w a t e r r e s e a r c h 4 7 ( 2 0 1 3 ) 5 4 3 1 e5 4 3 8

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Efficient degradation of atrazine by magnetic

porous copper ferrite catalyzed peroxymonosulfate
oxidation via the formation of hydroxyl and sulfate
radicals

Ying-Hong Guan a,c, Jun Ma a,*, Yue-Ming Ren b,**, Yu-Lei Liu a,
Jia-Yue Xiao a, Ling-qiang Lin b, Chen Zhang b
a
State Key Laboratory of Urban Water Resource and Environment, Harbin Institute of Technology, Harbin 150090,
People’s Republic of China
b
Key Laboratory of Superlight Materials & Surface Technology, Ministry of Education College of Materials Science
and Chemical Engineering, Harbin Engineering University, Harbin 150008, People’s Republic of China
c
School of Water Conservancy and Construction Northeast Agriculture University, Harbin 150030, People’s Republic
of China

article info abstract

Article history: Magnetic porous copper ferrite (CuFe2O4) showed a notable catalytic activity to perox-
Received 3 February 2013 ymonosulfate (PMS). More than 98% of atrazine was degraded within 15 min at 1 mM PMS
Received in revised form and 0.1 g/L CuFe2O4. In contrast, CuFe2O4 exhibited no obvious catalytic activity to per-
6 June 2013 oxodisulfate or H2O2. Several factors affecting the catalytic performance of PMS/CuFe2O4
Accepted 12 June 2013 were investigated. Results showed that the catalytic degradation efficiency of atrazine
Available online 20 June 2013 increased with PMS and CuFe2O4 doses, but decreased with the increase of natural organic
matters concentration. The catalytic oxidation also showed a dependence on initial pH.
Keywords: The presence of bicarbonate stimulated atrazine degradation by PMS/CuFe2O4 at low
Sulfate radical concentrations but inhibited the degradation at high concentrations. Furthermore, the
Hydroxyl radical reactive species for atrazine degradation in PMS/CuFe2O4 system were identified as hy-
droxyl radical (HO ) and sulfate radical ðSO$
4 Þ through competition reactions of atrazine


Peroxymonosulfate
Copper ferrite and nitrobenzene, instead of commonly used alcohol scavenging, which was not a reliable
Atrazine method in metal oxide catalyzed oxidation. Surface hydroxyl groups of CuFe2O4 were a
Oxone critical part in radical generation and the copper on CuFe2O4 surface was an active site to
catalyze PMS. The catalytic degradation of atrazine by PMS/CuFe2O4 was also effective
under the background of actual waters.
ª 2013 Elsevier Ltd. All rights reserved.

* Corresponding author. Tel.: þ86 451 86283010; fax: þ86 451 86282292.
** Corresponding author.
E-mail address: majun@hit.edu.cn (J. Ma).
0043-1354/$ e see front matter ª 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.watres.2013.06.023
5432 w a t e r r e s e a r c h 4 7 ( 2 0 1 3 ) 5 4 3 1 e5 4 3 8
1. Introduction
Atrazine is a kind of triazine herbicides widely used for crops
and weed control. Photolysis of atrazine by sunlight is slow
due to the weak absorption at the wavelength above 220 nm.
Atrazine is also resistant to microorganism degradation and
therefore persistent in water and soil. Various studies were
conducted to generate HO
for the destruction of atrazine,
such as photolysis of hydrogen peroxide (De Laat et al., 1999),
Fenton and photo/electrochemical-Fenton (De Laat et al.,
1999; Ventura et al., 2002), ozone and catalytic ozonation
(Acero et al., 2000; Ma and Graham, 2000).
Sulfate radical ðSO$4 Þ is a strong oxidant with the redox
potential of 2.5e3.1 V (Neta et al., 1988), similar to HO
. It is
usually generated from peroxymonosulfate (PMS) and perox-
odisulfate (PDS) by UV, heat, base, transition metals, or qui-
nones activation (Anipsitakis and Dionysiou, 2004; Fang et al.,
2013b; Furman et al., 2010; Guan et al., 2011; Waldemer et al.,
2007). Comparing with PDS, PMS is easy to be activated by
transition metals due to the asymmetric molecular structure.
Homogeneous catalytic oxidation by PMS coupled with tran-
sition metals showed efficient decontamination of organic
pollutants, among which Co(II) was found to be a best acti-
vator (Anipsitakis and Dionysiou, 2004). However, cobalt has
been recognized as a possible human carcinogen by Interna-
tional Agency for Research on Cancer (IARC). In order to
reduce the concentration of free cobalt ions, attentions have
been focused on heterogeneous catalysis of PMS by supported
cobalt, cobalt oxides, and metal-cobalt mixed oxides (Chan
and Chu, 2009; Qi et al., 2013; Yang et al., 2009).
Spinel ferrites, expressed as MeFe2O4 (Me ¼ Mn, Co, Ni, Cu,
Mg, etc.), are kinds of magnetic materials widely used in
electronic applications, which could be separated easily from
water under magnetic field. The ferrites were used to remove
heavy metals from water bodies due to the abundant surface
hydroxyl groups and magnetic property (Tang et al., 2013).
Studies were also conducted on the photocatalytic and cata-
lytic activities of spinel ferrites. ZnFe2O4 exhibited notable
photocatalytic activity for H2O2 under visible light irradiation
(Su et al., 2012). Catalytic ozonation by NiFe2O4 was also re-
ported to destruct di-n-butyl phthalate (Ren et al., 2012). Fer-
rites (Co, Cu, Mn) catalyzed H2O2 oxidation could decolorize


