Journal of Cleaner Production 314 (2021) 128119

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Journal of Cleaner Production

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

Effective removal of the heavy metal-organic complex Cu-EDTA from water

by catalytic persulfate oxidation: Performance and mechanisms
Qi Wang a, Yutong Li a, Yue Liu a, Jingyu Ren b, **, Ying Zhang c, Guangzhou Qu a, d,
Tiecheng Wang a, d, *
a
College of Natural Resources and Environment, Northwest A&F University, Yangling, Shaanxi Province, 712100, PR China
b
School of Petroleum Engineering and Environmental Engineering, Yan’an University, Yan’an, 716000, China
c
College of Information Science and Technology, Nanjing Forestry University, Nanjing, 210037, China
d
Key Laboratory of Plant Nutrition and the Agri-environment in Northwest China, Ministry of Agriculture, Yangling, Shaanxi, 712100, PR China

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

Handling editor: Prof. Jiri Jaromir Klemeš It is difficult to remove heavy metal-organic complexes from water by chemical precipitation because of the
strong complexation ability between heavy metal ions and organics. In this study, the removal of the Cu-
Keywords: ethylenediaminetetraacetic acid (Cu-EDTA) complex using autocatalytic persulfate (PS) oxidation was investi­
Persulfate gated. The Cu-EDTA removal efficiency reached up to 96.57% after 90 min of treatment by PS oxidation. A
Cu-EDTA
higher PS concentration favored Cu-EDTA removal; An increase in the initial concentration of Cu-EDTA benefited
Activation mechanisms
PS activation, and a greater removal performance was obtained at a lower Cu-EDTA initial concentration (0.1
Decomplexation
Removal mmol L− 1). Excessive Cu2+ accelerated Cu-EDTA removal, while superfluous EDTA suppressed it. Relatively
1
lower initial solution pH value favored Cu-EDTA removal. SO•-
4 , •OH, and O2 displayed significant roles in the
Cu-EDTA removal process, as they destroyed the chelating sites of the Cu(II) and EDTA molecules; finally small
molecular organic acids, alcohols, and NO−3 were produced. The released Cu(II) existed in the precipitates in the
forms of Cu-based carbonates, Cu-based hydroxides, and copper oxide. A possible decomposition pathway of Cu-
EDTA was proposed. Overall, multipathway activation of PS induced by heavy metal complexes could be an
effective technique for the removal of the heavy metal complexes.

1. Introduction Decomplexation is considered to be an essential step for effective

Ethylenediaminetetraacetic acid (EDTA), an organic complexing
agent, is widely used in textiles (Lee et al., 2015), printing and dyeing
(Kim and Baek, 2019), electroplating, and other industries because it can
well increase the activity of surfactants (Cuprys et al., 2018). As a result,
heavy metal-EDTA complexes are easily detected in various water
sources due to the powerful chelating ability of EDTA with heavy metals
(Lee et al., 2015). Compared with metal ions, the heavy metal complexes
are more toxic to environment and microorganisms (Ahamad et al.,
2019). Arruda et al. (2010) reported that the half lethal concentration of
Cu-EDTA for Aedes aegypti was 32 mg L− 1. Removal of the heavy metal
complexes has been a major challenge because they are extremely stable
over a wide pH range and strongly resistant to some conventional
removal methods (Wang et al., 2018). Thus, it has become a top priority
to remove these complexes.
removal of the metal complexes (Zhao et al., 2015). In the decom­
plexation process, the heavy metal ions can be released, which provides
convenience for subsequent recovery or precipitation of the free metal
ions. Many oxidation methods, including Fe(III)/ultraviolet irradiation
(UV) (Shan et al., 2018), photoelectrocatalysis (Zhao et al., 2015),
discharge plasma (Wang et al., 2019a; Liu et al., 2021), Fenton reaction
(Guan et al., 2018), and photocatalysis (Lan et al., 2018) have been used
to remove the heavy metal complexes. Electro-Fenton combined with
electrocoagulation was reported to be effective for Cu-EDTA elimination
from wastewater, whereas iron-bearing deposition in sludge needed
further treatment (Guan et al., 2018). Most nanophotocatalytic mate­
rials are composed of transition metals, which might lead to potential
ecological risks to the environment; and the catalytic activity of the
photocatalysts is limited by effective light absorption and materials (Lan
et al., 2018). Non-thermal plasma oxidation could effectively remove

* Corresponding author. College of Natural Resources and Environment, Northwest A&F University, Yangling, Shaanxi Province, 712100, PR China.
** Corresponding author.
E-mail addresses: renjingyuyau@163.com (J. Ren), wangtiecheng2008@nwsuaf.edu.cn (T. Wang).

