Applied Clay Science 147 (2017) 137–142

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Applied Clay Science

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

Research paper

Degradation mechanism of amoxicillin using clay supported nanoscale zero- MARK

valent iron
Xiulan Wenga, Wanling Caia, Shen Linb, Zuliang Chena,c,⁎
a
Fujian Key Laboratory of Pollution Control and Resource Reuse, School of Environmental Science and Engineering, Fujian Normal University, Fuzhou 350007, Fujian
Province, China
b
School of Chemistry and Chemical Engineering, Fujian Normal University, Fuzhou 350007, Fujian Province, China
c
Global Centre for Environmental Remediation, University of Newcastle, Callaghan, NSW 2308, Australia

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

Keywords: Antibiotics such as amoxicillin (AMX) have been considered emerging pollutants due to their persistence in the
nZVI aquatic ecosystem even at low concentrations. Thus, it is an emerging issue to develop materials effective for
Clay removal of antibiotics pharmaceuticals from wastewaters. Bentonite supported nanoscale zero-valent iron (B-
Amoxicillin nZVI) as one of the alternatives was used to remove amoxicillin. Batch experiments revealed that the de-
Adsorption
gradation of amoxicillin depended on pH value of the solution, initial concentration of B-nZVI, initial con-
Degradation
Mechanism
centration of amoxicillin and reaction temperature. The removal of AMX was based on an integration of ad-
sorption and reductive degradation, which was confirmed by either adsorption or reductive kinetics. The
potential AMX degradation pathway was proposed by analysis of the degraded products using high performance
liquid chromatography-mass spectrometry (HPLC-MS). The removal mechanism of amoxicillin using B-nZVI
includes: (1) the adsorption of amoxicillin onto iron corrosion products; and (2) reduction of AMX by nZVI on B-
nZVI. Finally, the reusability of B-nZVI for degradation of amoxicillin was tested.

1. Introduction
In the last years, the presence and fate of antibiotics in environ-
mental matrices have received attention since antibiotics are persistent
and resistant to biodegradation, accumulating in the environment, and
consequently they pose a risk for aquatic and terrestrial organisms
(Homem and Santos, 2011; Lissemore et al., 2006; Pan et al., 2008).
Antibiotics such as amoxicillin have been extensively used over the past
80 years in medicine, agriculture, veterinary practices, and fish
farming, where they are inevitably excreted into the environment
(Homem and Santos, 2011; Pan et al., 2008). Unfortunately, conven-
tional wastewater treatment technologies are unable to quantitatively
remove these largely non-biodegradable species (Homem and Santos,
2011; Pan et al., 2008). Therefore, new technologies are being used for
the purpose of removing antibiotics from wastewater. These include
adsorption (Adriano et al., 2005; Putra et al., 2009), ozonation
(Andreozzi et al., 2005) and membrane (RO-UF) filtration (Li et al.,
2004). However, these methods need to dispose of the adsorbed con-
taminants or they will prove ineffective in treating wastewaters con-
taining amoxicillin. Adsorption is considered to be the most effective
method for removing contaminants residing in wastewater, because it is
simple and cost-effective, where the removal of amoxicillin from was-
tewater using adsorbents such as chitosan beads (Adriano et al., 2005),
activated carbon and bentonite have been reported (Putra et al., 2009).
Magnetite nanoparticles (Fe3O4) have recently been reported in the
adsorption of chlorotetracycline from aqueous solution, and Fe3O4
certainly exhibits a high adsorption capacity (Zhang et al., 2011a,b).
While adsorbents are often used to remove various contaminants, the
adsorbed contaminants need further disposal (Zhang et al., 2011a,b).
Recently, nanoscale zero-valent iron (nZVI) has been extensively
investigated in numerous studies for the remediation of groundwater
and other environmental applications owing to their small size and
large surface area. However, the aggregation of nZVI particles into
chain-like structure constitutes one of their major characteristics, which
is responsible for reducing the surface area to volume ratio (O'arroll
et al., 2013). The stability of iron nanoparticles against aggregation can
be improved by imparting electrostatic repulsion, applying organic
surfactants, or through the use of capping agents (O'arroll et al., 2013).
Another approach that would serve this goal is to synthesize iron na-
noparticles in the presence of supporting inorganic material (Shi et al.,
2011; Su et al., 2011; Zhang et al., 2011a,b). A few studies have focused
on removing antibiotics using nZVI or supported nZVI. Recently, the

