Chemosphere 180 (2017) 373e378

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Chemosphere
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Adsorption of diclofenac onto goethite: Adsorption kinetics and effects

of pH
Yue Zhao a, Fei Liu a, *, Xiaopeng Qin b
a
School of Water Resources and Environment, and Beijing Key Laboratory of Water Resources and Environmental Engineering, China University of
Geosciences (Beijing), Beijing 100083, PR China
b
State Key Laboratory of Environmental Criteria and Risk Assessment, and Soil Pollution Effect and Environmental Criteria, Chinese Research Academy of
Environmental Sciences, Beijing 100012, PR China

h i g h l i g h t s

The increasing pH decreased the adsorption of diclofenac (DCF) to goethite.

DCF adsorption to goethite was well fitted with Pseudo-second-order model.

The carboxyl group (eCOOH) might be involved in the adsorption.

DCF and goethite formed bidentate chelate and bridging bidentate complexes.

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

Article history: The adsorption of diclofenac (DCF), one of the widely used non-steroidal anti-inflammatory drugs, onto
Received 7 July 2016 the surface of goethite was investigated with batch experiments. The adsorption at different pH values
Received in revised form (5.3, 7.4, and 10.0) were well fitted with the pseudo-second-order model. The results showed that the
18 January 2017
adsorption of DCF onto goethite was strongly depended on solution pH. The amount of adsorbed DCF
Accepted 2 April 2017
Available online 3 April 2017
decreased with increasing pH duo to electrostatic repulsive interactions. Fourier transform infrared
(FTIR) results indicated that carboxyl group (eCOOH) might be involved in the adsorption, and DCF
Handling Editor: Min Jang formed bidentate chelate and bridging bidentate complexes on the surface of goethite.
© 2017 Elsevier Ltd. All rights reserved.
Keywords:
Adsorption
Goethite
Diclofenac
pH
FTIR
Surface complexation

1. Introduction
Diclofenac (2-[(2,6-dichlorophenyl) amino] phenyl acetic acid,
DCF), a common non-steroidal anti-inflammatory, is always used
for the treatment of painful and inflammatory conditions for hu-
man and animals. The global consumption of DCF is estimated on
an annual basis to be about 940 tons (Zhang et al., 2008). DCF has
been detected in groundwaters and surface waters in different
areas, such as Germany (Ternes, 1998), Pakistan (Scheurell et al.,
2009), Spain (Lopez-Serna et al., 2013), Europe (Loos et al., 2010),
* Corresponding author.
E-mail address: feiliu@cugb.edu.cn (F. Liu).
China (Wang et al., 2010; Zhao et al., 2010), and the concentrations
of DCF detected range from not detected to 4400 ng L1 (Ternes,
1998; Heberer, 2002; Scheurell et al., 2009; Loos et al., 2010;
Wang et al., 2010; Zhao et al., 2010; Lopez-Serna et al., 2013). It is
also one of the few pharmaceutical and personal care products
(PPCPs) which could be detected in the drinking water (Vulliet and
Cren-Olive, 2011). The presence of DCF and its metabolites in
environment has adverse effects on organisms (Oaks et al., 2004;
Schmitt-Jansen et al., 2007).
Adsorption of PPCPs to soils/sediments is a major process
affecting their mobility and ultimate fate in the environment
(Scheytt et al., 2004; Yu and Bi, 2015). Previous studies showed that
DCF was retarded (Retardation factor ¼ 2.0) in the soil column