https://doi.org/10.1016/j.jclepro.2021.128119
Received 2 January 2021; Received in revised form 23 June 2021; Accepted 24 June 2021
Available online 25 June 2021
0959-6526/© 2021 Elsevier Ltd. All rights reserved.
Q. Wang et al.
Cu-EDTA; however, electric power consumption limits its wide appli­
cation (Wang et al., 2019b). Cu(II) in the Cu-EDTA could be replaced by
Fe(III) to produce more stable Fe(III)-EDTA, and then the Fe(III)-EDTA
was decomposed by subsequent UV to destroy the chelate (Shan et al.,
2018).
Recently, persulfate (PS) oxidation, as an in-situ chemical oxidation
technology, has received wide attention in pollutant removal (Pi et al.,
1
2019). SO•-4 , •OH, O2 , and O2 are probably generated by the activation
•-
of PS, which are responsible for organic pollutant degradation as re­
ported by Dong et al. (2019), Pi et al. (2019), and Xu et al. (2020). The
activation of PS requires exogenous materials or an energy supply such
as metal ions, heat, and UV irradiation. Cu-EDTA decomplexation and
removal from water was achieved by UV/PS oxidation (Xu et al., 2017).
The Co2+/PS oxidation system was proven to rapidly remove Cu-EDTA
from wastewater (Xu et al., 2020). It was reported that heat combined
with Fe(II)-complexes could activate PS to remove hydrolyzed poly­
acrylamide (Huang et al., 2020). It is expected that Cu-EDTA can be used
to activate PS, resulting in free Cu ion release; these released Cu ions
might also participate in the PS activation. Moreover, certain Cu-based
intermediates during Cu-EDTA decomposition might also contribute to
PS activation. In this case, effective decomposition of Cu-EDTA could be
achieved. However, some information on Cu-EDTA decomplexation
performance and the underlying mechanisms of the PS oxidation process
triggered by Cu-EDTA itself is still unknown.
In this study, Cu-EDTA was selected as the target pollutant because
Cu was widely used in electroplating and electrical industries, and it is
easily chelated with EDTA to form stable Cu-EDTA (Zeng et al., 2016a).
The removal of Cu-EDTA complex using autocatalytic PS oxidation was
investigated, and PS activation was triggered by Cu-EDTA itself (Su
et al., 2020). First, the influences of solution pH, initial Cu-EDTA con­
centration, and the molar ratio of Cu2+ and EDTA (nCu2+/nEDTA) on
Cu-EDTA removal and PS activation were assessed. Second, the gener­
ation and contributions of reactive oxygen species (ROS) were evalu­
ated. Finally, the PS activation mechanisms, decomposition processes
and mechanisms of Cu-EDTA were explored via the chemical structures
of Cu-EDTA, zeta potential, intermediate generation, Cu species distri­
bution, and precipitate composition.
2. Experimental
2.1. Chemicals
Analytically pure copper sulfate pentahydrate (CuSO4⋅5H2O, purity ˃
99%), iminodiacetic acid (IMDA, purity ˃ 99%), sodium persulfate (PS,
purity ˃ 98%), nitrilotriacetic acid (NTA, purity ˃ 99%), ethanol (purity ˃
99.7%), and ethylenediaminetetraacetic acid disodium salt (EDTA-2Na,
purity ˃ 99%) were provided by Sinopharm Chemical Reagent Co., Ltd.,
China. Chromatographically pure benzoquinone (BQ), 2,2,6,6-tetra-
methylpiperidine (TEMP), sodium azide (NaN3), 5,5-dimethyl-1-pyrro­
line N-oxide (DMPO), and isopropanol (IPA) were provided by Sigma-
Aldrich. The Cu-EDTA working solution was obtained with an equal
molar ratio of CuSO4⋅5H2O and EDTA-2Na.
2.2. Reaction system
Cu-EDTA removal experiments were conducted in a constant tem­
perature breeding shaker and 150 mL conical flasks. First, 100 mL of Cu-
EDTA solution was placed in a conical flask in the shaker with stable
parameters (solution temperature T = 25 ◦ C, and rotation speed 200 r
min− 1). Under this temperature, the activation of PS by heating could be
neglected. Then, the reactions were triggered by adding 1 mL of per­
sulfate stock solution (1 mol L− 1). After treatment, 1 mL solution was
collected and 100 μL pure methanol was immediately added to the so­
lution to quench the reaction. This solution was used for Cu-EDTA
measurement.
Cu2+ stock solution with an initial concentration of 0.05 mol L− 1 was
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Journal of Cleaner Production 314 (2021) 128119
prepared by dissolving 1.2485 g CuSO4⋅5H2O into 100 mL deionized
water. EDTA stock solution with an initial concentration of 0.05 mol L− 1
was prepared by dissolving 1.8612 g EDTA-2Na into 100 mL deionized
water. Cu-EDTA working solution was prepared by mixing the same
volume of Cu2+ and EDTA stock solutions into 100 mL. The initial pH
value of 0.1 mmol L− 1 Cu-EDTA working solution was 4.0 without
adjustment, which was comparable to the real electroplating wastewater
(Fu et al., 2021). For the effects of initial Cu-EDTA concentration, 0.1,
0.2, 0.3, and 0.4 mmol L− 1 Cu-EDTA working solutions were prepared
by mixing 200, 400, 600, and 800 μL Cu2+ and EDTA stock solutions into
100 mL, respectively; the experiments were carried out at 10 mmol L− 1
PS. For the effects of initial solution pH, 0.1 mmol L− 1 Cu-EDTA working
solution was prepared by mixing 200 μL Cu2+ and EDTA stock solutions
into 100 mL; then the initial solution pH was adjusted to 4, 6, 8, and 10
using 0.5 mol L− 1 H2SO4 and NaOH, respectively; the experiments were
carried out at 10 mmol L− 1 PS.
