Adsorption experiments
The adsorption behavior of CFS was investigated by using batch
technique in a thermostatic shaker bath. In doing so, 10 mL different
concentrations of CFS solution and 10 mg of the adsorbent were
added to a series of conical flasks. After adjusting the pH by a small
amount of HCl (1 mol/L) or NaOH (0.5 mol/L), the mixtures were
shaken at desired temperature for a certain time. Then the concentra-
tions of residual CFS in the supernatants were determined. All the ex-
periments were performed at natural pH (except the studies of the pH
effects).
The adsorption capacity and removal percentage of PS-[Hemim][Cl]
for CFS was calculated by Eqs. (1) and (2):
ðC 0 −C e ÞV
qe ¼ ð1Þ
m
C 0 −C e
R% ¼  100% ð2Þ
C0
326 M. Cheng et al. / Science of the Total Environment 662 (2019) 324–331
where qe represents the equilibrium adsorption capacity (mg/g), C0 and
Ce are the concentration of CFS in the aqueous phase before adsorption
and after equilibrium adsorption (mg/L), respectively. m is the mass of
PS-[Hemim][Cl] (mg), V is the volume of CFS solution (mL), and R (%)
stands for the removal efficiency. All the adsorption data were deter-
mined in triplicate.
3. Results and discussion
3.1. Characterization
FT-IR spectra of PS-CH2Cl and PS-[Hemim][Cl] were displayed in
Fig. 1A, it can be seen that the peaks at 671 cm−1 (C\\Cl stretching vi-
bration) and 1264 cm−1 (CH2\\Cl bending vibration) for PS-[Hemim]
[Cl] disappeared, while three new peaks emerged at 1070 cm−1
(C\\OH stretching vibration) (Wang et al., 2018), 1160 cm−1 (C\\N
stretching frequency) (Lin et al., 2014) and 1560 cm−1 (C_N stretching
vibration of the imidazolium ring) (Wang et al., 2012), which indicates
that the 1-(2-hydroxyethyl) imidazole was grafted onto the surface of
PS-CH2Cl successfully by C\\N bond formation. In comparison with
physical immobilization, chemical grafting could effectively improve
the stability of the ILs on the support, and avoid their loss.
To evaluate the thermal stability of the newly synthesized PS-
[Hemim][Cl], PS-CH2Cl and PS-[Hemim][Cl] were studied by thermal
gravimetric analysis (TGA) under the protection of N2. As illustrated in
Fig. 1B, the PS-CH2Cl exhibited high thermal stability without any no-
ticeable degradation up to 320 °C, and decomposed rapidly in the
range of 320–530 °C with a 73.8% loss. For the PS-[Hemim][Cl], a rapid
Fig. 1. (A) FT-IR spectra of (a) PS-CH2Cl and (b) PS-[Hemim][Cl]; (B) TGA curves of (a) PS-CH2Cl and (b) PS-[Hemim][Cl]; (C) FE-SEM images of (a) PS-CH2Cl and (b) PS-[Hemim][Cl].
and continuous decomposition was observed in the range of
270–480 °C with a 66.5% loss, and the slight weight loss in the
range of 100–200 °C might be attributed to the water evaporation
due to the hydrophilic nature of [Hemim][Cl] (Lin et al., 2014).
From the mass loss of PS-CH 2 Cl and PS-[Hemim][Cl], the grafting
content of the IL on the resin was calculated to be 0.88 mmol/g.
Field emission scanning electron microscopy (FE-SEM) was per-
formed to characterize the size and morphology of PS-CH2Cl and PS-
[Hemim][Cl]. The typical FE-SEM images of PS-CH2Cl before and after
grafting 1-(2-hydroxyethyl) imidazole were presented in Fig. 1C. It
was apparent that these materials were uniformly spherical in shape
with the diameter of approximately 100 μm. This result indicated that
the grafting of imidazole ring onto the resin surface did not destroy
the structure and morphology of the resin.
3.2. Effect of initial pH and temperature
pH is one of the most significant factors for adsorption because it
may have a great impact on the interaction between adsorbent and
CFS. Thus, the effect of pH on the adsorption of CFS was investigated
in the range from 1 to 12. As shown in Fig. 2, the removal efficiency
was only 13.8% at the initial pH 1, and it increased sharply with the in-
crease of initial pH from 1 to 3, then reached a plateau value and main-
tained the same level with a further increase of pH. This result might be
rationalized from the fact that under neutral conditions, CFS existed as a
negatively charged CF− in aqueous solution, which would form electro-
static attraction with the positively charged imidazole cations on the PS-
[Hemim][Cl]. At extremely low pH value, CFS would be protonated, and
 M. Cheng et al. / Science of the Total Environment 662 (2019) 324–331 327