http://dx.doi.org/10.1016/j.chemosphere.2017.04.007
0045-6535/© 2017 Elsevier Ltd. All rights reserved.
374 Y. Zhao et al. / Chemosphere 180 (2017) 373e378
(medium grained sand, 95.3%), whereas no significant degradation
was observed under the prevailing conditions (Scheytt et al., 2004).
Soil organic matter (SOM) was a key factor controlling the migra-
tion of DCF in two soils (Revitt et al., 2014), and adsorption of DCF to
sediments was also evidently affected by the content of SOM (foc) of
soils and sediments (Chefetz et al., 2008; Revitt et al., 2014; Styszko,
2015).
In fact, the interactions between PPCPs and soils/minerals were
very complex and included several mechanisms, such as cation
bridging (Wu et al., 2012), cation exchange (Wang et al., 2011),
hydrogen bonding (Paul et al., 2014) and surface complexation
(Paul et al., 2014). Iron (hydr)oxides are important minerals in
soils/sediments (Schwertmann and Latham, 1986; Schwertmann,
1988), which might influence the adsorption of DCF to soils/sed-
iments. Goethite is an abundant and important hydrous iron oxide
in soils, which is usually used as a model adsorbent to investigated
the adsorption of PPCPs to iron-rich soil minerals (Lin et al., 2012;
Zhao et al., 2011). However, the study on adsorption of DCF onto
goethite was scarcely reported. In this study, the effects of reac-
tion time and pH on the adsorption of DCF onto goethite were
investigated.
2. Materials and methods
2.1. Materials
Goethite (chemical reagent grade) was obtained from Sigma-
Aldrich (USA) and confirmed by X-ray diffraction (D8 ADVANCE,
Bruker, Germany) measurement. The specific surface area of
goethite was 18.3 m2 g1, which was determined using the BET
method (Micrometer, ASAP2020, USA). The intrinsic surface
deprotonation constants (pKa1 and pKa2) of goethite were
respectively 5.69 and 8.12 (Mamindy-Pajany et al., 2011), and the
point of zero charge (PZC) of goethite was 6.9 (Mamindy-Pajany
et al., 2011).
The target compound diclofenac sodium salt (>98%) was pur-
chased from Sigma-Aldrich (USA). The chemical formula of diclo-
fenac sodium is C14H10Cl2NNaO2, and the molecular weight is
318.14. The protonation constant (pKa) is 4.15 (Torrellas et al., 2015).
At pH < 4.15, uncharged molecules were formed, and they were
anionic by the deprotonation of carboxyl functional groups with
the increasing pH. Methanol (HPLC grade) was purchased from
Honeywell Burdick & Jackson (USA). All chemicals were purchased
in analytical purity or higher and used without any further purifi-
cation. All solutions were prepared using ultrapure water (MILLI-Q,
USA).
2.2. Batch experiment
Stock solution of DCF (100 mg L1) was prepared by dissolving
appropriate amount of diclofenac sodium salt in ultrapure water,
and stored at 4  C in the dark. The required DCF concentration was
obtained by dilution of the stock solution.
Experiments at different pH (5.3, 7.4, and 10.0) were conducted
at different reaction time. 0.4 g of goethite was weighed into 40 mL
amber sampler vial, and 20 mL DCF solution (1 mg L1, I ¼ 0.01 M
NaCl) was added. The pH of suspensions was adjusted by adding
0.01 M HCl or 0.01 M NaOH. The samples were mixed in a reciprocal
shaker at 175 rpm and 25  C in the dark, and were taken after
shaking for 5 min, 10 min, 20 min, 45 min, 67 min, 130 min,
240 min, 480 min, 720 min, 1440 min, and 2880 min. Then the
samples were centrifuged at 3000 rpm for 15 min. The superna-
tants (1 mL) were taken for analyzing the concentration of DCF. The
final pH of each sample was measured using a pH meter (Sartorius
PB-10, Germany).
The amounts of DCF adsorbed on goethite at time t were
calculated by the following equation:
VðC0  Ct Þ
qt ¼ (1)
M
where qt (mg g1) is the DCF concentration in soil-phase at time t; C0
(mg L1) and Ct (mg L1) are the DCF concentrations in aqueous-
phase at initial time and time t; V (L) is the volume of aqueous-
phase; M (g) is the mass of goethite.
In order to investigate the adsorption process, kinetic experi-
ment data were analyzed by the pseudo-first-order kinetic model
and pseudo-second-order kinetic model, respectively, which were
shown as follows:
Pseudo first-order kinetic model (Ho and McKay, 1998):
 