⁎
Corresponding author at: Global Centre for Environmental Remediation, University of Newcastle, Callaghan, NSW 2308, Australia.
E-mail address: zuliang.chen@newcastle.edu.au (Z. Chen).

http://dx.doi.org/10.1016/j.clay.2017.07.023
Received 22 March 2017; Received in revised form 11 July 2017; Accepted 23 July 2017
Available online 02 August 2017
0169-1317/ © 2017 Elsevier B.V. All rights reserved.
X. Weng et al.
removal of amoxicillin and ampicillin from aqueous solution using nZVI
has been reported, where amoxicillin and ampicillin completely dis-
appeared through a lactam ring opening mechanism followed by hy-
drolysis after 3 h of contact with nZVI (Ghauch et al., 2009). This is due
to nZVI having an intrinsic aggregation that may limit its reaction rate
(Shi et al., 2011). In addition, the mechanism, reaction intermediates
and effect of solution parameters on the degradation also provide new
requires to be provided new insight of the degradation process. Our
recent report on bimetallic bentonite/Fe/Ni nanoparticles used for
catalytic degradation of amoxicillin has shown that > 94% of AMX was
removed (Weng et al., 2014). However, Ni is leaching as Ni2 + which
could be toxic (Jiang et al., 2013), while nZVI shown that it was less or
no-toxicity (Liu et al., 2014).
For these reasons, we focused on bentonite supported nZVI (B-nZVI)
for the degradation of amoxicillin. Batch removal kinetics experiments
at various conditions, and reusing B-nZVI in the removal of AMX were
conducted. Moreover, analysis of the degraded products by HPLC-MS
was performed to understand the degradation mechanism of amox-
icillin using B-nZVI. Hence, the aspects include (1) conduct batch re-
moval kinetics experiments in various conditions and its kinetics and
(2) test intermediates by HPLC-MS to confirm the mechanism.
2. Experimental
2.1. Materials and chemicals
Bentonite was supplied by Longyan Kaolin Co. Ltd., Fujian, China.
The cation exchange capacity (CEC) was 32.4 meq/100 g. The chemical
composition (mass %) of bentonite was 62.5% SiO2, 18.5% Al2O3,
1.75% Fe2O3, 4.25% MgO, 0.95% CaO, and 2.75% Na2O as previously
reported (Chen et al., 2011). Raw bentonite was ground and sieved with
a 200 mesh screen prior to use. FeCl3·6H2O was obtained from Tianjin
Chemical Reagent Co. (Tianjin, China). NaBH4 was purchased from
Sinopharm Chemical Reagent Co. (Shanghai, China). AMX was supplied
from Shanghai Shize Biotechnology Co. (Shanghai, China), and the
structural formula of amoxicillin was shown in Fig. 1. All the chemicals
used in this study were analytical reagent grade and utilised without
further purification. A solution containing amoxicillin was prepared by
dissolving various amounts of amoxicillin with deionized water to the
desired initial concentrations.
2.2. Synthesis of bentonite supported zero-valent iron
B-nZVI particles were synthesized using the liquid-phase reduction
method with bentonite as a support material as previously reported
(Chen et al., 2011; Shi et al., 2011). A preparation of B-nZVI with
bentonite via Fe0 mass ratio of 1:1; FeCl3·6H2O was dissolved in 50 mL
of miscible liquids, along with 1 g of bentonite. The mixture was stirred
with an electric rod for 15 min in a nitrogen atmosphere, and then
100 mL NaBH4 solution (0.047 mol) was added dropwise with vigorous
stirring continuously for 30 min, the whole reaction process was carried
under nitrogen atmosphere. The ferric ion (Fe3 +) is reduced to zero-
valent iron (Fe0) by excessive NaBH4 according to the following reac-
tion:
Fig. 1. The structural formula of amoxicillin.
138
Applied Clay Science 147 (2017) 137–142
4Fe3 + + 3BH−4 + 9H2 O → 4Fe0 + 3H2 BO−3 + 12H+ + 6H2 ↑ (1)
Vacuum filtration was employed to separate the B-nZVI particles
and the residual solution. Residual concentration of ferric ion in the
filtrate was not detected with the atomic absorption spectrometer (AAS,
VARIAN AA240, U.S.A.) because the ferric ion (Fe3 +) is completely
reduced to zero-valent iron (Fe0) by excessive NaBH4. The B-nZVI
particles were quickly rinsed three times with distilled water and ab-
solute ethylalcohol. Doing so prevented the nZVI from being oxidized
and then it was dried at 333 K under vacuum overnight, and kept in a
nitrogen atmosphere prior to use.
2.3. Batch experiments
To investigate the removal efficiency of B-nZVI, an experiment was
carried out using B-nZVI (0.10 g), which was added to 25 mL solution of
