Chemosphere 303 (2022) 135057

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Chemosphere
journal homepage: www.elsevier.com/locate/chemosphere

Enhanced thermal activation of persulfate by coupling hydrogen peroxide

for efficient degradation of pyrene
Rui Qiu a, b, Peng Zhang a, b, Guojie Feng c, Xinxin Ni c, Zhu Miao c, Li Wei c, Hongwen Sun a, b, *
a
MOE Key Laboratory of Pollution Processes and Environmental Criteria, College of Environmental Science and Engineering, Nankai University, Tianjin, 300350, China
b
Tianjin Engineering Center of Environmental Diagnosis and Contamination Remediation, Tianjin, 300350, China
c
Beijing GeoEnviron Engineering & Technology Inc., Beijing, 100095, China

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

• The oxidation capacity of thermally

activated persulfate could be prompted
by adding H2O2.
• The activation energy was decreased
after introducing H2O2 into the ther­
mally activated persulfate system.
• The combined heat/persulfate/H2O2
process keep effective in a wide pH
condition.
• H2O2 can react with persulfate under
the thermal condition to produce more
active species.

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

Handling Editor: E. Brillas In this study, H2O2 was introduced into thermally activated persulfate oxidation system (T-HPS), and the
oxidation of pyrene (PYR) was investigated by the combined T-HPS technology. The results showed that H2O2
Keywords: could significantly improve the reactivity of the thermally activated persulfate system (T-PS), with 240-min PYR
Thermally activated persulfate degradation ratio increasing from 79.3% to 97.2% at 70 ◦ C. In the T-HPS system, as persulfate initial concen­
Dual oxidants
tration increased from 5 to 100 μM, the kinetic rate constant (kobs) of PYR degradation increased from 4.70 ×
PAHs
10− 3 to 3.01 × 10− 2 min− 1, but the kobs did not show a positive association with H2O2 concentration with the
Advanced oxidation processes
same range, and the highest kobs was obtained at the H2O2 initial concentration of 20 μM. The optimal ratio of PS
and H2O2 was set at 1:1 with the initial concentrations of the two oxidants both being 20 μM. Furthermore, PYR
could be removed efficiently in a wide range of pH, and the best PYR degradation performance was obtained
under neutral pH. Scavenging experiments demonstrated that •OH played a more important role in PYR
degradation in the T-HPS system than in the T-PS system. As suggested by the Arrhenius equation, the activation
energy decreased from 124.5 to 107.4 kJ mol− 1 after adding H2O2 to the T-PS system. This study provides a new
oxidation approach that could prompt the T-PS activity by adding a suitable dosage of H2O2.

* Corresponding author. Nankai University, 38# Tongyan Road, Haihe Education Park, Jinnan District, Tianjin, 300350, China.
E-mail address: [email protected] (H. Sun).

https://doi.org/10.1016/j.chemosphere.2022.135057
Received 14 March 2022; Received in revised form 3 May 2022; Accepted 19 May 2022
Available online 4 June 2022
0045-6535/© 2022 Elsevier Ltd. All rights reserved.
R. Qiu et al. Chemosphere 303 (2022) 135057