qt ¼ qe 1  ek1 t (2)
Pseudo second-order kinetic model (Ho, 2006):
k2 q2e t
qt ¼ (3)
1 þ k2 qe t
where t (min) is the reaction time, k1 (min1) and k2 (g mg1 min1)
represent the adsorption rate constants; qe and qt (mg g1) are the
adsorbed amount of DCF by goethite at equilibrium and time t
(min), respectively.
Adsorption edges were also obtained from batch experiments.
The initial concentrations of DCF were 250, 500, 1000, 1500, and
2000 mg L1. The final concentration of goethite was 20 g L1, and
the background electrolyte was 0.01 M NaCl. Acid or base (0.01 M
HCl or 0.01 M NaOH) was drop-wise added to adjust solution pH in
the range of 5e11. The experiments were conducted similarly as
detailed above, except that samples were conducted in the equi-
librium time of 24 h. All experiments were conducted in triplicates.
Meanwhile, blank samples (samples containing goethite but
without DCF) and control samples (only containing DCF) were also
carried out.
2.3. Chemical analysis
The concentration of DCF in solution was determined using a
high performance liquid chromatography (HPLC) (LC-20AT, Shi-
madzu) with an Inertsil® ODS-SP column (4.6 mm  250 mm, 5 mm
particle size). The mobile phase consisted of 75% methanol and 25%
phosphate (0.025 M, pH 2.5). The flow rate is 1 mL min1. 10 mL of
sample was injected using an auto-sampling device, with the
detection wavelength set to 277 nm. The column temperature was
kept at 35  C. No significant interferences were found from blank
and control samples.
2.4. Spectroscopic analysis
Samples for FTIR analysis were taken from three batch experi-
ments, the initial DCF concentration was 2000 mg L1, and the final
solution pH were 5.27, 7.13 and 9.21, respectively. At equilibrium
time, solids were separated by centrifugation and dried at 45  C for
48 h. Then the samples were diluted with KBr powder (sample:
KBr z 1:50) and pressed pellets for testing. The infrared spectra of
samples were recorded by a FTIR spectrometer (FTIR-650, Gang-
dong, Tianjin), operating in the wavenumber range of
400e4000 cm1 with a resolution of 4 cm1. Sixteen scans were
collected and averaged for each sample and background to get the
spectrum.
 Y. Zhao et al. / Chemosphere 180 (2017) 373e378
3. Results and discussion
3.1. Adsorption kinetics
The adsorption kinetics of DCF on goethite were shown in Fig. 1.
Different behaviors were observed at different pH conditions. At pH
5.26, DCF was aggregated quickly onto the goethite surface. Similar
phenomenon during the adsorption process of PPCPs (i.e. tetracy-
cline and sulfamethazine) on goethite was also reported (Zhao
et al., 2011; Guo et al., 2013). The sorption of DCF on goethite
reached the apparent equilibrium at 480 min. The amount of
adsorbed DCF was 23.53 mg g1 at 5 min, and then reached a con-
stant level of 25.47 mg g1. The adsorption process at pH 9.96 was
quite different from that at pH 5.26. At pH 9.96, the adsorption of
DCF on goethite obtained apparent equilibrium in 1440 min and the
adsorbed amount was 1.59 mg g1, which was much lower than that
at pH 5.26.
When solution pH increased, the amount of DCF adsorbed to
goethite decreased significantly (Fig. 1). In the pH range (pH 5e10)
of this study, DCF was anionic (pH > pKa). The surface of goethite
was positive at pH < PZC of goethite (6.9), and was negative at
pH > PZC. At pH 5.26, more DCF was adsorbed due to the electro-
static attraction between the negative charged DCF molecules and
the positive charged goethite. At pH > 6.9, adsorption of DCF to
goethite decreased with the increasing pH, because of the elec-
trostatic repulsion between DCF molecules and the surface of
goethite.
At pH 7.40, the equilibrium adsorbed amount of DCF was
9.33 mg g1. As shown in Fig. 1, the fluctuation of adsorbed amount
of DCF with reaction time was relatively large. This had negatively
correlation with solution pH (Fig. S1). However, the adsorbed
amount of DCF had no significant correlation with system pH at pH
5.26 and pH 9.96 (Figs. S2 and S3). At pH 7.40, the solution pH was
close to the point of zero charge (PZC) of goethite, and the net
charge of goethite surface gradually changed into negative charge.
The fluctuation in the amounts of DCF adsorbed to goethite was
caused by the electrostatic interactions. We should notice that
some DCF was still adsorbed to goethite at pH > PZC, so other
mechanisms (i.e. surface complexation) might be also involved. And