an initial concentration of 20 mg/L of AMX. The obtained dispersion
were left at their initial pH level stirred at 250 r/min at 298 K to the
desired time intervals. Various parameters affecting the reaction rate of
amoxicillin in aqueous solution by B-nZVI particles were investigated,
such as pH, dosage of B-nZVI, initial concentration of amoxicillin, and
temperature of the amoxicillin solution. All these experiments were
carried out in triplicate.
The concentration of amoxicillin solution was measured using a UV-
Spectrophotometer (722N, Shanghai, China) at λ = 228.3 nm (Zhang
et al., 2011a,b).
C0 − Ct
R (%) = × 100%
C0 (2)
where R (%) represented the AMX removal, C0 (mg/L) was the initial
concentration of AMX in the solution and Ct (mg/L) stood for the
concentration of AMX at t min.
2.4. Characterization and method
X-ray diffraction analysis of bentonite and prepared B-nZVI was
conducted by a Philips-X'Pert Pro MPD (Netherlands) diffractometer at
40 kV and 40 mA. Copper Kα radiation was used to produce X-rays with
a wavelength of 0.154 nm. All samples were scanned from 5° to 70° 2θ
at a scanning rate of 3° 2θ per minute in glass holder.
2.5. HPLC-MS analysis
HPLC-MS analysis of degraded products was performed by HPLC/Q-
TOF-MS (Bruker, Germany) with a C18 analytical column
(2.1 × 100 mm, 1.7 μm particle size). The mobile phase consisting of A
(methanol)-B (distilled water) at a flow rate 0.3 mL/min, i.e.: 0–1 min
10% A; 1–11 min 75% A; 11–14 min 10% A. The sample was used to
perform 20 μL of the samples were injected at 303 K. The mass spec-
trometers were operated under the following conditions: an ESI inter-
face in positive mode; 6.0 L/min of drying gas; 453 K of gas dry tem-
perature; 0.6B bar of Nebulizer; 70–500 m/z of mass range; 5.0 eV of
quadrupole ion energy.
3. Results and discussion
3.1. Characterization
X-ray diffraction (XRD) pattern of bentonite, the synthesized B-nZVI
is shown in Fig. 2. Fig. 2(a) demonstrated that bentonite was composed
primarily of montmorillonite, with the characteristic diffraction peaks
at 2θ = 6.0°, 19.8°, 34.9°, 36.5° and 61.8° (Chen et al., 2017). Other
important minerals such as quartz, kaolinite, and feldspar were present
in the bentonites (Chen et al., 2017; Sun et al., 2015). The XRD pattern
of synthesized B-nZVI (Fig. 2(b)) showed that the largest peak at the 2θ
of 44.8° indicated the presence of Fe0 and confirmed its existence in
X. Weng et al.
M M-montmorillonite
Q-quartz
K-kaolinite
Intensity / counts
M Q F-feldspar
Q an increase in total surface area and available active sites for AMX
F M
Q M
K
44.8°
35.5°
30.3° 62.8°
57.8°
0 10 20 30 40 50 60
2 theta
Fig. 2. XRD pattern of bentonite (a), B-nZVI (b) and B-nZVI after reaction (c).
freshly prepared B-nZVI (Liu et al., 2016). Furthermore, the peaks
corresponding to bentonite still occurred in Fig. 2(b). This indicated
that nZVI particles were supported on the bentonite. XRD patterns of B-
nZVI after reaction with AMX are shown in Fig. 2(c), where a peak
relative to the presence of Fe3O4 (2θ = 35.5°) (Shi et al., 2011) and
Fe2O3 (2θ = 30.3°, 57.8°, 62.8°) appears (Shi et al., 2011; Chen et al.,
2011b). This is attributed to the iron corrosion products such as Fe3O4
and Fe2O3 formed during B-nZVI's reaction with AMX (Shi et al., 2011;
Chen et al., 2011b).
3.2. Degradation kinetics of amoxicillin at various conditions
Degradation kinetics was conveniently expressed as a pseudo first-
order reaction (Chen et al., 2011,2013):
C nZVI (Chen et al., 2011).
ln = −kobs t
C0
here kobs is the observed rate constant of a pseudo first-order reaction
(min− 1) and can be calculated from the slope of the line by plotting ln
(C/C0) versus t (min− 1).
The degradation of amoxicillin using B-nZVI at various conditions
showed the linear relationship between ln (C/C0) and time, indicating
that the reductive degradation of amoxicillin by B-nZVI was in ac-
cordance with the pseudo first-order kinetics model as described below.
3.2.1. Effect of initial solution pH
The degradation of AMX by B-nZVI was conducted at an initial pH
of 3.0, 5.0, 6.7 and 11.0, and is presented in Fig. 3(a), where the kobs
were 0.114, 0.079, 0.067, and 0.037 min− 1, respectively. It can be seen
that the AMX removal rate increased as pH decreased, and maximum
removal efficiency was observed at initial pH value of 3.0 (Hussain
et al., 2017; Li et al., 2017). This is because a low solution pH favours
the corrosion of iron in aqueous solution, including the formation of