Table 1
Kinetic parameters for the adsorption of CFS by PS-[Hemim][Cl].

C0 (mg/L) Pseudo-first-order model Pseudo-second-order model

k1 (min−1) qe (mg/g) R2 k2 (g/(mg·min)) qe (mg/g) R2

10 0.1580 7.56 0.993 0.0589 10.13 0.999

20 0.1733 13.53 0.945 0.0316 20.34 0.999
50 0.1997 46.75 0.991 0.0108 50.81 0.999

described by pseudo-second-order model. Moreover, the qe values

estimated by pseudo-second-order kinetic model were found to be
more close to the experimental data.

3.4. Adsorption isotherms

The adsorption isotherms express the equilibrium distribution of

CFS between the solutions and PS-[Hemim][Cl]. As shown in Fig. 3,
with the increase of concentrations, the adsorption capacity of CFS
Fig. 2. Effect of initial pH on the adsorption of CFS by PS-[Hemim][Cl]. Conditions: CCFS = first increased significantly then tended to level off gradually until ad-
20 mg/L, T = 25 °C and t = 30 min. sorption was saturated with the maximum adsorption capacity of
1260.5 mg/g. This tendency suggested that before the adsorption sites
were saturated, the driving force to overcome the mass transfer resis-
the dominant CFS species was CFH+, which could not be adsorbed effi-
tance of CFS from aqueous solution to PS-[Hemim][Cl] increased with
ciently onto the surface of the adsorbent due to its electrostatic repul-
increasing concentration gradient of solid-liquid interface (Wu et al.,
sion with the positively charged imidazole cations. With increasing
2014). In particular, the adsorbent exhibited surprisingly high removal
pH, the protonation of CFS became weak, hydrogen bond and electro-
efficiency in a wide initial concentration range of CFS. For example,
static attraction between CFS and the adsorbent were enhanced, so
the removal efficiency of CFS was higher than 97% even if its initial con-
the removal efficiency was increased. When the initial pH increased
centration was as high as 1000 mg/L, indicating that PS-[Hemim][Cl]
from 3 to 11, the removal efficiency showed little changes, which indi-
was an excellent adsorbent for the removal of CFS from aqueous
cated that the adsorbent had a widely used pH range and well environ-
solutions.
mental adaptability. However, when the initial pH N11, the gradually
In order to investigate how the CFS interacted with the adsorbent at
increased OH− would compete with CF− for the adsorbing sites on
equilibrium state, three theoretical models: Langmuir model (Eq. (5)),
the adsorbent, so that the removal efficiency decreased slightly.
Freundlich model (Eq. (6)) and Tempkin model (Eq. (7)) were used to
The removal efficiency of CFS by PS-[Hemim][Cl] was evaluated at
correlate the adsorption isotherm (Zheng et al., 2019).
various temperatures (5–50 °C). The results depicted in Fig. S1 revealed
that the change of removal efficiency was not significant in the temper-
ature range investigated. This characteristic suggested that PS-[Hemim] Ce Ce 1
¼ þ ð5Þ
[Cl] could be very attractive in real application because temperature qe qm qm K L
tended to fluctuate frequently in such cases.
where qe is the amount of CFS adsorbed by the absorbent at equilibrium
3.3. Effect of contact time and the adsorption kinetics (mg/g), qm is the theoretical monolayer capacity (mg/g), Ce describes
the equilibrium concentration of CFS (mg/L), and KL is the Langmuir
Fig. S2 showed the adsorption kinetic curves of PS-[Hemim][Cl] to-
ward CFS at different initial concentrations. It can be seen that the ad-
sorption equilibrium time increased with increasing CFS concentration.
At the initial stage, rich active sites were available on PS-[Hemim][Cl],
the adsorption rate and capacity of CFS rapidly increased. When the ac-
tive sites were gradually occupied, the adsorption rate became slow and
the equilibrium could be reached within 30 min.
To understand the adsorption kinetics, pseudo-first order model
(Eq. (3)) and pseudo-second order model (Eq. (4)) were applied.