synthetic dyes via the generation of HO (Baldrian et al., 2006).
PDS catalyzed by magnetite nanoparticles were investigated
to degrade 2,4,40 -trichlorobiphenyl and sulfamonomethoxine
(Fang et al., 2013a; Yan et al., 2011). CoFe2O4 was used to
catalyze PMS to reduce the concentration of free cobalt ion
(Yang et al., 2009). Our preliminary study found that CuFe2O4
was also effective to activate PMS among the ferrites (Mn, Co,
Ni, Cu, Zn), although not as effective as CoFe2O4. Furthermore,
copper is not recognized as potential carcinogen by IARC.
Considering the catalytic activity and the risk of metal
leaching of solid catalysts, CuFe2O4 might be applicable to
activate PMS in water treatment.
The purpose of this research was 1) to investigate the cat-
alytic activities of porous CuFe2O4 on peroxides (PMS, PDS and
H2O2), which was convenient to be separated from water due
to its large size compared with nanoparticles, 2) to identify the
reactive species for atrazine degradation and possible
mechanism on radical formation in the PMS/CuFe2O4 system,
3) to investigate the influences of water quality parameters on
the catalytic performance of PMS/CuFe2O4 including pH value,
PMS and CuFe2O4 doses, natural organic matters (NOM), and
inorganic salts, as well as the influences of actual water
backgrounds.
2. Experimental
2.1. Materials
Potassium peroxymonosulfate (available as Oxone, PMS),
potassium peroxodisulfate (PDS), atrazine, sodium phosphate
monobasic monohydrate, sodium phosphate dibasic were of
ACS reagent grade and purchased from SigmaeAldrich.
Hydrogen peroxide (35% w/w) was obtained from Alfa Aesar.
Methanol (Thermo Fisher Scientific) and acetic aid (Dima-
Tech) were of HPLC grade. Suwannee River natural organic
matter (SRNOM) was purchased from the International Humic
Substances Society. Tert-butyl-alcohol (TBA) was of guaran-
teed reagent grade and purchased from Tianjin Chemical
Reagent Co., Ltd., China. Copper nitrate, ferric nitrate, sodium
hydroxide, perchloric acid, sodium bicarbonate were all of
analytical-reagent grade and purchased from Sinopharm
Chemical Reagent Co., Ltd., China. All solutions were prepared
in Milli-Q water produced on a Milli-Q Biocel water system.
2.2. Preparation and characterization of CuFe2O4
Magnetic porous CuFe2O4 was prepared by a solegel process
with egg white at the copper and ferric molar ratio of 1:2,
referring to the preparation of NiFe2O4 reported previously
(Ren et al., 2012). Detailed information sees Text S1.
The surface morphologies were obtained on a Hitachi S-
3000N scanning electron microscopy (SEM). The X-ray powder
diffraction (XRD) was performed on a TTR-III diffractometer
(Rigaku, Japan) with Cu Ka radiation. The magnetic property
was measured by a vibrating sample magnetometer (JDM-14D,
China). Fourier transform infrared (FTIR) spectra were per-
formed on an IS10 FTIR spectrometer (Nicolet, America) in the
range of 500e4000 cm1. Raman spectra were taken on a
LabRAM HR800 confocal microscopic Raman spectrometer
(HORIBA Jobin Yvon, France) with 488 nm laser irradiation. X-
ray photoelectron spectroscopy (XPS) analysis was performed
with PHI 5700 ESCA System (Physic Electronics, America)
using an Al Ka excitation source (1486.6 eV). All lines recorded
were calibrated to the C 1 s line at 284.6 eV. The pHPZC of