atomic hydrogen and molecular hydrogen at the B-nZVI surface (Bokare
et al., 2008), which is important for the degradation of AMX (Ghauch
et al., 2009). In contrast, while in the alkaline solution, slow production
of H2 limited the degradation of AMX, and precipitation of iron oxides
also formed on the B-nZVI surface (Chen et al., 2011). Hence, the de-
gradation of AMX decreased significantly as pH increased, suggesting
that optimum AMX reduction occurs under acidic conditions.
3.2.2. Effect of initial concentration of B-nZVI
The impacts of B-nZVI concentration (B-nZVI loading 2, 4, and 8 g/
L) on the removal rate of AMX were tested. As shown in Fig. 3(b), the
Applied Clay Science 147 (2017) 137–142
kobs were 0.043, 0.067, and 0.092 min− 1, respectively, where it can be
concluded that the pseudo first-order kinetics constants increased as the
B-nZVI concentration also rose. In this study, increasing the amount of
B-nZVI in the AMX solution led to an increase in the amount of nZVI.
This is mainly caused by an increase in the amount of nZVI leading to
(Bokare et al., 2008; Shih et al., 2011). This agrees with the results
a observed in other studies, where conventional B-nZVI was applied to
reduce azo dye methyl orange (Bokare et al., 2008) and nZVI was ap-
plied to reduce hexachlorobenzene (Shih et al., 2011).
b 3.2.3. Effect of initial concentration of AMX
Reactions of the different concentrations of AMX with the B-nZVI
being investigated are presented in Fig. 3(c). It is evident that the kobs
c decreased with the increase of initial AMX. They were 0.067 min− 1 for
20 mg/L of AMX, 0.015 min− 1 for 40 mg/L of AMX and 0.0089 min− 1
70 80 for 60 mg/L of AMX. This trend agreed with the finding in the study
using bare nZVI (Fan et al., 2009) and the entrapment of nanoscale
zero-valent iron in chitosan beads to remove hexavalent chromium
from wastewater (Liu et al., 2010). As a result, the higher the con-
centration of initial AMX, the more nZVI in B-nZVI would be oxidized
and loose activity, leading to the decline in reaction efficiencies and
rate constants.
3.2.4. Effect of solution temperature
The effect of reaction temperature on AMX removal is shown in
Fig. 3(d). As expected the AMX removal rate increased when tem-
perature rose. The kobs under the selected four temperatures (293, 298,
303 and 308 K) were determined as 0.047, 0.067, 0.087 and
0.13 min− 1, respectively. It is therefore proved that a higher reaction
temperature can reduce the time required for AMX. At a higher tem-
perature, the degradation of AMX using B-nZVI proved to be more ef-
ficient and indicated that an increase in temperature is favorable for
breaking down the bond of CeN of β-lactam and accelerating the re-
action (Chen et al., 2011; Ghauch et al., 2009). Similar results have
been previously reported on the degradation of methyl orange using B-
(3) Generally, the observed rate constant was logarithmically plotted
versus the reciprocal of temperature and a distinct linear relationship
resulted, in which Ea is calculated from the Arrhenius formula (Chen
et al., 2011,2013):
Ea
ln kobs = − + ln A0
RT (4)
where Ea (kJ/mol) is the apparent activation energy; and A0 is pre-
exponential factor with the same dimension as kobs.
The plots of ln kobs and 1/T are shown in Fig. 4. It is indicated that ln
kobs and 1/T have a strong linear relationship (R2 = 0.9867). The Ea of
B-nZVI reacting with AMX has been calculated by applying the Ar-
rhenius formula; the value is obtained at 49.65 kJ/mol (Fig. 4). An
activation energy is 49.65 kJ/mol, demonstrating that the ultimate
degradation process of AMX using B-nZVI can be regarded as a surface-
limiting reaction (Chen et al., 2011). However, the high activation
energy in this study suggested that the rate determining step of AMX
degradation using B-nZVI was breaking down the bond of CeN of β-
lactam at the B-nZVI surface (Chen et al., 2011; Ghauch et al., 2009). It
is thereby concluded that surface reactions including adsorption and
chemical reactions controlled the degradation under experimental
conditions.
3.3. Adsorption kinetics of amoxicillin
On the basis of the above results of reductive degradation, it is
concluded that the AMX removal in B-nZVI also involves adsorption. To
understand the adsorption of AMX onto the Fe3O4 which was formed by
iron corrosion, the pseudo second-order kinetic model was used to fit
139
X. Weng et al. Applied Clay Science 147 (2017) 137–142