1. Introduction of PYR degradation by T-HPS process.

Advanced oxidation processes (AOPs), which are characterized by 2. Materials and methods
reactive oxidative species (ROSs) (e.g., hydroxyl radicals, •OH, E0 =
1.8–2.7 V; sulfate radicals, , E0 = 2.5–3.1 V), have become prom­ 2.1. Chemicals
ising treatment approaches for the degradation of recalcitrant organic
pollutants such as polycyclic aromatic hydrocarbons (PAHs), pharma­ Pyrene (PYR, C16H10, CAS129-00-0) was obtained from Sigma-
ceuticals, and dyes (Matzek and Carter, 2016; Liao et al., 2019). AOPs Aldrich, USA. Hydrogen peroxide (H2O2, 30%) was purchased from
are achieved by activating oxidants, including hydrogen peroxide Damao Chemical Company (Tianjin, China). Sodium persulfate
(H2O2), persulfate (PS, S2O2−8 ), ozone (O3), permanganate (MnO4 ), or a
−
(Na2S2O8), sodium bicarbonate (NaHCO3), solid chloride (NaCl), so­
combination of these (Liao et al., 2019; Dominguez et al., 2021; Qi et al., dium nitrate (NaNO3), and potassium iodide were purchased from
2021). Macklin Company (Shanghai, China). Tert-butanol (TBA, C4H10O) and
The AOPs based on PS can largely generate by various acti­ isopropanol (IPA, C3H8O) were bought from Concord Technology
vation methods, including heat, ultraviolet, ultrasound, and catalysts in (Tianjin, China). L-Histidine (L-HIS, C6H9N3O2) and p-benzoquinone (p-
homogeneous or heterogeneous forms (Matzek and Carter, 2016; Zhou BQ, C6H4O2) were obtained from Meryer Company (Shanghai, China).
et al., 2019). Among these activation methods, thermally activated Deionized water was used as reaction media. All chemicals were of
persulfate (T-PS) is considered to be a promising method for practical analytical grade and were used without further purification.
application by virtue of its high efficiency and nontoxicity without the
necessity of adding other chemicals (Valdes et al., 2015; Wen et al., 2.2. Experimental setup
2022). The T-PS technology has been applied in removing different
kinds of organic chemicals like trichloroacetic acid, dimethyl phthalate, All kinetic tests were carried out in 15 mL glass vials containing 10
and p-nitrophenol (Zhou et al., 2019). During the T-PS process, the mL reaction solution with PYR initial concentration of 100 μg L− 1
peroxide bond in the PS molecule can be split to produce (Ji et al., (approximately equals to 500 μM, determined according to its water
2015). It has been reported that the reaction stoichiometric efficiency in solubility, 135 μg L− 1). The vials were immersed in a thermostatic water
the T-PS system is higher than other activation methods like Fe2+ and bathing shaker (SHA-B, Boyuan Instrument Manufacture Company,
ultraviolet (Qi et al., 2021). However, the removal efficiency of pollut­ Changzhou, China), which was pre-heated to desired temperatures
ants in the traditional T-PS process is greatly limited by the reaction (50–80 ◦ C) or carried out at ambient temperature (T ≈ 25 ◦ C) immedi­
temperature, which needs the consumption of heating energy, leading to ately after the adding of preset amounts of oxidants (0–100 μM). When
a higher cost (Qian et al., 2022). Meanwhile, plenty of can be studying the influence of pH, HCl or NaOH solution (1 M) was used to
formed in the T-PS process at a higher reaction temperature, which may adjust the initial pH of reaction solution (in the range of 3–11), and no
lead to a low radical utilization ratio due to radical-scavenging reaction buffer was added during all the experiments so as to rule out the
(Khan et al., 2019). Thus, novel methods are needed to reduce energy quenching effects on radicals by buffers. The experiment lasted for 240
consumption and improve radical utilization performance in the T-PS min.
process. For quenching experiments, quenching agents (IPA and TBA with the
Hydrogen peroxide has always been known as an effective oxidant, concentration of 100 mM, p-BQ and L-HIS with the concentration of 0.1