ln ðqe −qt Þ ¼ lnqe −k1 t ð3Þ

t 1 t
¼ þ ð4Þ
qt k 2 qe 2 qe

where qt and qe are the amount of CFS adsorbed by PS-[Hemim][Cl]

(mg/g) at time t and equilibrium condition. k1 and k2 are the rate con-
stants of first-order adsorption (min−1) and pseudo-second-order
adsorption (g/(mg·min)), respectively. Table 1 summarized these
parameters for each model obtained from experimental data analysis
together with the related correlation coefficients. In comparison
with the pseudo-first-order model, the pseudo-second-order model
provided higher correlation coefficient, which suggested that the ad- Fig. 3. Adsorption isotherm and removal efficiency of CFS by PS-[Hemim][Cl]. Conditions:
sorption kinetic process of CFS by PS-[Hemim][Cl] could be better T = 25 °C, t = 60 min and pH = 5.8.
328 M. Cheng et al. / Science of the Total Environment 662 (2019) 324–331
adsorption constant (L/mg), which is related to the affinity of binding
sites and the adsorption energy.
1 their potentially adverse effects, the ability of PS-[Hemim][Cl] in the re-
ln qe ¼ ln K F þ lnC e
n moval of low concentration CFS was evaluated. For this purpose, a series
where KF and n are Freundlich constant related to the maximum ad-
sorption capacity and the adsorption intensity, respectively.
qe ¼ K T ln C e þ K T ln f
In this equation, KT and f (L/mg) are Tempkin constant (reflecting
the adsorption heat) and the maximum combine energy, respectively.
Table 2 presented fitting results of the experimental adsorption iso-
therms. It is clear that Langmuir model (R2 = 0.999) gave the better fit
to the equilibrium data than Freundlich model (R2 = 0.854) and
Tempkin model (R2 = 0.948), revealing the monolayer coverage of
CFS on the homogeneous adsorbent surface. Based on the Langmuir
model, the maximum adsorption capacity of CFS was 1253.26 mg/g,
which was slightly lower than the experimental value (1260.5 mg/g).
The dimensionless parameter KL (0.078) fell within the range of 0–1,
confirming the favorable adsorption nature of PS-[Hemim][Cl] for CFS.
Since Tempkin model is based on electrostatic attraction between posi-
tive and negative charges, the higher correlation coefficient (R2 =
0.948) demonstrated that there might be a stronger interaction be-
tween CFS and PS-[Hemim][Cl] (Liang et al., 2018; Ma et al., 2008).
3.5. Thermodynamic analysis
Although the effect of temperature on adsorption data was small, the
adsorption isotherms of CFS onto PS-[Hemim][Cl] at 298, 308 and 318 K
were used to derive Langmuir equilibrium constants at each tempera-
ture. Then, thermodynamic parameters including standard Gibbs free
energy (ΔG0), standard enthalpy (ΔH0) and standard entropy (ΔS0),
were calculated by Eqs. (8) and (9):
ΔG0 ¼ −RTlnKL
lnKL ¼ −ΔH0 =RT þ ΔS0 =R
where R and T are the ideal gas constant (8.314 J/(mol·K)) and thermo-
dynamic temperature (K), KL represents Langmuir equilibrium constant
(L/mol). ΔH0 and ΔS0 were calculated from the linear plots of lnKL ver-
sus 1 / T, and the results were shown in Table S1.
As shown in Table S1, the negative ΔG0 values revealed the favorable
adsorption of ceftiofur sodium by the IL functionalized polymer (Yao
et al., 2016). Generally, the values of ΔG0 in the range from 0 to
−20 kJ/mol and from −80 to −400 kJ/mol refer to physical and chem-
ical adsorptions, respectively. Therefore, both physisorption and chem-