For the effects of the molar ratio of nCu2+/nEDTA, two series of ex­
periments were conducted. On the one hand, the Cu2+ concentration
was maintained at 0.1 mmol L− 1, but the EDTA concentrations were
changed to 0.1, 0.2, 0.3, and 0.4 mmol L− 1, respectively. On the other
hand, the EDTA concentration was maintained at 0.1 mmol L− 1, but the
Cu2+ concentrations were changed to 0.1, 0.2, 0.3, and 0.4 mmol L− 1,
respectively. Other detailed experiment designs are shown in Table S1 in
the Supplementary Materials.
2.3. Analysis
Cu-EDTA was measured using high-performance liquid chromatog­
raphy (SCL-10ACP, Shimadzu) at 254 nm. 8% acetonitrile and 92%
oxalic acid solutions were the eluents, and the flow rate was 1.0 mL
min− 1. The Cu-EDTA removal processes were described using a first-
order reaction kinetic model as follows:
2O•−2 + 2H + →1 O2 + H2 O2 (1)
where C0 (mmol L− 1) represents the initial Cu-EDTA concentration and
Ct (mmol L− 1) represents its residual concentration after t min of
treatment, and k (min− 1) represents the kinetic constant.
The solution pH was measured with a pH meter (Shanghai INESA
Scientific Instrument CO., Ltd). A manometer laser particle size meter
(Mastersizer APA200, UK) was applied to determine the zeta potential
(ζ-potential). PS content was determined by iodimetry (Berkel et al.,
2006; Liang et al., 2008). Fourier transform infrared spectroscopy
(TENSOR-27, Bruker) was applied to characterize the chemical structure
of Cu-EDTA. ROS was detected as reported previously (Wang et al.,
2019a). Intermediates were detected by gas chromatograph-mass spec­
trometer (GC-MS, 7890B–5977B, Agilent, USA) and ion chromatog­
raphy (IC, ICS-90, DIONEX) (Wang et al., 2019a), and the pretreatment
processes and detection conditions are described in S1.
After decomplexation, precipitates were collected via alkaline pre­
cipitation as described in S2, and the physical and chemical properties of
the precipitates were analyzed using FTIR (Vetex 70, Bruker), X-ray
diffraction (XRD, Rigaku Ultima IV, Japan), X-ray fluorescence spec­
trometer (XRF, ARL PERFORM’X 4200, Thermo Fisher), and X-ray
photoelectron spectroscopy (XPS, Thermo ESCALAB 250XI).
3. Results and discussion
3.1. Cu-EDTA removal under different conditions
3.1.1. PS dosage
PS could be activated to produce ROS for organic pollutant removal,
and its dosage significantly affects pollutant removal performance
(Fernandes et al., 2019). Fig. 1a illustrates the effects of PS dosage on
Cu-EDTA removal efficiency. The solution pH was 4, and the initial
Cu-EDTA concentration was 0.3 mmol L− 1. The removal efficiency of
Q. Wang et al.
Fig. 1. Cu-EDTA removal performance under different operation conditions (a. effect of initial PS concentration on Cu-EDTA removal; b. effect of initial Cu-EDTA
concentration on it removal; c. EPR spectra at different Cu-EDTA concentrations; d. effect of molar ratio of nCu2+/nEDTA on Cu-EDTA removal).
Cu-EDTA was 54.17% at the PS concentration of 2 mmol L− 1 after 90
min of treatment. This result indicated that autocatalysis of PS induced
by Cu-EDTA occurred, which then contributed to Cu-EDTA removal. The
Cu-EDTA removal efficiency increased with the PS concentration,
reaching 100% when the PS concentration further increased to 80 mmol
L− 1 after 90 min. This could be due to the fact that the amount of ROS
increased with the PS concentration when the amount of reaction sub­
strates (Cu-EDTA) was constant. In addition, the consumption of radicals
by PS itself can also be another reason (Kan et al., 2020a). The rate
constant of parathion removal by microwave activated PS oxidation was
also enhanced with PS dosage (Kan et al., 2020a). The concentration of
10 mmol L− 1 PS was selected for the subsequent experiments, in order to
save the use of PS.
3.1.2. Cu-EDTA initial concentration
Fig. 1b shows the Cu-EDTA removal efficiency at different initial
concentrations. The Cu-EDTA removal efficiency was enhanced when
the initial Cu-EDTA concentration increased from 0.1 to 0.4 mmol L− 1 in
the first 30 min. Interestingly, after 90 min of treatment, a higher Cu-
EDTA removal efficiency was obtained with a lower initial concentra­
tion. Typical EPR signals at different Cu-EDTA initial concentrations are
shown in Fig. 1c. The intensity of the ROS signals increased with
increasing initial Cu-EDTA concentration. These results demonstrated
that more ROS were generated in the presence of a higher concentration
of Cu-EDTA, because more amounts of PS was activated by Cu-EDTA,
which favored Cu-EDTA removal at the first treatment stage (0–30
min). The species and contributions of ROS are identified and analyzed
in Section 3.2. Wang et al. (2019c) reported that the PMS-EDTA-Fe2+
system performed better oxidation and dewatering during sludge
treatment than the PMS-Fe2+ system. At the later stage (30–90 min),
most of PS was consumed by Cu-EDTA, and the residual PS concentra­
tion was relatively lower when the initial Cu-EDTA concentration was
higher. In this case, relatively higher Cu-EDTA concentration was
3
Journal of Cleaner Production 314 (2021) 128119
exposed to a relatively lower PS concentration. Cu-EDTA removal effi­
ciency was directly related to the PS dose. Due to the limited PS dosage,
the Cu-EDTA removal performance was lower when the initial Cu-EDTA