which constitutes Fenton reaction together with Fe2+ to generate •OH. mM due to the limitation of soluble ability) were added before oxidants.
More recently, it has been reported that H2O2 can act as an additional IPA was applied as a quenching agent for both and •OH (Jorfi et al.,
oxidant to enhance the activation efficiency of PS by heterogeneous 2017; Watts et al., 2017). TBA was employed as a selective •OH scav­
catalysts (e.g., Fe–Mn binary oxides, magnetic fly ash, iron powder, enger (Chen et al., 2018). In addition, p-PBQ and L-HIS were employed
etc.), generating reactive species including , •OH and superoxide as and 1O2 scavengers, respectively (Xu et al., 2019b).
radical ( ) to removal refractory organic chemicals effectively (Li Reactor vials were taken out from the water bath and the reactions
et al., 2017; Xu et al., 2019a, 2019b). Usually, these Fe-containing were immediately quenched in an ice bath at the predetermined times.
heterogeneous catalysts could be transferred to Fe(III) oxides in AOPs, Subsequently, samples were taken and filtered through 0.22 μm syringe
producing red mud that needs to be recovered from the water system, filters for PYR measurement. Residual PYR and oxidants, solution tem­
which elevates the risk and cost of remediation technologies (Zhao et al., perature and pH were determined, and PYR degradation intermediates
2013; Lee et al., 2020). Hence, it is desired to develop a homogeneously of typical reaction system were explored. All the experiments were
activated dual oxidant AOP approach, like H2O2 activated T-PS system repeated three times and the average values were calculated.
(i.e. T-HPS), however, no related study could be found. Moreover, it has
been reported that the activation of PS by H2O2 in the presence of the 2.3. Analytical methods
above Fe-containing heterogeneous catalysts is due to the homolysis of
O–O bond in PS molecular by heat generated from the decomposition of PYR was determined using high-performance liquid chromatography
H2O2 (Sun et al., 2019a; Chen et al., 2021). This reaction mechanism (HPLC) (Agilent 1200) equipped with an FLD detector and an Inertsil
between PS and H2O2 needs confirmation in T-HPS system. Here, we ODS-SP reverse-phase C18 column (4.6 mm × 150 mm × 5 μm, Agilent).
propose a new combined activation method of PS by adding H2O2 to The injection volume was 10 μL, and the eluent (1 mL min− 1) was a
T-PS system for the remediation of refractory organic pollutants. mixture of water and acetonitrile at a volume ratio of 20:80. The
Moreover, the mechanism of the reaction between PS and H2O2 in the wavelengths of Ex and Em of the detector were set at 250 nm and 410 nm,
homogeneous-thermally activated PS process was intended to explore. respectively. The intermediates produced in the degradation reaction
Pyrene (PYR), which contains four benzene rings and is difficult to be were analyzed by GC-MS (Agilent 7890) equipped with a capillary col­
removed for its highly persistent and hydrophobic characteristics (Sun umn (0.25 mm × 30.0 m × 0.25 μm, HP-5-MS) in full scan mode after
et al., 2010), was employed as the target refractory organic pollutant to extraction and concentration of the reaction solution by n-hexane.
evaluate the applicability of T-HPS and to elucidate the underlying Oxidant concentrations (including PS, H2O2 and the mix of oxidants)
mechanism. The influences of several critical reaction conditions were monitored with a modified iodide spectrophotometry method (Sun
including temperature, oxidants concentration and pH were studied. et al., 2020a). Samples were measured after 20 min mixing with KI-N­
The ROSs generated in the T-HPS process were investigated and their aHCO3 solution using a spectrophotometer (Model-UV752, Lei-Ci Pre­
contribution to PYR degradation was evaluated. At last, the oxidation cision & Scientific Instrument Company, Shanghai, China) at a
intermediates of PYR were identified to elucidate the reaction pathway wavelength of 352 nm. In addition, pH values were detected using a pH