CuFe2O4 was determined by mass titration.
The CuFe2O4 was characterized as a magnetic porous ma-
terial of tetragonal-type structure, with the average particle
diameter and pore size being 50e100 mm and 1e5 mm (SI Text
S2 and Fig. S1).
2.3. Experimental procedure
Experiments were performed in 250 mL conical flask at
25  2  C, mixed at 150 rpm. Desired amount of PMS and
atrazine stock solutions were added to solution to a final
 w a t e r r e s e a r c h 4 7 ( 2 0 1 3 ) 5 4 3 1 e5 4 3 8
volume of 100 mL. Solution pH was adjusted by perchloric acid
and sodium hydroxide. Then the reaction was initiated once
the catalyst was added. Samples were withdrawn and filtrated
by Whatman GF/F glass fiber membranes, and then quenched
by sodium nitrite or ascorbic acid before analysis. In the case
of actual water backgrounds, effluents from different stages of
a water treatment plant in Huainan, China, were used. Raw
surface water was treated in sequence by coagulation, sedi-
mentation, dissolved air flotation (DAF), biological activated
carbon (BAC), and sand filtration (SF) before disinfection. The
effluents from DAF, BAC, and SF were filtrated through
Whatman GF/F glass fiber membranes and used as the water
backgrounds in comparison tests. All the experiments were
conducted in triplicate and error bar represented the standard
deviation of the replicate experimental data.
2.4. Analysis
Atrazine and nitrobenzene were quantified by high perfor-
mance liquid chromatography described previously (Guan
et al., 2011), at l ¼ 221 nm and 263 nm with an eluent of
water (0.25& acetic acid) and methanol with ratio of 35:65 and
40:60 (v/v) at a flow rate of 1.0 mL/min. Method detection
limits (MDL) were 6.5 mg/L (0.03 mM) and 9.8 mg/L (0.08 mM). Free
copper and iron ions were quantified by an ICP-MS (AB Sciex
Qtrap 5500) with MDL of 0.2 mg/L and 6 mg/L. Dissolved organic
carbon (DOC) was measured by TOC analyzer (Analytik Jena
Multi N/C 3100). Excitation emission matrix (EEM) fluores-
cence spectra were recorded on a Jasco FP-6500 fluorescence
spectrometer. The solutions of PMS and PDS were standard-
ized using iodometric titration (Ball et al., 1967; Güpta, 1961).
H2O2 was quantified by its absorbance at 240 nm
(ε ¼ 38.1 M1 cm1) (Morgan et al., 1988).
3. Results and discussions
3.1. Catalytic oxidation of atrazine
Atrazine was fast degraded by PMS/CuFe2O4 and more than
98% of atrazine was destructed within 15 min at 1 mM PMS
and 0.1 g/L CuFe2O4. Meanwhile, PMS alone showed no
degradation of atrazine and less than 5% of atrazine was
adsorbed onto CuFe2O4 (Fig. 1). Ferrites were effective photo-
catalysts in visible and UV region, capable of producing reac-
tive oxygen species (Su et al., 2012). In order to exclude the role
of light in catalytic oxidation, experiments were further con-
ducted under dark condition (covered by aluminum foil) and
normal interior lighting condition (Fig. 1). Results showed that
there was almost no difference of atrazine degradation effi-
ciencies under the two conditions, which indicated the role of
light being negligible at the intensity of normal interior
lighting. So the catalytic oxidation of atrazine would be due to
the synergistic effect of PMS and CuFe2O4.
Concentrations of leached free metal ions from CuFe2O4