concentration was higher at this stage. The following experiments were
conducted with 0.1 mmol L− 1 Cu-EDTA.
3.1.3. Molar ratio of nCu2+/nEDTA
Fig. 1d illustrates the Cu-EDTA removal efficiency at different nCu2+/
nEDTA ratios. A sharp decrease in the Cu-EDTA removal was observed as
the nCu2+/nEDTA ratio decreased from 1:1 to 1:2, and nearly no removal
performance was observed at the molar ratio of 1:4. These results
indicated that excess EDTA was not conducive to the Cu-EDTA removal.
Free EDTA molecules can not only compete with Cu-EDTA for ROS, but
also chelate again with the Cu2+ released from Cu-EDTA. Excess EDTA
depressed the Cu-EDTA removal in a discharge plasma oxidation system
(Wang et al., 2018). By contrast, the increase in the nCu2+/nEDTA ratio
promoted Cu-EDTA removal. 46.01% of Cu-EDTA was removed after 20
min of treatment when the nCu2+/nEDTA ratio was 1:1, and the Cu-EDTA
removal efficiency significantly increased to 69.36% when the
nCu2+/nEDTA ratio was 4:1. These findings suggested that excess Cu2+
participated in the PS activation, favoring Cu-EDTA removal (Wang
et al., 2018). Lei et al. (2015) has elucidated the mechanism of PS
activation by Cu(II) and its potency for phenol removal.
3.1.4. Solution pH
The existing forms of organic substances in aqueous solution are
significantly affected by the solution pH value. Relatively lower solution
pH favored Cu-EDTA removal. Cu-EDTA removal efficiency reached up
to 98.9% after 90 min of treatment at an initial pH of 2, and it decreased
to 67.37% at the solution pH of 10, as shown in Fig. 2a. This might be
due to the different hydrolysis forms of Cu-EDTA at different solution pH
values (Guan et al., 2018). As depicted in Fig. 2b, CuH2EDTA and
CuHEDTA− are the major components at the solution pH 2, CuEDTA2−
Q. Wang et al.
Fig. 2. Effect of initial pH on Cu-EDTA removal (a. removal efficiency; b. Cu-EDTA speciation at various pH values).
and CuHEDTA− are the major components at the solution pH 4, and
CuEDTA2− is the dominant component at the solution pH values of 6, 8,
and 10 (Zeng et al., 2016a). Completely deprotonated CuEDTA2− has
more difficulty reacting with ROS than the protonated Cu complexes
(Wang et al., 2018). Zhao et al. (2013) also reported that basic condi­
tions were not beneficial for Cu-EDTA removal due to the existing form
CuOHEDTA3− .
4 and
In addition, the solution pH also affects the conversion of SO•-
•OH in the PS oxidation system. SO•- 4 is easily converted to •OH under
alkaline conditions. The redox potential of •OH is 2.7 V at acid condi­
tions and 1.8 V at alkaline conditions (Zeng et al., 2016a). Therefore,
acid conditions are more conducive to the removal of pollutants in the
PS system. Zeng et al. (2016b) reported that acidic conditions were
beneficial to the Cu-EDTA decomplexation process.
Cu-EDTA removal performance in this study was compared with
other methods. As shown in Table S2, it took 180 min to remove 72% of
Fig. 3. ROS detection and contributions to Cu-EDTA removal (a. ROS detection by EPR; b. DMPO spin-trapping spectra; c. TEMP spin-trapping spectra; d. inhibition
rate on Cu-EDTA removal after adding ROS quenchers).
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Journal of Cleaner Production 314 (2021) 128119
Cu-EDTA by the photoelectrocatalytic oxidation (Zhao et al., 2013).
Ion-exchanger/nanoscale zero-valent iron also needed 240 min to
remove 90% of Cu-EDTA (Liu et al., 2017). Great removal efficiencies
were obtained by bicarbonate-activated H2O2 oxidation (Wang et al.,
2019a), TiO2 photocatalysis (Lee et al., 2015), and interior micro­
electrolysis (Ju and Hu, 2011) within 60 min. In addition, the total cost
based on the equivalent removal of Cu-EDTA was also listed in Table S2.
Herein, the total fund contained energy consumption and reagent con­
sumption. The total cost of this study was approximately 0.22 USD/m­
mol Cu-EDTA. It was comparable with that of interior microelectrolysis
(0.19 USD/mmol Cu-EDTA), but much lower than those of other
mentioned methods. In this study, Cu-EDTA itself was used to activate
PS for Cu-EDTA removal, which saved the consumption of other
chemicals. Therefore, PS oxidation can be used as an effective method to
remove Cu-EDTA from wastewater.
Q. Wang et al.
3.2. Identification of ROS for Cu-EDTA removal
1
ROS including SO•- 4 , •OH, and O2 can be generated after PS acti­
vation (Liu et al., 2018), which would then contribute to contaminant
removal (Guo et al., 2021). EPR was used to detect the formation of ROS,
and its roles in Cu-EDTA removal was identified by ROS quenching
experiments (Kan et al., 2020b; Li et al., 2020a). The signals of 1:2:2:1
and 1:1:1:1:1:1 were observed in the EPR (Fig. 3a), which were sepa­
rately attributed to DMPO-•OH and DMPO-SO•- 4 , providing evidence
that SO•-
4 and •OH were generated after PS activation by Cu-EDTA. The
signals of •OH were much higher than those of SO•- 4 , due to the rapid
reaction of •OH with DMPO, as suggested by Wang et al. (2019c) and
Chen et al. (2019a). As the reaction proceeded, more amounts of •OH
was generated, as shown in Fig. 3b. In addition, the signals of 1:1:1 were
observed, which were attributed to TEMP-1O2, suggesting the formation
of 1O2 (Fig. 3c).
NaN3 and IPA were separately applied as the quenchers of 1O2 and