isorption might be involved in the adsorption of CFS onto PS-[Hemim]
[Cl] investigated in the present work (with ΔG0 values of −26 to
−27 kJ/mol). The negative ΔH0 value indicated the adsorption of CFS
onto PS-[Hemim][Cl] was an exothermal process, which was in agree-
ment with the result of temperature effect. The positive ΔS0 could be ra-
tionalized from the fact that dehydration of ceftiofur sodium resulted in
the large entropy increase in their transfer process from water to the ad-
sorbent (Wu et al., 2014).
Table 2
The adsorption isotherm parameters for CFS adsorption by PS-[Hemim][Cl].
Langmuir model Freundlich model Tempkin model
KL (L/mg) qm (mg/g) R2 KF n R2 KT (L/mg) f R2
0.078 1253.26 0.999 102.46 2.78 0.854 135.22 5.19
3.6. Adsorption of CFS at ppb level and enrichment factor
Considering the low concentration of antibiotics in real waters and
ð6Þ
of samples with different concentrations of CFS (0.005–0.1 mg/L) and
PS-[Hemim][Cl] (0.01–0.2 mg/L) were examined by batch experiments.
The CFS adsorbed on the adsorbent was then desorbed with 2 mL of
5 mol/L HCl, and its content was determined to obtain the percent re-
ð7Þ covery of CFS. As shown in Table S2, 93.15% of CFS could be effectively
removed from water even if its concentration was as low as 5 μg/L
(ppb), as a result, the enrichment factor was as high as 465.8. Therefore,
the adsorbent is promising for the removal of CFS at ppb level from
aqueous solution.
3.7. The effect of inorganic ions
Inorganic ions widely exist in wastewaters and natural water, which
may affect the CFS adsorption. Therefore, the CFS removal efficiency by
PS-[Hemim][Cl] was studied in the presence of 100–100,000 ppm
(10–10,000 times) of typical ions with an initial CFS concentration of
10 ppm, and the results were shown in Fig. 4. It was found that the ad-
sorption efficiency of CFS was related to the valence and interference
ratio of the ions. Under the condition of equal interference ratio, mon-
atomic ions had much less effect than polyvalent ions. The adsorption
efficiency of CFS remained almost at the same level even if the concen-
tration of Na+, K+ and Cl− was 10,000 times higher than that of CFS. On
the other hand, the presence of divalent and trivalent ions, such as Ca2+,
Mg2+, SO42− and PO43−, showed very limited influence on the adsorption
of CFS when their concentrations were within 1000 times that of CFS,
but the removal efficiency decreased by about 13–15% when their con-
centrations were 10,000 times higher than that of CFS. These results
demonstrated the strong anti-interference capability of PS-[Hemim]
[Cl] in the adsorption of CFS, and suggested that PS-[Hemim][Cl] was
an excellent adsorbent for the removal of CFS from high salinity
wastewater.
ð8Þ
3.8. The adsorption of other antibiotics
ð9Þ To extend the adsorption application of the adsorbent developed in
this work, adsorption efficiencies of the PS-[Hemim][Cl] for nine differ-
ent antibiotics (their molecular formulas and structures were shown in
Table S3) were investigated under the same experimental conditions,
the results were shown in Fig. 5. As can be seen, the adsorption
Fig. 4. Effect of co-existing ions on the removal of CFS by PS-[Hemim][Cl]. Conditions: T =
0.948
25 °C, CCFS = 10 mg/L, pH = 5.8.
 M. Cheng et al. / Science of the Total Environment 662 (2019) 324–331 329