were monitored since they might activate PMS to produce HO
and/or SO$4 . In the absence of PMS, the concentrations of iron
and copper ions in the filtrate of CuFe2O4 suspension were
within 50 mg/L and 30 mg/L (data not shown). In the presence of
PMS, the concentration of free iron ion kept below 40 mg/L,
5433
Fig. 1 e Degradation efficiency of atrazine and
concentrations of leached metal ions. Conditions:
[PMS] [ 1.0 mM, [CuFe2O4] [ 0.1 g/L, [atrazine] [ 2.0 mM,
initial pH [ 7.5 ± 0.2.
while the concentration of free copper ion increased signifi-
cantly with reaction time and reached about 620 mg/L by
15 min (Fig. 1). Meanwhile, PMS still remained 92% of the
initial concentration after 15 min. Then atrazine degradation
by the filtrate of PMS and CuFe2O4 suspension (reaction for
15 min) was investigated. But the filtrate showed almost no
degradation of atrazine (Fig. 1), indicating that the formation
of reactive species for atrazine degradation would occur at the
surface of CuFe2O4.
3.2. Influences of several factors
3.2.1. Effect of PMS and catalyst doses
Atrazine degradation was enhanced with the increase of PMS
dose. The degradation efficiency was 16% by 2 min at 0.1 mM
PMS, and kept increasing to 49% at 1 mM PMS and 57% at
2.5 mM PMS (Fig. 2a). It could be deduced that the active sites
on CuFe2O4 surface were still not totally occupied by PMS even
at the concentration of 1 mM with CuFe2O4 dose of 0.1 g/L,
since the degradation efficiency kept increasing with the in-
crease of PMS concentration although the radical-scavenging
ability of PMS also increased.
Atrazine degradation also showed a positive dependence
on CuFe2O4 dose (Fig. 2b). Degradation efficiency increased
continuously from 8% to 67% by 2 min as CuFe2O4 dose
increased from 0.05 g/L to 1 g/L. Previous study showed that
the decontamination rate reached a maximum and then
decreased in catalytic ozonation due to radical scavenging or
ineffective ozone consumption at higher catalyst dose (Zhang
et al., 2012). Fe3O4 nanoparticles showed the maximal cata-
lytic activity to PDS at a dose of 0.55 g/L (2.4 mM) (Yan et al.,
2011). In the present study, the continuous increase of atra-
zine degradation efficiency at the initial stage (0e5 min) with
CuFe2O4 dose, reflected that the detrimental effect of high
dose of CuFe2O4 was overwhelmed by its stimulation effect.
This would be a solution to reduce costs in actual application
by high dose of CuFe2O4 and low dose of PMS. Whilst, the
lower degradation efficiency for higher catalyst dose (0.5 g/L)
5434 w a t e r r e s e a r c h 4 7 ( 2 0 1 3 ) 5 4 3 1 e5 4 3 8
Fig. 2 e Influences of PMS dose (a) and CuFe2O4 dose (b) on
atrazine degradation Conditions: [atrazine] [ 2.0 mM,
[NaHCO3] [ 2 mM, initial pH [ 7.5 ± 0.2, [CuFe2O4] [ 0.1 g/L
for (a), [PMS] [ 0.1 mM for (b).
at late stage of reaction (10e15 min), might be due to the fast
decomposition of PMS.
3.2.2. Role of pH
Metal oxides catalysts have amphoteric characteristics in
water suspension as depicted in Eqs. (1) and (2) (Ma et al.,
2005). The surface charge property of catalyst depends on
the difference between solution pH and pHPZC of the catalyst