Fig. 3. Degradation kinetics of amoxicillin under different

0.0
pH=3.0 k=0.114
a 0.0 b parameters.
-0.5 pH=5.0 k=0.079 a. Effect of initial solution pH. Conditions: 25 mL;
-0.5 C0 = 20 mg/L; 298 K; dosage of B-nZVI: 4 g/L; pH = 3.0,
pH=6.7 k=0.067
Ln(C/C0 )

Ln(C/C0 )
-1.0 pH=11.0 k=0.037 5.0, 6.7, 11.0.
-1.0
b. Effect of initial concentration of B-nZVI. Conditions:
-1.5 -1.5 25 mL; C0 = 20 mg/L; 298 K; dosage of B-nZVI: 2 g/L, 4 g/
L, 8 g/L; pH = 6.7.
-2.0 -2.0 2g/L k=0.043 c. Effect of initial concentration of AMX. Conditions:
4g/ L k=0.067
-2.5 -2.5 25 mL; C0 = 20 mg/L, 40 mg/L, 60 mg/L; 298 K; dosage of
8g/L k=0.092
B-nZVI: 4 g/L; pH = 6.7.
-3.0 -3.0 d. Effect of solution temperature. Conditions: 25 mL;
0 10 20 30 40 50 60 -5 0 5 10 15 20 25 30 35 40 45
Reaction time / min C0 = 20 mg/L; 293 K, 298 K, 303 K, 308 K; dosage of B-
Reaction time / min
nZVI: 4 g/L; pH = 6.7.

0.0 c 0.0 d
-0.5 -0.5 293 K k=0.047

Ln(C/C0 )
298 K k=0.067
-1.0 303 K k=0.087
Ln(C/C0 )

-1.0
308 K k=0.13
-1.5 -1.5

-2.0 20 mg/L k=0.067 -2.0

40 mg/L k=0.015
-2.5 60 mg/L k=0.0089 -2.5

-3.0 -3.0
0 10 20 30 40 0 10 20 30 40 50 60
Reaction time / min Reaction time / min

-1.8 2.5
100
-2.0
0 min

Removal efficiency / %
80
-2.2 y=17.32-5970.51x 2.0
5 min 60
R2=0.9955
B-nZVI
-2.4 10 min
Adsorbance

20 min 40
1.5
lnkobs

-2.6 30 min 20
40 min
-2.8 60 min 0
1.0 0 10 20 30 40 50 60
-3.0 Reaction time / min