•OH (Huang and Zhang, 2019; Li et al., 2020b), and ethanol was applied
to capture •OH and SO•- 4 (Luo et al., 2019). Fig. S1 depicts the removal
reaction rate constants of Cu-EDTA with various quenchers. The
Cu-EDTA removal performance dramatically decreased after adding
these three quenchers, suggesting that they all contributed to Cu-EDTA
degardation. Then, the inhibition rate on Cu-EDTA removal after adding
ROS quenchers was calculated based on the changes in the removal
reaction rate constant (Wang et al., 2018). Fig. 3d depicts the inhibition
rate on Cu-EDTA removal after adding ROS quenchers. The inhibition
degrees followed the order: NaN3 ˃ ethanol ˃ IPA at the same quencher
dose. The inhibition rates were 96.12%, 92.29%, and 87.23% after
adding 1.0 mmol L− 1 NaN3, ethanol, and IPA, respectively. Based on the
above results, it can be deduced that the roles of ROS in the Cu-EDTA
removal process followed the order: 1O2>•OH>SO•- 4 . Wang et al.
(2020a) also reported that SMZ decomposition was mainly attributed to
4 and •OH oxidation in a Cu0–Cu2O/PS/UV system.
SO•-
3.3. Cu-EDTA decomposition process
3.3.1. Analysis of solution composition
Fig. 4a depicts the ζ-potential and solution pH during the Cu-EDTA
removal process. The absolute value of the ζ-potential and solution pH
both decreased with the treatment time. The ζ-potential decreased from
− 4.82 mV to − 2.37 mV after 90 min treatment. The decrease in the
absolute value of ζ-potential indicated the weaker electrostatic repulsion
between the organic molecules in the solution (Hu et al., 2018). In the
EDTA molecules, there existed some hydroxyl and carboxyl groups, and
these groups could be negatively charged to produce large electrostatic
repulsive force. After decomposition, these groups were cleaved, and the
electrostatic repulsion decreased, and the absolute value of the ζ-po­
tential decreased (Wang et al., 2019d). These findings demonstrated that
Cu-EDTA was decomposed by the PS oxidation. The solution pH also
Fig. 4. Variations of solution properties after Cu-EDTA decomposition (a. ζ-potential; b. solution pH).
5
Journal of Cleaner Production 314 (2021) 128119
decreased gradually to 3.29 after 90 min of treatment, suggesting that
some small molecular acids were produced after Cu-EDTA
decomposition.
The typical byproducts were detected and this information is shown
in Fig. S2 and Table S3. Several byproducts, including formic acid, 2-
hydroxypropanoic acid, oxalic acid, butanediol, ethanediol, propane­
diol, carbamic acid, and CH3COOH were identified. CH3COOH and NO−3
were gradually accumulated throughout the treatment period. Cu-IMDA
and Cu-NTA were considered preliminary intermediates during Cu-
EDTA decomposition by ROS (Wang et al., 2019a). Zhao et al. (2014)
also reported that Ni-EDTA decomposed into Ni-IMDA and Ni-NTA in a
photoelectrocatalytic process. Then, these Cu-containing complexes
(Cu-IMDA and Cu-NTA) were further oxidized and decomposed into
other byproducts (IMDA and NTA), accompanied by Cu release (Zhao
et al., 2013; Huang et al., 2016; Xu et al., 2017). In addition, Toxicity
Estimation Software Tool (T.E.S.T.) was applied to predict the quanti­
tative structure–activity relationship of these generated byproducts, as
shown in Table S4.
3.3.2. Analysis of precipitate composition
Chemical precipitation is widely used to remove the heavy metals
from water environment (Yan et al., 2019). After Cu-EDTA decom­
plexation, the released Cu species were collected by precipitation. Cu, O,
and C existed in the EDX mapping of sedimentary solids (Fig. 5), indi­
cating the formation of Cu-based oxides and Cu-base carbonates. Char­
acteristic peaks of CuCO3, CuO, Cu2(OH)2CO3, and Cu(OH)2 were
present in the XRD analysis of the precipitates (Fig. 6a). Most diffraction
peaks in the XRD pattern were in accordance with the XRD pattern of
CuO (JCPDS#80–1916), with 2θ values of 35.20, 38.42, 48.48, 53.3,
57.96, 61.24, 67.82, 72.10, and 74.88 (Abdelkader et al., 2020). This
suggested that CuO was the main species in the precipitates. Similar
results were also reported by Lee et al. (2015) and Xu et al. (2017).
Fig. 6b depicts the FTIR spectrum of the precipitates. –OH vibrations
were observed at 3417 and 1612 cm− 1 (Wu et al., 2011). Cu-based
carbonates showed peaks at 1500 and 1413 cm− 1. C–O and Cu–O–O
vibrations were observed at 1188 and 1107 cm− 1 (Schrader et al., 2014).
Carbonates were represented at 975 and 705 cm− 1. In addition, Cu(II)-O
vibrations were observed at 619 and 543 cm− 1 (Jiang et al., 2019).
These results suggested that some Cu-based carbonates and oxides were
produced in the precipitates. The occurrence of -CO3 group in the FTIR
spectrum suggested that some portions of Cu-EDTA were mineralized
and C element in the Cu-EDTA was converted to CO2, which resulted in
the appearance of CO2− 3 in the solution.
The valence distribution of Cu species in the precipitates was further
explored by XPS, as shown in Fig. 7. The binding energies of approxi­
mately 934.77, 531.87, and 284.87 eV corresponding to Cu2p, O1s, and
C1s, espectively, were present (Fig. 7a). For the Cu2p, two bands at
954.47 eV and 934.47 eV were observed, which indicated that Cu(II)
was the primary component of Cu species due to the energy gap of 20 eV
Q. Wang et al. Journal of Cleaner Production 314 (2021) 128119