(pH at the point of zero charge). The surfaces of catalyst have a
net positive (negative) charge at pH lower (higher) than pHPZC,
while the net particle charge is zero at pH around pHPZC.
hMeOHþ
2 #hMeOH þ H
þ
hMeOH#hMeO þ Hþ
Besides, the pKa of PMS (second pKa of its parent acid) was
9.4 (Rani et al., 2009) and its parent acid (H2SO5) was a strong
acid as sulfuric acid (Lawrance and Ward, 1985). Thus, in the
investigated pH range of 4e10.5, the existed form of PMS
depended mainly on solution pH and the second pKa.
Catalytic oxidation of atrazine by PMS/CuFe2O4 showed a
dependence on initial pH (Fig. 3 and Fig. S2). Atrazine degra-
dation was enhanced as the initial pH increased from 4 to 9.5,
and then declined from pH 9.5 to pH 10.5. Heterogeneous
catalytic ozonation by a-FeOOH or NiFe2O4 showed the
Fig. 3 e Influence of initial pH on atrazine degradation by
PMS/CuFe2O4. Conditions: [PMS] [ 1.0 mM,
[atrazine] [ 5.2 mM, [CuFe2O4] [ 0.1 g/L.
maximal decontamination efficiency around pHPZC of the
catalyst (Ren et al., 2012; Zhang et al., 2008). However, the
pHPZC of CuFe2O4 was measured as 8.5, which was not
consistent with the optimal initial pH (Fig. 3). Metal oxides
usually acted as buffer and might change solution pH. So pH
variation during the reaction was monitored roughly (Fig. S3).
pH increased gradually with reaction time at pH 4 and pH 5.5
due to the buffer effect of CuFe2O4. Meanwhile, it reached
around or below pH 8.5 (pHPZC) within 2 min at initial pH range
of 6.5e9.5. At initial pH 10.5, pH decreased with time and
finally kept above pH 9.5, which made the surface of CuFe2O4
negatively charged. Meanwhile, PMS existed mostly in the
form of SO2 5 at pH range of 9.5e10.5. Repulsive force from
electrostatic charge reduced the interaction chance of PMS
and CuFe2O4, resulting in the decline of atrazine degradation
when pH ranging from 9.5 to 10.5. At 4 < pH < 8.5, PMS mostly
existed as HSO 5 . With the decrease of pH, the surfaces of
CuFe2O4 would have a net positive charge and facilitate the
contact of PMS and CuFe2O4 by attractive force, but atrazine
degradation was declined. This indicated that the surface
hydroxyl groups in neutral state would be responsible for the
catalysis of PMS. Furthermore, the relative higher degradation
efficiency of atrazine at pH 10.5 than that at pH  8.5, indicated
SO2 
5 was easier to be activated than HSO5 in heterogeneous
catalytic oxidation.
3.2.3. Influence of bicarbonate
(1)
Bicarbonate was the representative of inorganic carbon existed
in natural water at the range of 50e200 mg/L (Ma and Graham,
(2)
2000), which usually acted as radical scavengers in advanced
oxidation process (De Laat et al., 2011). In the PMS/CuFe2O4
system, bicarbonate showed enhancement on atrazine degra-
dation at lower concentration (2 mM) and detrimental effect at
higher concentration (4 mM) as shown in Fig. 4. Final solution
pH was measured for its obvious influence on atrazine degra-
dation. It was around 6.2 in the absence of bicarbonate (Fig. S3)
and 7.3 in the presence of 2 mM bicarbonate (not shown). So the
higher solution pH during reaction might be one reason for the
enhancement of bicarbonate at low concentration. Bicarbonate