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R. Qiu et al. Chemosphere 303 (2022) 135057

meter (Lei-Ci Precision & Scientific Instrument Company, Shanghai, (1)

China), and the temperature was monitored by a digital thermometer
(Mitir Technology Company, Guangdong, China). All experiments were
3.2. The influence of initial H2O2 and PS concentrations
repeated in triplicate, and relative standard deviations were calculated.
To investigate the role of H2O2 and PS in T-HPS system, a series of
3. Results and discussion
experiments were employed by separately changing the initial concen­
trations of H2O2 ([H2O2]0) and PS ([PS]0) from 5 to 100 μM, respec­
3.1. Reaction kinetics of different oxidation systems
tively, while other conditions were maintained identically (Fig. 2). The
PYR degradation increased slightly as [H2O2]0 increased from 5 to 20
The PYR exhibited strong thermal stability at 80 ◦ C and can be hardly
μM in T-HPS system ([PS]0 was set at 20 μM), while decreased obviously
degraded by the two oxidants at room temperature (Fig. S1 in sup­
over 20 μM. The highest kobs of 15.25 × 10− 3 min− 1 was achieved at 20
porting materials). When the system was thermally activated (T =
μM H2O2. As the [H2O2]0 increased to 100 μM, the kobs decreased to 7.62
70 ◦ C), the PYR degradation was insignificant in T-H2O2 system
× 10− 3 min− 1. This result suggests that the activation of PS could be
(Fig. 1a), suggesting that H2O2 could not be activated by heat to produce
promoted by certain concentration of H2O2 under the thermal condition.
active species, which are able to degrade PYR. It has been reported that
However, excess concentration of H2O2 could obviously limit the PYR
H2O2 can be activated by microwave to produce •OH, which can effec­
degradation rate. This phenomenon could be explained by the scav­
tively degrade p-nitrophenol (Chen et al., 2020). Moreover, ultraviolet
enging effect of excess amount of H2O2 on the reactivity of that is
and vacuum ultraviolet could also remarkably enhance the degradation
responsible for PYR degradation in T-HPS system. Species with low
of an antibiotic, fluoroquinolone by H2O2 under the neutral pH condi­
oxidative activity, such as HO2• and , were generated from •OH,
tion (Sun et al., 2019b). These results suggest that H2O2 can be mainly
and highly reactive oxidants at higher H2O2 concentration (Eqs.
activated by non-thermal activation methods, such as transition metals,
(2)–(5)), thereby decreasing the PYR degradation efficiency (Yan et al.,
microwave, and ultrasound, etc.
2015; Xu et al., 2019a).
Rapid degradation of PYR occurred in T-PS oxidation system, and
79.3% of the initial 100 μg L− 1 PYR was removed at 240 min. When (2)
H2O2 was introduced, i.e., the T-HPS system, PYR degradation was
(3)
promoted further, and 97.2% of PYR was degraded after 240 min with
20 μM PS and 20 μM H2O2 under 70 ◦ C. The degradation of PYR followed (4)
pseudo-first-order kinetics. The kobs of the reaction in the T-HPS system
(15.25 × 10− 3 min− 1) was 2.21 times of that in the T-PS system (6.89 × (5)
10− 3 min− 1) (Fig. 1b), indicating that synergistic effects happened be­ Fig. 2c shows the effect of the initial PS concentration ([PS]0) on PYR
tween the two oxidants and thus accelerated the oxidation process and removal efficiency. It can be observed that the 240 min removal effi­
stimulated the PYR degradation. ciency of PYR increased from 43.9% to 100% as [PS]0 increased from 5
Even though 31.2% of H2O2 was decomposed by heat after reacting to 40 μM, and then maintained at 100% within a shorter operation time
for 240 min in T-H2O2 system (Fig. S2), the temperature changed as [PS]0 was increased from 40 to 100 μM. Correspondingly, kobs
insignificantly. Similar results occurred as well in T-HPS system increased from 4.70 × 10− 3 to 3.01 × 10− 2 min− 1 as [PS]0 increased
(Fig. S3), suggesting that thermal effect produced by H2O2 decomposi­ from 5 to 100 μM (Fig. 2d). These results indicated that PYR could be
tion was insignificant. Previous studies have illustrated that both •OH acceleratively degraded by increasing [PS]0. Similar result was also
and could be generated when H2O2 contacted with PS (Eq. (1)) observed in T-PS process for chloroxylenol degradation (Sun et al.,
(Monteagudo et al., 2015; Song et al., 2022). This might also happen in 2019a). Overall, on the view of eco-friendly factor, the optimal [H2O2]0
the T-HPS system. As well known, the generation of •OH and and [PS]0 were both set at 20 μM with a ratio of 1:1.
significantly determine the degradation of refractory organic contami­ The effects of various [PS]0 and [H2O2]0 used in binary oxidant
nants in AOPs (Wei et al., 2022). Moreover, it was found that •OH and system (HPS) were compared with the literature, with experimental
could coexist to degrade 2,4-dichlorophenoxy acetic acid effi­ conditions and oxidation performance being summarized in Table 1. For
ciently (Liu et al., 2021). Thus, the significant degradation of PYR in example, the optimal ratio of [PS]0 and [H2O2]0 in Fe–Mn binary oxides
T-HPS system could be achieved by the synergistic effects of •OH and catalyzed HPS system was 2:1 (Xu et al., 2019a). The degradation effi­
through the reaction between H2O2 and PS under the thermal ciency of 2,4-dinitrotoluene decreased with higher or lower [H2O2]0 (10
condition. mM), while the degradation efficiency of 2,4-dinitrotoluene decreased

Fig. 1. Reaction kinetic curve and kobs of PYR degradation (a, b). Experimental conditions: [PYR]0 = 100 μg L− 1, [PS]0 = [H2O2]0 = 20 μM, T = 70 ◦ C,
pH unadjusted.