this result was reported in previous studies on the adsorption of
Fig. 1. Effect of reaction time on adsorption of DCF onto goethite. Symbols represent
the experimental data, whereas the lines represent the simulated data fitted using the
Pseudo-second-order model with the parameters listed in Table 1. Error bars (±1
standard deviation, n ¼ 3) are shown in the figure.
375
other antibiotics containing carboxyl group (Trivedi and
Vasudevan, 2007; Paul et al., 2014; Qin et al., 2014b).
The pseudo-first-order kinetic and pseudo-second-order kinetic
models were used to simulate the experiment data (Table 1), and
only the pseudo-second-order model could fit the adsorption ki-
netics well (R2 > 0.96, P(prob > F) < 107). And qcal
e that obtained
with the pseudo-second-order model were similar to qexp e . The rate
constants (k2) at different pH conditions were 4.40  103,
1.40  103, and 3.00  103 g mg1 min1 respectively. Obviously,
the rate constant (k2) was related to the solution pH since it
decreased in the following pH order: 5.26 > 9.96 > 7.40. It was also
reported that protons took part in the chemical complexation be-
tween functional groups on PPCPs and goethite (Paul et al., 2012).
Therefore, the low pH was more favorable for adsorption. The
minimum kinetic rate constant (k2) was observed at pH 7.40, which
due to unstable charge of goethite surface at this condition.
3.2. Effect of pH
The adsorption edges of DCF to goethite were shown in Fig. 2. In
order to investigate the adsorption behavior of DCF at both low and
high concentration to goethite adequately, the initial concentra-
tions of DCF ranged from 250 to 2000 mg L1. With increasing initial
concentration of DCF, the adsorbed amount of DCF also increased at
different pH. The initial concentrations of DCF ranged from 250 to
2000 mg L1, the adsorbed amount of DCF increased from 6.29 to
45.96 mg g1 at pH 5.23, while the adsorbed amount increased from
0.19 to 2.39 mg g1 at pH 8.84. These phenomena might be
explained by the higher utilization of available active sites of
goethite at higher DCF concentration. Simultaneously, higher initial
concentration of DCF would increase the mass transfer driving force
and collision number between DCF molecules and goethite.
As shown in Fig. 2, at different initial concentration of DCF, the
trends that the amount of DCF adsorbed to goethite varied with
system pH were similar. The amount of adsorbed DCF decreased
with the increasing pH. Similar results were reported previously for
the adsorption of DCF to other adsorbents (Nam et al., 2015;
Thanhmingliana and Tiwari, 2015; Tiwari et al., 2015) and the
adsorption of flumequine to goethite (Zhang and Huang, 2007). In
our study, the feature of note was that the maximum adsorbed
amounts of DCF to goethite were appeared at pH 5.23, which was
close to pKa (4.15) of DCF. Similar result was found for the
adsorption of flumequine to goethite, in which the maximum
adsorbed amount of flumequine was gained around pH closed to
the pKa value of protonation in the carboxyl group (Zhang and
Huang, 2007). The adsorption edges of some organic acids (e.g.
benzoic, phenylacetic and 3-phenylpropionic) to goethite also
showed similar phenomena (Evanko and Dzombak, 1998).
At pH around PZC of goethite, the amount of adsorbed DCF
decreased very fast, which was caused by the change in the charges
of goethite surface. In the studied pH range (5.0e11.0), DCF existed
mostly in its anionic form, and the charges on goethite surface
changed with solution pH. At pH < PZC, the positive charges on
goethite decreased, and the adsorption of DCF to goethite also
decreased linearly. As shown in Table 2, the adsorption of DCF to
goethite was fitted well using the Linear model (R2 > 0.97). This also
supported the conclusion that electrostatic interactions played an
important role in the adsorption process at phase I (pH < 7). At
pH > PZC, goethite and DCF were negative charged, as a conse-
quence, the adsorption was rather weak. The adsorbed amount of
DCF was mainly contributed by complexation reaction, which was
similar to the adsorption of antibiotics to goethite (Qin et al., 2014a,
b; Zhao et al., 2014; Gu et al., 2015). So the amount of adsorbed DCF
decreased slowly. And the absolute value of the slope in the Linear
model at pH > PZC was an order magnitude smaller than that at
376 Y. Zhao et al. / Chemosphere 180 (2017) 373e378