-3.2
0.5
-3.4
0.00325 0.00330 0.00335 0.00340 0.00345

1/T /K-1 0.0

Fig. 4. Relationship between ln kobs and 1/T.
200 220 240 260 280 300 320

the experimental data (Chen et al., 2013; Zhang et al., 2011a,b): Wavelength / nm
Fig. 5. UV–Vis spectra of the degradation of amoxicillin at various times.
t 1 t
= +
qt k2 qe2 qe (5)
3.4. Proposed mechanism for the removal of AMX using B-nZVI
here qt and qe are the amount adsorbed (mg/g) of AMX at a time t (min)
and at equilibrium, respectively, k2 (g/mg·min) is the pseudo second- 3.4.1. UV–Vis analysis
order rate constant. The values of k2 and r22 are summarized in Table 1. As shown in Fig. 5, the change in the removal of AMX by B-nZVI at
As listed in Table 1, k2 increased as the reaction temperature rose, while different time internals was observed by UV–Vis. The decrease in AMX
qe decreased as the reaction temperature rose. The calculated qe values absorbance indicates that the AMX in aqueous solution was removed
fitted well with high correlation coefficients (r22) > 0.9890. These using B-nZVI after 60 min. The band at 228.3 nm which originated from
indicate that the pseudo second-order kinetic model can be used to the β-lactam bond was significantly reduced when the B-nZVI was
describe chemisorption of AMX onto iron oxides of B-nZVI. added to the solution containing AMX (Bhattacharyya and Cort, 1978;
Ghauch et al., 2009). The bands at about 195 nm and 264 nm relating
to aromatic rings (Bhattacharyya and Cort, 1978) were reduced after
Table 1
Adsorption kinetic model rate constants for AMX adsorption onto iron corrosion products
being treated with B-nZVI.
at different temperatures.

Temperature (K) k2 (g/mg·min) qe (mg/g) r22 3.4.2. HPLC-MS analysis

The main fragments observed in the mass spectra of AMX and the
293 0.0084 6.23 0.9910 products are indicated on Fig. 6 and a possible removal pathway of
298 0.02013 5.50 0.9890
AMX using B-nZVI is described in Fig. 7. Firstly, the removal of AMX by
303 0.05858 4.96 0.9954
308 0.3009 4.71 0.9996 B-nZVI was thought to adsorb AMX onto iron corrosion products; sec-
ondly, AMX by B-nZVI started with opening of the four-membered β-

140
X. Weng et al. Applied Clay Science 147 (2017) 137–142

Fig. 6. Mass spectra of AMX. (a) AMX before reaction; (b)

AMX after reaction.

lactam (m/z 339 C15H21N3O4S, Fig. 7(a)), deamination (m/z 324 100
C15H20N2O4S, Fig. 7(b)), carboxyl-reducing reaction and then opening
the five-membered thiazolidine ring (m/z 314 C15H26N2O3S, Fig. 7(c)).

Removal efficiency / %
80
Moreover a very weak peak of m/z at 350, 324 and 314 is presented in
Fig. 6(b) where C15H21N3O4S, C15H20N2O4S, C15H26N2O3S are inter-
mediate products being immediately reduced by B-nZVI. The structure 60
of this degradation product was confirmed by the appearance of the
characteristic fragment at m/z 300 (C14H24N2O3S) which is the product 40
of a demethylation reaction (Fig. 7(d)). This was consistent with the
results obtained from UV–Vis analysis and our previous reports (Weng
20
et al., 2013,2014).

3.5. Reuse in degradation of AMX 0

1 2 3 4 5
Reuse times
Repeated use of B-nZVI for degrading AMX is shown in Fig. 8, which
indicates that reactivity of B-nZVI decreased as reuse increased. For B- Fig. 8. Reuse of B-nZVI particles in the degradation of AMX.
nZVI treatment, the removal efficiencies of five reuse cycles were
93.5%, 78.2%, 52.5%, 28.3% and 9.1%, respectively. B-nZVI reducing
its reactivity is attributed to the corrosion of nZVI, leading to the

Fig. 7. Proposed mechanism for the removal of AMX using

B-nZVI nanoparticles.