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R. Qiu et al. Chemosphere 303 (2022) 135057

Fig. 2. Effects of [H2O2]0 (a, b) and [PS]0 (c, d) on PYR degradation and the corresponding kobs. Experimental conditions: [PYR]0 = 100 μg L− 1, the fixed [PS]0 =
[H2O2]0 = 20 μM, T = 70 ◦ C, pH unadjusted.

Table 1
Comparison of binary oxidant systems reported in the literature.
Catalysts Pollutant and concentration H2O2 (mM) PS (mM) Degradation efficiency Reference

Siderite (2.5 g L− 1) Methyl orange (50 mg L− 1) 15 2.5 Almost 100% within 480 min Song et al. (2022)
FMBOs (1.0 g L− 1) 2,4-dinitrotoluene (10 mg L− 1) 10 10 Almost 100% within 180 min Xu et al. (2019a)
Magnetic fly ash (2.0 g L− 1) Bisphenol A (50 mg L− 1) 15 5 97.3% within 60 min Xu et al. (2019b)
Fe2+ (0.15 mM) Naproxen (17.25 μg L− 1) 0.75 0.75 Almost 100% within 60 min Dulova et al. (2017)
Microwave (450 W) Dinitrodiazophenol (526.58 mg L− 1) 3.7 3.7 98.1% within 16 min Chen et al. (2020)
Heat (70 ◦ C) PYR (100 μg L− 1) 0.02 0.02 97.2% within 240 min The present study

as the [PS]0 increased beyond 20 mM. These results confirmed the temperature increased to 70 ◦ C, while 79.3% of PYR was removed in the
scavenging reactions between excess oxidants and reactive oxygen T-PS system at the same time. In addition, the degradation rate of PYR
species, which are also observed in the present study. Different catalysts was faster in the T-HPS system than in the T-PS system under the same
may have different activation mechanisms, thus the optimal ratios condition, and the gap between the two systems on PYR degradation
([PS]0/[H2O2]0) were different (Dulova et al., 2017; Xu et al., 2019b; rate became more obvious as the temperature increased (Fig. 3c). It
Song et al., 2022). Moreover, the same optimal ratio of [PS]0 and could be concluded that the degradation of PYR in T-HPS system was not
[H2O2]0 (1:1) was also observed in the HPS system activated by mi­ only due to the thermal activation of PS, but also attributable to the
crowave (Chen et al., 2020), which might be because microwave also reaction between the two oxidants.
possesses thermal effect, thus obtaining some results similar to ther­ To determine the temperature dependency of PYR degradation in the
mally activated process. T-HPS and the T-PS systems, the activation energy (Ea) was estimated by
correlation analysis between ln kobs of PYR degradation and reaction
temperatures (T− 1) based on Arrhenius equation (Eq. (6) and Fig. 3d).
3.3. Effect of temperature
Ea
ln kobs = lnA − (6)
The influence of the reaction temperature on the reactivity for PYR RT
degradation was examined. As the reaction temperature increased from The Ea value in T-PS system was 124.5 kJ mol− 1, which is close to
50 to 80 ◦ C, an acceleration effect on PYR degradation was observed in previous studies for diethyl phthalate (125.4 kJ mol− 1) (Wang et al.,
both T-HPS and T-PS systems (Fig. 3a and b), while PYR could not be 2019), triclosan (121.1 kJ mol− 1) (Gao et al., 2016), and chloroxylenol
degraded in the T-H2O2 system under 25–80 ◦ C (Fig. S4). The T-HPS (130.0 kJ mol− 1) (Sun et al., 2019a). The Ea value in T-HPS system
system presented a better performance of PYR degradation than the T-PS (107.4 kJ mol− 1) was significantly lower, suggesting that the introduc­
system. It could be seen in Fig. 3b, only 9.3% of PYR was removed in the tion of H2O2 in the T-HPS system in the present study could prompt the
T-PS system under 50 ◦ C after 240 min, and 25.8% of PYR was degraded PYR degradation efficiently from the view of energy.
in the T-HPS system under the same condition. Furthermore, PYR was
almost completely removed in the T-HPS system as the reaction

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R. Qiu et al. Chemosphere 303 (2022) 135057

Fig. 3. Effect of reaction temperature on PYR degradation kinetics in T-HPS system (a) and T-PS system (b), kobs in the two reaction systems (c), and plots of ln kobs vs
T− 1 for Ea calculation by Arrhenius equation (d).