Table 1
Sorption rate constants associated with Pseudo-first-order and Pseudo-second-order kinetic models.

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

pH ¼ 5.26 ± 0.09 pH ¼ 7.40 ± 0.26 pH ¼ 9.96 ± 0.43 pH ¼ 5.26 ± 0.09 pH ¼ 7.40 ± 0.26 pH ¼ 9.96 ± 0.43
1 1
qexp
e (mg g ) 25.47 9.33 1.59 qexp
e (mg g ) 25.47 9.33 1.59
k1 (min1) 4.61  104 4.61  104 1.38  103 k2 (g mg1 min1) 4.40  103 1.40  103 3.00  103
qe (mg g1)
cal
1.58 3.92 1.26 qe (mg g1)
cal
25.32 8.84 1.64
R2 0.3948 0.2889 0.9517 R2 0.9997 0.9658 0.9658
F test 1.96 (1.95  101) 3.25 (1.09  101) 155.13 (5.60  107) F test 26537.79 (1.11  1016) 254.48 (6.60  108) 253.92 (6.67  108)

Fig. 2. Adsorption of DCF to goethite under different pH conditions at 0.01 M NaCl. The
lines represent the simulated data by Linear regression using the parameters in Table 2.
The concentration of goethite is 20 g L1. Error bars (±1 standard deviation, n ¼ 3) are
shown in the figure.

pH < PZC (Table 2). In the adsorption edge of flumequine to

goethite, a turning point was observed on the curve at pH value
around PZC of goethite, which was opposite to the results in this
study. These differences might be caused by the different functional
groups between DCF (eCOOH and eNH) and flumequine (eCOOH
and eC]O) (Zhang and Huang, 2007). The complex reaction that
occurred between the goethite surface and carboxyl or/and ketone
groups in PPCPs was the main adsorption mechanism of PPCPs to
goethite (Trivedi and Vasudevan, 2007; Paul et al., 2014; Qin et al.,
2014a, b).

3.3. FTIR analysis

Fig. 3 shows the FTIR spectra of DCF and goethite under different
pH conditions. DCF had strong absorbance bands such as those at
3388 cm1 (nN-H), 3257 cm1 (nNeH/O due to intermolecular
Fig. 3. (1) FTIR spectra of DCF and goethite before adsorption (a) and after adsorption
under different pH conditions (b pH 5.27, c pH 7.13, d pH 9.21). (Fig. 3 (2) shows the
enlarged park in Fig. 3 (1).).

Table 2
The Linear regression parameters of DCF adsorbed to goethite at different pH.

Initial concentration of DCF (mg L1) Phase I (pH < 7) Phase Ⅱ (pH > 7)