water and deionized water. When the initial concentration of CFS was
increased to 1000 mg/L, the removal efficiency could still reach up to
about 97%, and the adsorption capacity was 968.03 and 970.17 mg/g, re-
spectively. However, the adsorption capacity of CFS in tap water, river
water and sewage effluent was slightly lower than that in deionized
water and snow water.
The possible reason is that some organic matters possessing similar
structure with CFS in the snow water was less than that in tap water,
river water and sewage effluent, which would likely compete with CFS
for the adsorption sites on PS-[Hemim][Cl]. Even so, the removal effi-
ciency in four real water samples was still above 95% at low CFS concen-
trations, and was all above 85% with the adsorption capacity exceeding
850 mg/g when the initial CFS concentration was as high as 1000 mg/L.
The results indicated the great potential of PS-[Hemim][Cl] in the re-
moval of CFS from various water sources.

3.10. Adsorption mechanism

Fig. 5. Comparison of removal efficiency of different antibiotics by PS-[Hemim][Cl].
Conditions: T = 25 °C, C0 = 10 mg/L, pH = 5.8.
efficiencies decreased in the order: ceftriaxone sodium (CTX) ≈
ceftiofur sodium (CFS) N cephalexin (CPX) ≥ cefradine (CFD) N amoxicil-
lin (AMX) ≫ sulfanilamide (SAD) ≥ ciprofloxacin (CIP) N metronidazole
(MET) ≥ 2-mercapto-1-methylimidazole (MMI). This result might be at-
tributed to structure and existence forms of these antibiotics in aqueous
solution. At natural pH, CFS and CTX existed mainly in anionic form,
which was beneficial for the adsorption due to their electrostatic attrac-
tion with imidazole cations on the PS-[Hemim][Cl]. SAD and CIP were
mainly in their molecular or cationic form (Liang et al., 2018), and
MET and MMI had similar imidazole ring with PS-[Hemim][Cl], which
negatively affected their adsorption. Since CPX, CFD and AMX have sim-
ilar structure with CFS, a portion of the functional groups on their
surface remained in molecular form, which did not favor for the adsorp-
tion, thus their removal efficiencies were slightly lower than that of CFS
and CTX. These results demonstrated the excellent adsorption perfor-
mance of PS-[Hemim][Cl] for CFS and other antibiotics with similar
structures.
3.9. Application to real samples
To verify the potential application of PS-[Hemim][Cl] in real water
samples subjected to CFS contamination, snow water, tap water, river
water and sewage effluent were used as the matrices of the adsorption
solution. It was found that CFS was not detected in snow water collected
from our campus, tap water from our laboratory, river water from
Weihe River (Xinxiang, China), and sewage effluents from a municipal
sewage treatment plant (Xinxiang, China). Thus, different amounts of
CFS were, respectively, added into the above water samples to form dif-
ferent concentrations CFS solutions. Then 10 mL of each solution with
10 mg of PS-[Hemim][Cl] was shaken at 25 °C for 40 min, and the Re-