reacts with HO or SO$ 4 to form carbonate radical. At high
 w a t e r r e s e a r c h 4 7 ( 2 0 1 3 ) 5 4 3 1 e5 4 3 8 5435

Fig. 4 e Influence of bicarbonate on atrazine degradation Fig. 5 e Influence of NOM on atrazine degradation by PMS/
by PMS/CuFe2O4. Conditions: [PMS] [ 1.0 mM, CuFe2O4. Conditions: [PMS] [ 1.0 mM, [CuFe2O4] [ 0.1 g/L,
[CuFe2O4] [ 0.1 g/L, [atrazine] [ 2.0 mM, initial [atrazine] [ 2.0 mM, initial pH [ 7.5 ± 0.2.
pH [ 7.5 ± 0.1.

Therefore, TBA was used as scavenger for HO and methanol

concentration (4 mM), bicarbonate would mostly act as HO

as scavenger for HO and SO$ 4 .

and SO$ As shown in Fig. 6, TBA and methanol indeed inhibited

4 scavengers and therefore inhibit atrazine degradation.
At lower concentration, carbonate radical might act as a pro- atrazine degradation and the inhibition were enhanced with
moter stimulating PMS decomposition into HO or SO$

the increased of their dosages. At low concentration (1 mM),
4 , similar
to the enhancement of bicarbonate in catalytic ozonation (Zhao methanol did not inhibit atrazine degradation as much as TBA
et al., 2010). Furthermore, carbonate could form complexes on while methanol inhibited atrazine degradation more signifi-
hematite surface (Bargar et al., 2005) and bicarbonate enhanced cantly than TBA at high concentration (100 mM). Methanol

the oxidation of ferrous by oxygen (King, 1998). The complexes reacts with HO and SO$ 4 to form hydroxylmethyl radical
of bicarbonate on CuFe2O4 surface might also be a reason for the (
CH2OH), which might stimulate the decomposition of PMS
enhancement at low concentration. into radicals (Guan et al., 2011), and further alleviate the in-
hibition of methanol on atrazine degradation at low concen-
3.2.4. Influence of NOM tration. The different inhibition effects of the two alcohols at
NOM usually act as radical scavenger via competing for HO
high concentration (Fig. 6), seemed due to the formation of
and SO$ 4 . However, TBA inhibited the non-radical interface
SO$
4 . Phenolic hydroxyl and carboxyl groups of NOM
might also be adsorbed onto catalyst surface and block reac- oxidation of oxalate possibly due to its adsorption onto cata-
tive sites. Whilst, semiquinone radicals, formed from hydro- lyst (Zhang et al., 2012). The different inhibition effect of al-
quinones, quinones and phenols in NOM, might also cohols might not only be due to their different abilities for
stimulate the decomposition of PMS into HO or SO$

scavenging radicals, but also due to their different adsorption
4 , similar


to the way of reducing H2O2 to HO (Zhu et al., 2002). In the properties onto CuFe2O4 and subsequent occupation for active
PMS/CuFe2O4 system, atrazine degradation was inhibited by sites. Hence, it was not a reliable method to use TBA and
the addition of SRNOM. The degradation efficiency at 15 min
decreased from 98% to 77% and 23% when SRNOM concen-
tration increased from 0 mg/L to 1.0 mg/L and 3.2 mg/L (Fig. 5).
It indicated that the stimulated effect of NOM was over-
whelmed by its detrimental effect in the range of
1.0e3.2 mg/L.

3.3. Reactive species and possible mechanism

3.3.1. Reactive species

Atrazine was rarely adsorbed on CuFe2O4 (Fig. 1) and the
structure of atrazine (Fig. S4) did not facilitate itself to undergo
non-radical interface reaction. Furthermore, catalytic ozona-
tion of atrazine by metal oxide was proved mainly via radical
attack rather than non-radical interface reaction (Zhang et al.,
Fig. 6 e Inhibition of tert-butyl alcohol (TBA) and methanol


2012). PMS could generate HO and/or SO$ 4 by homogeneous or
heterogeneous activation. Peroxomonosulfate radical ðSO$ 5 Þ (Me) on atrazine degradation by PMS/CuFe2O4. Conditions:
might also be formed, but would not contribute to atrazine [PMS] [ 1.0 mM, [CuFe2O4] [ 0.1 g/L, [atrazine] [ 2 mM,
degradation for its lower redox potential (Neta et al., 1988). [phosphate] [ 5 mM, initial pH [ 7.5 ± 0.2.
5436 w a t e r r e s e a r c h 4 7 ( 2 0 1 3 ) 5 4 3 1 e5 4 3 8


methanol to identify HO and SO$ 4 in heterogeneous metal
oxides catalyzed oxidation. Further experiments were con-
ducted to identify the reactive species in PMS/CuFe2O4 system.


Nitrobenzene was selected as HO probe compound due to
its low reactivity with SO$4 (Guan et al., 2011). Nitrobenzene
and atrazine were rarely removed by PMS or CuFe2O4 alone
(data not shown). However, nitrobenzene was degraded
obviously by PMS/CuFe2O4 (Fig. 7), which verified the forma-


tion of HO in PMS/CuFe2O4 system.
If the reactive species for atrazine degradation were both