141
X. Weng et al.
leaching out of the nZVI from the system (Yang et al., 2015). Therefore
further research is needed toward improving the stability of B-nZVI.
4. Conclusion
The study shows that AMX in solution can be removed by B-nZVI
and the reaction rate of the AMX may be influenced by a number of
factors such as the initial solution pH values, the initial concentration of
B-nZVI, the initial concentration of AMX, and the reaction temperature.
AMX was thought to adsorb onto the surface of B-nZVI and then reduce
AMX by nZVI of B-nZVI, which was confirmed by the kinetics study. In
addition, the analysis of degraded products by HPLC-MS shows that the
removal mechanism of amoxicillin using B-nZVI was based on reduc-
tion of AMX by nZVI on B-nZVI. This study provides a new insight into
degradation of β-lactam antibiotic using B-nZVI, and further work on
improving the stability of B-nZVI and simultaneous catalytic degrada-
tion of the antibiotics such as amoxicillin, ampicillin and penicillin is
progressing.
Acknowledgements
The financial support of Natural Science of Fujian Province
(2016J05028), China and Regional Major Project (2015YZ0001-1),
Fujian Province, China are gratefully acknowledged.
References
Adriano, W.S., Veredas, V., Santana, C.C., Goncalves, L.R.B., 2005. Adsorption of
amoxicillin on chitosan beads: kinetics, equilibrium and validation of finite batch
models. Biochem. Eng. J. 27, 132–137.
Andreozzi, R., Canterino, M., Marotta, R., Paxeus, N., 2005. Antibiotic removal from
wastewaters: the ozonation of amoxicillin. J. Hazard. Mater. 122, 243–250.
Bhattacharyya, P.K., Cort, W.M., 1978. Amoxicillin. Anal. Prof. Drug Subst. 7, 19–41.
Bokare, A.D., Chikate, R.C., Rode, C.V., Paknikar, K.M., 2008. Iron-nickel bimetallic na-
noparticles for reductive degradation of azo dye Orange G in aqueous solution. Appl.
Catal B Environ. 79, 270–278.
Chen, Z.X., Jin, X.Y., Chen, Z.L., Megharaj, M., Naidu, R., 2011. Removal of methyl or-
ange from aqueous solution using bentonite-supported nanoscale zero-valent iron. J.
Colloid Interface Sci. 363, 601–607.
Chen, Z.X., Wang, T., Jin, X.Y., Chen, Z.L., Megharaj, M., Naidu, R., 2013. Multifunctional
kaolinite-supported nanoscale zero-valent iron used for the adsorption and de-
gradation of crystal violet in aqueous solution. J. Colloid Interface Sci. 398, 59–66.
Chen, Y.G., Jia, L.Y., Li, Q., Ye, W.M., Cui, Y.J., Chen, B., 2017. Swelling deformation of
compacted GMZ bentonite experiencing chemical cycles of sodium-calcium exchange
and salinization-desalinization effect. Appl. Clay Sci. 141, 55–63.
Fan, J., Guo, Y.H., Wang, J.J., Fan, M.H., 2009. Rapid decolorization of azo dye methyl
orange in aqueous solution by nanoscale zerovalent iron particles. J. Hazard. Mater.
166, 904–910.
Ghauch, A., Tuqan, A., Assi, H.A., 2009. Antibiotic removal from water: elimination of
amoxicillin and ampicillin by microscale and nanoscale iron particles. Environ.
142
Applied Clay Science 147 (2017) 137–142
Pollut. 1626–1635.
Homem, V., Santos, L., 2011. Degradation and removal methods of antibiotics from
aqueous matrices - a review. J. Environ. Manag. 92, 2304–2347.
Hussain, I., Li, M.Y., Zhang, Y.Q., Li, Y.C., Huang, S.B., Du, X.D., Liu, G.Q., Hayat, W.,
Anwar, N., 2017. Insights into the mechanism of persulfate activation with nZVI/BC
nanocomposite for the degradation of nonylphenol. Chem. Eng. J. 311, 163–172.
Jiang, C.H., Liu, Y., Chen, Z.L., Megharaj, M., Naidu, R., 2013. Impact of iron-based
nanoparticles on microbial denitrification by Paracoccus sp. strain YF1. Aquat.
Toxicol. 142-143, 329–335.