Fig. 4. Effects of pH on PYR degradation efficiency and kobs in T-HPS system (a, b) and T-PS system (c, d), respectively.

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R. Qiu et al. Chemosphere 303 (2022) 135057

3.4. Effect of pH These results indicate that and •OH were the dominant reactive
species, and the degradation of PYR process just followed the radical
Five initial pH values (3.03, 5.05, 6.68, 9.06 and 11.01) ranging from pathway. In T-HPS system, and •OH accounted for 48.9% and
acid to basic pH were employed at 70 ◦ C, and both [PS]0 and [H2O2]0 40.3% of PYR degradation, respectively. In addition, p-BQ and L-HIS
were set at 20 μM (Fig. 4). As depicted in Fig. 4a and b, PYR could be exhibited no influence on the PYR degradation efficiency in T-PS system
degraded with high rates when the initial pH was in the range of 3–9 in (Fig. 5b), indicating that the PYR degradation process also completely
T-HPS system. The highest PYR removal performance was achieved at depended on the production of and •OH in the T-PS system, and the
pH 6.68, however, it suddenly decreased as the pH was adjusted to the contribution of and •OH accounted for 72.7% and 27.3%,
basic condition. When the initial pH was adjusted to 11.01, only 57.5% respectively. These results indicate that more •OH was produced in
of PYR could be degraded after 240 min with kobs of 4.06 × 10− 3 min− 1. T-HPS system. The higher PYR degradation efficiency in T-HPS could be
The pH of reaction solution did not change significantly due to the low attributed to the synergetic effects of the two ROSs.
concentrations of oxidants (Fig. S5). This result is consistent with pre­
vious studies of thermally activated PS for degradation of chloroxylenol
(Sun et al., 2019a), bisoprolol (Ghauch and Tuqan, 2012) and trichlo­ 3.6. Degradation pathway and toxicity estimation
roethylene (Liang et al., 2007), in which the highest remediation effi­
ciency occurred at near-neutral pH. PYR was degraded efficiently in T-HPS system and the intermediates
Additionally, the PYR degradation in T-PS system (Fig. 4c and d) was were identified after reacting for 30 min and 240 min by GC-MS
slower as compared to those in T-HPS system within the whole pH range, (Fig. S7). Three intermediates, i.e. dibutyl phthalate, phthalic acid,
illustrating that PYR degradation in the T-PS system could be acceler­ and 3,5-dimethlcyclohexanol, were detected at 30 min, and other 5 in­
ated by introducing H2O2 in a wide pH range. However, it should be termediates with smaller molecules, among which most are of alkyl
noted that T-PS system kept relatively stable performance at pH of 9.06 structure were found at 240 min (Fig. 6). Based on the chemical struc­
(Fig. 4d), while the efficiency of T-HPS system decreased suddenly at pH tures detected, PYR was deduced to decompose via the following way
of 9.06 (Fig. 4b) as compared to those at neutral pH. (Fig. 6): (1) the rings in the PYR molecule were disrupted into dibutyl
H2O2 could not keep stability under the basic condition (Mola­ phthalate, 3,5-dimethylcyclohexanol and 2,7-dimethyl-1-octanol, due
mahmood et al., 2021), 56.47% and 85.8% of H2O2 were decomposed at to the attack effect of ROSs in T-HPS system; (2) the ROSs could take
pH 9.06 and 11.01 under the 70 ◦ C (Fig. S6). Moreover, it has been effect on the intermediates and transform them into smaller molecules
reported that could transferred to HO• under basic condition, and further (Wu et al., 2022). Among all the intermediates, dibutyl phthalate
then HO• could be scavenged by OH− (Ji et al., 2015; Bruton and Sedlak, and phthalic acid were also detected as the intermediates of PYR in
2018). In addition, the synergetic reaction between PS and H2O2 could previous studies (Jamshidi et al., 2020; Wu et al., 2022).
be interrupted due to the decomposition of H2O2 and the transformation Moreover, the toxicities of the intermediates were analyzed by T.E.S.
of (Eq. (1)). Thus, the degradation efficiency of PYR decreased. T. to estimate the safety of the T-HPS system after PYR degradation (Kan
et al., 2021). As depicted in Fig. S8, the estimated 96 h LC50 values of
Fathead minnow, 48 h LC50 values of Daphnia magna and oral LD50 of
3.5. Identification of predominant species rat of the intermediates of PYR were all greater than PYR, suggesting
that the acute toxicities of PYR significantly decreased after the oxida­
To further explore the degradation mechanisms of PYR in both T-PS tion treatment. Moreover, the bioaccumulation factors of these oxida­
and T-HPS systems, IPA, TBA, p-BQ and L-HIS were employed as scav­ tion intermediates declined sharply (Fig. S8d). Therefore, it is a
engers to identify the generation of reactive species (Fig. 5a and b). In T- promising AOP method by introducing H2O2 into the thermal activation
HPS system, IPA reduced the PYR degradation efficiency from 97.2% to of PS process. It should be noted that more aspects should be investi­
16.7%, indicating that both and •OH contributed to PYR degra­ gated before this method could be recommended as a novel AOP
dation (Fig. 5a). The inhibition effect of TBA was also substantial, and approach in the remediation of contaminated soil.
PYR removal efficiency decreased to 47.5%, suggesting that •OH played
an important role in PYR degradation in T-HPS system. Moreover, 4. Conclusions
89.7% and 95.2% of PYR were removed when p-BQ and L-HIS were
added, respectively, illustrating that both and 1O2 presented a In the present study, we developed a novel AOP approach by intro­
negligible impact on the PYR degradation in T-HPS system. It has been ducing H2O2to thermally activated PS, i.e. T-HPS system, and the effects
reported that 1O2 plays an important role in PS oxidation system acti­ of H2O2 and other environmental factors on this AOP system were
vated through non-radial pathway (Wan et al., 2019; Sun et al., 2020b). explored by analyzing PYR degradation in the T-HPS system. The results