moval efficiency was reported in Table 3. It was observed that there
was little difference between the adsorption capacity of CFS in snow
Table 3
Removal efficiency of CFS by PS-[Hemim][Cl] from real water samples.
Sample CInitial CFS = 10 CInitial CFS = 100 CInitial CFS = 1000
mg/L mg/L mg/L
To understand the adsorption mechanism of antibiotics is helpful to
determine their environmental fates and develop wastewater treat-
ment technologies. As discussed in the effect of initial pH and Tempkin
model, electrostatic attraction between the CFS anions and imidazole
cations on the PS-[Hemim][Cl] was considered to be one of the promi-
nent driving forces for the adsorption of CFS on PS-[Hemim][Cl]. Hydro-
gen bond was also reported in the adsorption of antibiotics by adsorbent
with oxygen-containing functional groups such as \\OH and \\COOH
(Peiris et al., 2017; X. Zhang et al., 2016). To verify these points, FT-IR
spectra of PS-[Hemim][Cl] before and after adsorption of CFS were in-
vestigated, and the results were shown in Fig. S3.
It was clearly noted that after the adsorption of CFS by PS-[Hemim]
[Cl], the adsorption peak of PS-[Hemim][Cl] at 1560 cm−1 (C_N
stretching vibration) became weak and the peak of CFS at 1758 cm−1
corresponding to C_O for \\COONa (Zhao et al., 2015) moved to
1766 cm−1, indicating that positively charged C_N+ in the adsorbent
and the negatively charged \\COO− in the surface of the ionized CFS
were involved in the adsorption process due to their electrostatic attrac-
tion (Wu et al., 2014).
It was also found that the adsorption peak of PS-[Hemim][Cl] at
1070 cm−1 (C\\OH stretching vibration) (Wang et al., 2012) became
weak, while the adsorption peaks of CFS at 1029 cm−1 (C\\O\\C
stretching vibration) (Li et al., 2017), 1355 cm−1 (N\\H amide III
band) (Zhao et al., 2015), 1525 cm−1 (\\NH2 bending vibration)
(Unal et al., 2010) and 1600 cm−1 (C_O stretching vibration of ketone
group) (Goyne et al., 2005; Guo et al., 2017; Zhao et al., 2015) shifted to
1032 cm−1, 1349 cm−1, 1513 cm−1 and 1603 cm−1, respectively. These
changes indicated that the \\OH functional groups of PS-[Hemim][Cl]
may form hydrogen bonds with C_O,\\NH and\\NH2 groups in CFS.
In addition, we speculate that there may exist ion exchange between
Cl− of PS-[Hemim][Cl] and ionized CFS. To confirm this, 10 mg of PS-
[Hemim][Cl] was added into 2 mL deionized water (containing one
drop of 0.5 mol/L AgNO3), and no AgCl precipitate was observed in the so-
lution (Fig. S4A). However, when 1 mL of 1000 mg/L CFS was added in the
above solution, AgCl precipitate was immediately found (Fig. S4B), which
suggested the existence of ion exchange between Cl− of PS-[Hemim][Cl]
and the ionized CFS. Therefore, electrostatic attraction, hydrogen bonding
and ion exchange were synergistically responsible for the excellent ad-
sorption performance of PS-[Hemim][Cl] for CFS. The possible interac-
tions between PS-[Hemim][Cl] and CFS were schematically illustrated
in Fig. S5.