Li, S.Z., Li, X.Y., Wang, D.Z., 2004. Membrane (RO-UF) filtration for antibiotic waste-
water treatment and recovery of antibiotics. Sep. Purif. Technol. 34, 109–114.
Li, P.J., Lin, K.R., Fang, Z.Q., Wang, K.M., 2017. Enhanced nitrate removal by novel
bimetallic Fe/Ni nanoparticles supported on biochar. J. Clean. Prod. 151, 21–33.
Lissemore, L., Hao, C., Yang, P., Sibley, P.K., Mabury, S., Solomon, K.R., 2006. An ex-
posure assessment for selected pharmaceuticals within a watershed in Southern
Ontario. Chemosphere 64, 717–729.
Liu, T.Y., Zhao, L., Sun, D.S., Tan, X., 2010. Entrapment of nanoscale zero-valent iron in
chitosan beads for hexavalent chromium removal from wastewater. J. Hazard. Mater.
184, 724–730.
Liu, Y., Li, S.B., Chen, Z.L., Megharaj, M., Naidu, R., 2014. Influence of zero-valent iron
nanoparticles on nitrate removal by Paracoccus sp. Chemosphere 108, 426–432.
Liu, J., Liu, A.R., Zhang, W.X., 2016. The influence of polyelectrolyte modification on
nanoscale zero-valent iron (nZVI): aggregation, sedimentation, and reactivity with Ni
(II) in water. Chem. Eng. J. 303, 268–274.
O'arroll, D., Sleep, B., Krol, M., Boparai, H., Kocur, C., 2013. Nanoscale zero valent iron
and bimetallic particles for contaminated site remediation. Adv. Water Res. 51,
104–122.
Pan, X.L., Deng, C.N., Zhang, D.Y., Wang, J.L., Mu, G.J., Chen, Y., 2008. Toxic effects of
amoxicillin on the photosystem II of synechocystis sp. characterized by a variety of in
vivo chlorophyll fluorescence tests. Aquat. Toxicol. 89, 207–213.
Putra, E.K., Pranowo, R., Sunarso, J., Indraswati, N., Ismadji, S., 2009. Performance of
activated carbon and bentonite for adsorption of amoxicillin from wastewater: me-
chanisms, isotherms and kinetics. Water Res. 43, 2419–2430.
Shi, L.N., Zhang, X., Chen, Z.L., 2011. Removal of Chromium (VI) from wastewater using
bentonite-supported nanoscale zero-valent iron. Water Res. 45, 886–892.
Shih, Y.S., Hsu, C.Y., Su, Y.F., 2011. Reduction of hexachlorobenzene by nanoscale zero-
valent iron: kinetics, pH effect, and degradation mechanism. Sep. Purif. Technol. 76,
268–274.
Su, J., Lin, S., Chen, Z.L., Megharaj, M., Naidu, R., 2011. Dechlorination of p-chlor-
ophenol from aqueous solution using bentonite supported Fe/Pd nanoparticles:
synthesis, characterization and kinetics. Desalination 280, 167–173.
Sun, Z.M., Qu, X.S., Wang, G.F., Zheng, S.L., Frost, R.L., 2015. Removal characteristics of
ammonium nitrogen from wastewater by modified Ca-bentonites. Appl. Clay Sci. 107,
46–51.
Weng, X.L., Lin, S., Zhong, Y.H., Chen, Z.L., 2013. Chitosan stabilized bimetallic Fe/Ni
nanoparticles used to remove mixed contaminants-amoxicillin and Cd (II) from
aqueous solutions. Chem. Eng. J. 229, 27–34.
Weng, X.L., Sun, Q., Lin, S., Chen, Z.L., Megharaj, M., Naidu, R., 2014. Enhancement of
catalytic degradation of amoxicillin in aqueous solution using clay supported bime-
tallic Fe/Ni nanoparticles. Chemosphere 103, 80–85.
Yang, B., Tian, Z., Zhang, L., Guo, Y.P., Yan, S.Q., 2015. Enhanced heterogeneous Fenton
degradation of Methylene Blue by nanoscale zero valent iron (nZVI) assembled on
magnetic Fe3O4/reduced graphene oxide. J. Water Process Eng. 5, 101–111.
Zhang, X., Lin, S., Chen, Z.L., Megharaj, M., Naidu, R., 2011a. Kaolinite-supported na-
noscale zero-valent iron for removal of Pb2 + from aqueous solution: reactivity,
characterization and mechanism. Water Res. 45, 3481–3488.
Zhang, D., Niu, H.Y., Zhang, X.L., Meng, Z.F., Cai, Y.Q., 2011b. Strong adsorption of
chlorotetracycline on magnetite nanoparticles. J. Hazard. Mater. 192, 1088–1093.