Fig. 5. Effects of radical scavengers IPA (100 mM), TBA (100 mM), p-BQ (0.1 mM) and L-HIS (0.1 mM) on PYR degradation efficiencies in T-HPS system (a) and T-PS
system (b).

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R. Qiu et al. Chemosphere 303 (2022) 135057

Fig. 6. Possible degradation pathways of PYR in the T-HPS system with framed chemicals being detected at 30 min and the other 5 detected at 240 min in GC-MS.

showed that the oxidation capacity of T-PS could be significantly Development Program of China (2018YFC1802006, 2018YFC1802001),
improved after adding H2O2. The PYR could be degraded efficiently the special fund for Technology Innovation Guidance of Tianjin
under the identified condition ([PYR]0 = 100 μg L− 1, [PS]0 = [H2O2]0 = (21YDTPJC00270), Major Scientific and Technological Innovation
20 μM, 70 ◦ C, pH unadjusted) with the degradation rate constant of Project of Shandong Province (2021CXGC011206), Science and Tech­
15.25 × 10− 3 min− 1, which is 2.21 times of the value in T-PS system. As nology Major Project of Tianjin (18ZXSZSF00110), and Ministry of Ed­
[H2O2]0 increased, the PYR degradation rate increased first and then ucation of China (T2017002).
decreased, indicating the importance of the ratio of [H2O2]0 and [PS]0.
As the reaction temperature increased, the PYR degradation rate Appendix A. Supplementary data
increased significantly in both T-HPS and T-PS systems, and the reactive
energy decreased from 124.5 to 107.4 kJ mol− 1 after introducing H2O2 Supplementary data to this article can be found online at https://doi.
into the T-PS system. The influence of pH (ranged from 3 to 9) on the org/10.1016/j.chemosphere.2022.135057.
PYR degradation was insignificant under neutral and acid pH, however,
as the initial pH increased to 11, the PYR degradation process was References
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Declaration of competing interest Ji, Y., Dong, C., Kong, D., Lu, J., Zhou, Q., 2015. Heat-activated persulfate oxidation of
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This work was supported by the National Key Research and

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