HO and SO$ 4 , the kinetic expressions of atrazine and nitro-
benzene degradation could be expressed as follows.
dCNB
 ¼ k1 ½HO$ CNB ¼ k0;NB CNB
dt
 
dCAT
 ¼ k2 ½HO$ CAT þ k3 SO$
4 CAT ¼ ko;AT CAT
dt


where k1 (k2) was the rate constant between HO and nitro-
benzene (atrazine), k3 was the rate constant between SO$4 and
atrazine. k0,NB and k0,AT were the pseudo first order rate con-
stants of nitrobenzene and atrazine degradation. CNB and CAT
were the concentrations of nitrobenzene and atrazine.
k1 and k2 were in the ranges of 3.2e4.7 109 M1 s1 and
2.5e3 109 M1 s1 (Balci et al., 2009; Buxton et al., 1988;
Gallard et al., 1998). And k2/k1 would be in the range of
0.5e1. However, the value of k0,AT/k0,NB, obtained from linear
fit of atrazine and nitrobenzene degradation (Inset of Fig. 7),
was 6.4. It was much larger than the value of k2/k1, indicating
the contribution of SO$4 to atrazine degradation. Thus, both


HO and SO$ 4 were the reactive species for atrazine degrada-
tion in PMS/CuFe2O4 system.
3.3.2. Possible active sites
The role of surface hydroxyl groups of catalyst was investi-
gated via the substitution by phosphate since phosphate had
stronger affinity to active sites (Zhang et al., 2008). As shown
in Fig. 6, phosphate showed significant inhibition on atrazine
degradation, which confirmed the role of surface hydroxyl
groups of CuFe2O4 in the catalysis of PMS. Besides, the
maximal efficiency of atrazine degradation was obtained
Fig. 7 e Degradation of nitrobenzene (NB) and atrazine (AT)
by PMS/CuFe2O4. Conditions: [PMS] [ 1 mM,
[CuFe2O4] [ 0.1 g/L, [nitrobenzene] [ 6.4 mM,
[atrazine] [ 2.0 mM, initial pH [ 7.5 ± 0.2.
around pHPZC of CuFe2O4 (Fig. 3), indicating that the surface
hydroxyl groups in neutral state would be major part
responsible for the activation of PMS.
A red-shift of 10 cm1 of the peak at 1200 cm1 in the IR
spectra was observed when CuFe2O4 was added to PMS solution
(see SI Text S3 and Fig. S5), indicating the change of SeO bond.
The newly emerging peak of the OeO bond in Raman spectrum
of PMS/CuFe2O4, might indicate the complexes of PMS on
CuFe2O4 surface (see SI Text S4 and Fig. S6). Furthermore, the
increased concentration of leached copper ion during reaction
(Fig. 1), indicated that Cu on the surface of CuFe2O4 might be the
active sites to catalyze PMS. The analysis of XPS spectra of
CuFe2O4 before and after catalytic reaction (Fig. S7), showed that
(3) the valence of Fe on the surface of CuFe2O4 did not change, while
the valence of Cu changed from Cu2þ to the mixture of Cu2þ and
Cuþ (see SI Text S5). SO$