R (%) qe (mg/g) R (%) qe (mg/g) R (%) qe (mg/g) 3.11. Comparison with other commercially available adsorbents
Deionized water 100 10 99.50 99.50 97.02 970.17
Snow water 100 10 99.56 99.56 96.80 968.03 The comparison of the adsorption performance of PS-[Hemim][Cl]
Tap water 99.04 9.90 96.86 96.86 89.31 893.09 for CFS with commercially available adsorbents was listed in Table 4.
River water 97.13 9.71 95.24 95.24 87.56 875.59 It can be clearly seen that under the same conditions, the adsorbent de-
Sewage effluent 95.93 9.59 94.28 94.28 85.34 853.56
veloped in this work was much superior to several commercially
330 M. Cheng et al. / Science of the Total Environment 662 (2019) 324–331
Table 4
The comparison for the adsorption of CFS using different adsorbents (adsorbent, 1 g/L;
contact time, 40 min; temperature, 25 °C).
Adsorbent CInitial CFS = 5 mg/L CInitial CFS = 1000
mg/L
Removal qe Removal
(%) (mg/g) (%)
Silica gel 1.03 0.05 0.21
Artificial zeolite 5.06 0.25 2.30
Weak-base anion exchange 23.71 1.19 13.18
resin
Activated aluminium oxide 1.03 0.05 2.50
Activated carbon 1.23 0.06 1.72
PS-[Hemim][Cl] 100 5.00 97.02
available adsorbents such as silica gel, artificial zeolite, weak-base anion
exchange resin, activated aluminium oxide and activated carbon in the
removal of CFS (both at high and low concentrations), the adsorption
capacity of PS-[Hemim][Cl] was about 4–468 times higher than that of
these commercial adsorbents. Such a comparison suggests that PS-
[Hemim][Cl] may be an effective adsorbent for CFS removal.
To further reveal the advantages of PS-[Hemim][Cl], a comparison of
adsorption capacity for different cephalosporins with that of other ad-
sorbents available in literatures was given in Table S4. It can be seen
that PS-[Hemim][Cl] developed in this work was much superior to
other adsorbents both in the adsorption capacity and equilibrium
time. These results strongly indicate that PS-[Hemim][Cl] is promising
for the removal of CFS from contaminated water.
3.12. Reusability
Regeneration is an important property for evaluating the economical
applicability of an adsorbent (Zhao et al., 2018). On the basis of
systematical study on pH effect, acidic condition was found to be propi-
tious to desorption. Then, through a series of optimization experiments,
5 mol/L HCl was selected for the desorption experiments. During the re-
generation process of PS-[Hemim][Cl], most of CFS could be removed
from the adsorbent by using 2 mL of aqueous HCl with the aid of a vor-
tex mixing for 20 min. The adsorption-desorption experiments were
conducted five times and the results were presented in Fig. S6. It can
be seen that the regenerated adsorbent still retained a high adsorption
capacity after five cycles, and the small decrease of the adsorption ca-
pacity might be due to an irreversible occupation of partial adsorption
sites. Nonetheless, the adsorption capacity of 883.65 mg/g for CFS in
the fifth cycle was still much higher than that of other previously re-
ported adsorbents. These results indicate that PS-[Hemim][Cl] has
good stability and reusability, and it is an excellent candidate for the re-
moval of CFS from water.
4. Conclusion
In this work, we developed a polymer supported hydroxyl-
functionalized ionic liquid adsorbent (PS-[Hemim][Cl]) to remove CFS
from water. It was found that PS-[Hemim][Cl] exhibited an remarkably
high maximum adsorption capacity of 1260.5 mg/g for CFS, in particu-
lar, the adsorbent still had a high removal efficiency (97.2%) even at
both high CFS concentration (1000 mg/L) and trace CFS level (5 ppb).
Moreover, the PS-[Hemim][Cl] had a well environmental adaptability
and anti-interference ability since pH (3−12), temperature (5–50 °C)
and co-existing ions (such as 1000 times Ca2+, Mg2+, SO42− and
PO43−) had little influence on the removal of CFS. Thus, this adsorbent
had been successfully applied to remove CFS in environmental water
samples. Compared with commercially available adsorbents and those
reported in literature, the adsorption capacity of PS-[Hemim][Cl] was
4–468 times higher. The adsorbent also had good stability and
recyclability. Hence, the PS-[Hemim][Cl] would be a promising adsor-
bent for the removal of CFS and other antibiotics with similar structures.
Acknowledgements
qe This work was supported financially from the National Natural Sci-
(mg/g) ence Foundation of China (No. 21777038, No. U1704251).
2.07
22.76 Appendix A. Supplementary data
131.81
25.00 Supplementary data to this article can be found online at https://doi.
17.21 org/10.1016/j.scitotenv.2019.01.223.
970.17
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