Fig. 5. EDX mapping of precipitates after treatment (a. Cu mapping; b. O mapping; c. C mapping).

Fig. 6. XRD and FTIR of precipitates after treatment (a. XRD; b. FTIR).

(Fig. 7b) (Wang et al., 2019d). For Cu2p3/2, four bands at 932.7, 933.8,
934.6, and 935.0 eV corresponding to Cu(OH)2, CuO, Cu2CO3(OH)2, and
CuCO3 were separately observed (Fig. 7c) (Isahak et al., 2013), and the
proportions of these peaks were 15.73%, 23.27%, 32.91%, and 28.09%,
3.4. Autocatalytic activation mechanisms
There were two ways for metal ions to homogeneously catalyze PS to
produce radicals, such as SO•-4 and •OH (Zhou et al., 2016); SO4 could be
•-

respectively. For the resolution spectrum of O1s in Fig. 7d, three peaks at
531.5, 531.2, and 529.7 eV were observed, which corresponded to
–C–– O, –OH, and Cu–O (Peng et al., 2016), and their proportions were
53.7%, 34.4%, and 11.9%, respectively. According to the above anal­
ysis, Cu(OH)2, CuO, Cu2CO3(OH)2, and CuCO3 were the main compo­
nents of the sediment. In addition, the precipitate composition was
0.09Cu(OH)2⋅0.11CuO⋅0.079Cu2CO3(OH)2⋅0.07CuCO3 based on the
XRF analysis.
easily converted to •OH, and O•- 2 could be generated by the hydrolysis
and reduction of PS (Qi et al., 2016), resulting in the formation of 1O2
and the reduction of Cu2+, as shown in reactions 2–11 (Chen et al.,
2019b). Xu et al. (2017) reported that Cu-EDTA and its intermediates all
have the capability to activate PS. As shown in Fig. 8a, Cu2+, Cu-IMDA,
and Cu-NTA were selected to activate PS. Obvious signals from •OH
were observed after the addition of certain amounts of Cu2+, Cu-IMDA,
and/or Cu-NTA to the PS solution. These findings further demonstrated
that Cu2+, Cu-IMDA, and Cu-NTA can participate in PS activation. Wang
et al. (2020b) reported that the homogeneous activation of PMS by Cu2+