4 and HO might be generated during the
(4) cycle of Cu2þ/Cuþ via the electron transfer from PMS to Cu2þ and
the reduction of PMS by Cuþ (Ding et al., 2013; Gilbert and Stell,
1990). Although one electron transfer from PMS to Cu2þ
seemed unfavorable based on the standard reduction potential
of Cu2þ/Cuþ (0.17 V) and SO2  2
5 /HSO5 (1.1 V) or SO5 /SO5 (0.81 V)
$
(Das et al., 1999; Ding et al., 2013; Neta et al., 1988), the low con-
centration of SO$5 would render the actual reduction potential of
SO2  2
5 /HSO5 or SO5 /SO5 to a relative low value in the investi-
$
gated system. CuFe2O4 exhibited significant catalytic activity on
PMS while leached or free copper ions showed almost no cata-
lytic activity on PMS as shown in Fig. 1 and the results reported
previously (Zhang et al., 2013). It indicated that the heteroge-
neous catalytic activity of CuFe2O4 on PMS might not only be
decided by the standard reduction potential of redox couple of
cycled metal, but also influenced by the heterogeneous reaction
system and the complexation of copper on the surface of
CuFe2O4 with PMS, which might make the reaction complicated.
Further investigations are needed to clarify the mechanisms on
the radical formation pathway and the cycle of metal ions in the
future studies.
3.4. Comparison of peroxides
The decontamination efficiencies by PDS/CuFe2O4 and H2O2/
CuFe2O4 were investigated in comparison with PMS/CuFe2O4.
However, PDS/CuFe2O4 and H2O2/CuFe2O4 showed almost no
degradation of atrazine (Fig. 8). Previous study reported that
CuFe2O4 could decolorize synthetic dyes at H2O2 and CuFe2O4
doses of 100 mM and 1.25e25 g/L (Baldrian et al., 2006). The
catalytic activity of CuFe2O4 on H2O2 reported in the literature
might be due to the high doses of H2O2 and CuFe2O4, as well as
the long reaction time. The different reactivity of peroxides in
heterogeneous CuFe2O4 catalytic oxidation, was similar to the
result in homogeneous catalytic oxidation, in which PMS
showed significant reactivity with the majority of metals espe-
cially under neutral pH (Anipsitakis and Dionysiou, 2004). This
indicated that the asymmetric structure of PMS made it also
easy to be activated in the heterogeneous catalytic oxidation.
3.5. Degradation of atrazine under actual water
background
Water quality parameters of the effluents from DAF, BAC, and
SF were given in Tab. S1 with almost the same alkalinity and
 w a t e r r e s e a r c h 4 7 ( 2 0 1 3 ) 5 4 3 1 e5 4 3 8
Fig. 8 e Atrazine degradation by peroxides/CuFe2O4 in
Milli-Q water and actual water backgrounds. Conditions:
[oxidants] [ 1.0 mM, [CuFe2O4] [ 0.1 g/L,
[atrazine] [ 2.0 mM, [NaHCO3] [ 2 mM for Milli-Q water,
initial pH [ 7.5 ± 0.2.
pH value but a little difference in DOC. EEM fluorescence
spectra were used to characterize the compound-class
composition of dissolved organic matter in the effluents and
the fluorescence characteristics of the effluents were different
(SI Text S6 and Fig. S8), which might affect the abilities of NOM
to complex with metals and scavenge radicals. Atrazine
degradation by PMS/CuFe2O4 was inhibited in actual water
compared with in Milli-Q water to some extent (Fig. 8), which
would be due to the presence of NOM and inorganic salts. The
difference of the degradation efficiencies under the back-
grounds of three kinds of effluents was not obvious, which
indicated that the decontamination efficiency of PMS/CuFe2O4
was hardly influenced by the fluorescence characteristics, but
might be affected mainly by other parameters such as DOC,
pH value, and alkalinity.
4. Conclusions
- The magnetic porous CuFe2O4, synthesized by a solegel
method, was applied to the catalysis of peroxides. CuFe2O4
exhibited a notable catalytic activity to PMS for atrazine
degradation but almost no catalytic activity to PDS and
H2O2.
- Atrazine degradation by PMS/CuFe2O4 was enhanced with
the increase of PMS and CuFe2O4 doses at respective range
of 0.1e2.5 mM and 0.05e1 g/L. It showed a dependence on
initial pH and the maximal degradation efficiency was
obtained at initial pH 9.5. Bicarbonate stimulated atrazine
degradation in the catalytic oxidation at the concentration
of 2 mM but inhibited at >4 mM. NOM inhibited the cata-
lytic degradation of atrazine at the range of 1.0e3.2 mg/L.
- Both HO and SO$


4 were identified in PMS/CuFe2O4 system
by competition reactions of atrazine and nitrobenzene, a
more reliable method than alcohol scavenging in hetero-
geneous catalytic oxidation.
- Surface hydroxyl groups of CuFe2O4 played an important
role in the generation of radicals from PMS/CuFe2O4 and
5437
the Cu on CuFe2O4 surface was the active sites to catalyze
PMS via the cycle of Cu2þ/Cuþ.
- Catalytic degradation of atrazine by PMS/CuFe2O4 was also
effective under the backgrounds of investigated actual
waters, which provide a reference for application.
Acknowledgments
This research was supported by the Funds for Creative
Research Groups of China (Grant No. 51121062), the Natural
Science Foundation of China (Grant No. 51178134,
No.51108111), the National Science & Technology
Pillar Program of China (Grant No. 2012BAC05B02), and
Fundamental Research Funds for the Central Universities
(HEUCF).
Appendix A. Supplementary data
Supplementary data related to this article can be found at
http://dx.doi.org/10.1016/j.watres.2013.06.023.
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