Linear fitting equation R2 Linear fitting equation R2

250 y ¼ 19.811e2.440x 0.985 y ¼ 2.533e0.248x 0.787

500 y ¼ 41.693e5.308x 0.999 y ¼ 5.324e0.472x 0.797
1000 y ¼ 81.148e10.509x 0.978 y ¼ 12.766e1.137x 0.758
1500 y ¼ 101.961e12.311x 0.990 y ¼ 11.290e0.967x 0.860
2000 y ¼ 123.332e14.762x 0.986 y ¼ 15.446e1.390x 0.839
 Y. Zhao et al. / Chemosphere 180 (2017) 373e378
Fig. 4. Types of interactions between a carboxyl group of DCF and iron ion.
hydrogen bonding), 3077/3037 cm1 (nCeH, arom), 1577 cm1 (nas COO),
1558 cm1 (dNeH), 1508/1500 cm1 (nC]C, arom), 1452/1400 cm1 (ns
1
COO), 1305/1284 cm (nCeN, arom), and 765/746/715 cm1 (dCeH, arom)
(Bucci et al.,1998; Bartolomei et al., 2006). In the spectrum of goethite,
the broad band near 3116 cm1 was the stretching vibrations of
structural OH groups (Krehula and Music, 2008; Guo et al., 2013). A
strong intensity bands at 904 and 796 cm1 were caused by defor-
mation vibrations (dOH and gOH, respectively) and a band at 604 cm1
due to FeeO stretching vibrations (Krehula and Music, 2008;
Cagnasso et al., 2010; Tan et al., 2015).
As shown in Fig. 3(2), some bands which were similar to those of
original DCF also appeared in the spectra of goethite after adsorp-
tion (Fig. 3(2) b, c), for example 1577 cm1 (nas COO), 1558 cm1
(dNeH), 1508/1500 cm1 (nC]C, arom) and 1452/1400 cm1 (ns COO).
FTIR spectrum of DCF showed that the intensity at 1577 cm1 (nas
1
COO) was much higher than that at 1558 cm (dNeH) and 1452 cm1
(ns COO), while FTIR spectra of goethite after adsorption showed that
the intensity at 1577 cm1 (nas COO) was lower than that at
1558 cm1 (dNeH) and 1452 cm1 (ns COO). And the band at
1452 cm1 (ns COO) shifted to a band at 1459 cm1. This observation
suggested that comparing with the two carboxyl oxygen atoms in
original DCF, the two oxygen atoms carboxyl groups (eCOOH) in
some of the adsorbed DCF species were in different bonding envi-
ronments. These observations indicated that the functional group
(eCOOH) of DCF was involved in the adsorption process. These
were similar to the adsorption of fluoroquinolone antibiotics onto
goethite (Trivedi and Vasudevan, 2007; Paul et al., 2014). There
might be chemical complexation between carboxyl groups of DCF
and the surface groups of goethite.
As reported by others, the value Dn of the metal-carboxylate
complex (DnMe-COO) subtract the Dn of the free carboxyl complex
(Dnfree COO) revealed the types of interactions between a carboxyl
group and a metal ion (Tackett, 1989; Brisdon, 2010). DnMe-
COO > Dnfree COO meant forming a monodentate complex, DnMe-
COO < Dnfree COO meant forming a bidentate chelate, and
DnMeeCOO z Dnfree COO meant forming a bridging bidentate com-
plex. The value Dn was calculated using Eq. (4) as follow:
Dn ¼ nCOOas - nCOOs
The calculated value of DnDCF were 125 cm1 and 177 cm1,
377
respectively. Nevertheless, the values of DnDCF-goethite were
117 cm1 and 177 cm1, respectively. It indicated that the structures
of DCF complexation on the surface of goethite were bidentate
chelate and bridging bidentate complexes (Fig. 4).
Additionally, as shown in Fig. 3(2), the bands (i.e. 1558 cm1 dN-
1
H, 1508/1500 cm nC]C, arom) on goethite after adsorption at pH
5.27 (b) were much higher than those at neutral (c) and basic
condition (d). This phenomenon supported the conclusion that low
pH was beneficial to DCF adsorption on goethite.
4. Conclusion
This work studied the kinetics of DCF upon adsorption to
goethite under different pH conditions and the effect of pH on DCF
adsorption under different DCF initial concentrations. The sorption
kinetic data of DCF at each of three pH values (5.3, 7.4, and 10.0)
were fitted well by pseudo-second-order kinetic model. Adsorption
of DCF on goethite was greatly influenced by pH in solutions, and
more DCF was adsorbed on goethite at low pH according to pH-
edge adsorption experiments. Electrostatic interactions can
contribute to the overall sorption. FTIR results supported that there
was chemical complexation between carboxyl groups and the
surface groups of goethite. And proposed types of interaction for
DCF complexation on the goethite were bidentate chelate and
bridging bidentate. The results acquired in the study help us to
better estimate the distribution and mobility of similar ionization
pharmaceuticals in the environment.
Acknowledgements
This research was supported by the Natural Science Foundation
of China (4152229), and the project (DD20160312) from the China
Geological Survey.
Appendix A. Supplementary data
(4)
Supplementary data related to this article can be found at http://
dx.doi.org/10.1016/j.chemosphere.2017.04.007.
378 Y. Zhao et al. / Chemosphere 180 (2017) 373e378

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