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Q. Wang et al. Journal of Cleaner Production 314 (2021) 128119

Fig. 7. XPS of the precipitates after treatment (a. full spectrum; b. core level spectrum of Cu2p; c. resolution spectrum of Cu2p3/2; d. resolution spectrum of O1s).

Fig. 8. PS activation by Cu2+, Cu-IMDA, and Cu-NTA (a) and Cu release (b).

relied on Cu(III) and/or Cu(I). In this study, Cu(III) was not detected by the release of Cu2+. Then, PS was further activated by the Cu-containing
the periodate method (Balikungeri et al., 1977); this might be inter­ intermediates and Cu2+ via Cu(I) conversion to produce more ROS,
preted as the Cu(III) being extremely unstable, and usually not exist promoting Cu-EDTA removal. This was in accordance with the results in
under acidic conditions (Lee et al., 2013). Cu(I) was detected and its Fig. 2b, in which the Cu-EDTA removal efficiency increased with the
amount was positively related to the treatment time (Fig. 8b), indicating Cu-EDTA initial concentration in the first 30 min.
that the activation of PS by Cu2+ followed reactions 3–4 (via Cu(I)
Cu2+ + S2 O2−8 →Cu3+ + SO•−4 + SO2−4 (2)
conversion). In addition, the Cu2+ concentration was 12.5 mg L− 1 after
90 min of treatment by PS oxidation, and it decreased to 0.38 mg L− 1
Cu2+ + O•−2 →Cu+ + O2 (3)
after alkaline precipitation, which met the discharge standard of Cu (0.5
mg L− 1) of the integrated wastewater discharge standard
Cu+ + S2 O2−8 →Cu2+ + SO•−4 + SO2−4 (4)
(GB18918-2002). Based on the above analysis, the autocatalytic acti­
vation mechanisms of PS for Cu-EDTA removal were proposed. First, PS
SO•−4 + OH − →SO2−4 + • O H (5)
was activated by Cu-EDTA to produce ROS, which would attack
Cu-EDTA, resulting in the formation of Cu-containing intermediates and

7
Q. Wang et al. Journal of Cleaner Production 314 (2021) 128119

SO•−4 + H2 O2 →SO2−4 + • O H + H + (6) and Cu-IMDA would also be produced after Cu-EDTA decomposition,
and then they were further decomposed to produce NTA and IMDA,
S2 O2−8 + H2 O→HO−2 + 2SO2−4 + 3H + (7) accompanied by Cu2+ release. NTA and IMDA were then oxidized and
decomposed into glycine, which was further converted to oxamic acid,
S2 O2−8 + HO−2 →SO•−4 + O•−2 + SO2−4 + H + (8) formic acid, and ammonium. Finally, CO2, H2O, and nitrate would be
generated after the decomposition of these organic acids (Xiang et al.,
Cu2+ + O•−2 →Cu+ + O2 (9) 2021).
Furthermore, the removal performances of different metal com­
O•−2 + • O H→1 O2 + OH − (10) plexes by PS oxidation, such as Cu-EDTA, Fe(III)-EDTA, and Ni-EDTA
were also evaluated. The experimental conditions were as follows. The
2O•−2 + 2H + →1 O2 + H2 O2 (11) solution temperature was 25 ◦ C, initial solution pH was 4, nMn+/nEDTA =
1:1, the PS initial concentration was 10 mmol L− 1, and the initial con­
According to the aforementioned analysis, possible decomposition
centration of each metal complex was 0.1 mmol L− 1. As shown in Fig. S3,
pathways of Cu-EDTA by the autocatalytic activation of PS are proposed
the removal efficiencies of Fe(III)-EDTA and Ni-EDTA were both lower
in Fig. 9. On the one hand, Cu-EDTA was undergone N–C bond cleavage
than 20% after 90 min of treatment. These different removal perfor­
and decomposed into CH3COOH and Cu-containing byproducts, such as
mances may be attributed to the different activation capacities of Cu-
Cu-EDDA (Xu et al., 2017). The Cu-containing byproducts were then
EDTA, Fe(III)-EDTA, and Ni-EDTA to PS. These results suggested that
oxidized to ethylene glycol and Cu2+ (Huang et al., 2016). Next,
the proposed process has a selectivity for heavy metal complexes
ethylene glycol was further oxidized to certain organic acids, which
removal.
were finally decomposed into CO2 and H2O. On the other hand, Cu-NTA

Fig. 9. Possible decomposition pathways of Cu-EDTA.

8
Q. Wang et al.
4. Conclusions
Cu-EDTA complex removal was successfully achieved by catalytic PS
oxidation at an acidic condition (pH = 4), and the multipathway acti­
vation of PS induced by Cu-EDTA was demonstrated. Cu-EDTA removal
efficiency was positively related to the PS dose. PS activation was first
triggered by Cu-EDTA, and a higher removal performance was observed
with a higher initial Cu-EDTA concentration in the early treatment stage.
Acidic conditions and an appropriate amount of Cu2+ facilitated Cu-
EDTA removal; however, negative effects were observed in the pres­
ence of EDTA. 1O2, •OH, and SO•- 4 were generated after PS activation,
which contributed to Cu-EDTA removal. ROS attacks resulted in chem­
ical structure destruction of Cu-EDTA, accompanied by the formation of
small molecular acids and alcohols. Cu-containing byproducts and the
released Cu(II) derived from Cu-EDTA decomposition participated in PS
activation, promoting more Cu-EDTA decomposition. Cu(I) conversion
was the main pathway for PS activation by Cu species. Overall, Cu-
EDTA, as a promising autocatalytic activator, can induce the multi­
pathway activation of PS, realizing effective removal of Cu-EDTA com­
plex itself from wastewater.
CRediT authorship contribution statement
Qi Wang: Conceptualization, Methodology, Data treatment, Data
curation, Writing – original draft, Writing-Review-Editing, Writing –
review & editing. Yutong Li: Investigation, Formal analysis, Resources.
Yue Liu: Investigation, Formal analysis, Resources. Jingyu Ren:
Conceptualization, Formal analysis, Methodology, Data treatment, Data
curation. Ying Zhang: Formal analysis, Methodology. Guangzhou Qu:
Formal analysis, Methodology. Tiecheng Wang: Methodology, Writing-
Review-Editing, Project administration, Funding acquisition, Writing –
review & editing.
Declaration of competing interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Acknowledgement
National Natural Science Foundation of China (No. 21976143) and
Chinese Universities Scientific Fund (2452018330.7) provided financial
supports to this study.
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.jclepro.2021.128119.
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