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Degradation of tricyclazole from aqueous solution and real wastewater by

electron-beam irradiation

Duy Ngoc Nguyen, Hieu Trung Nguyen, Thanh-Luu Pham, Cong

Tien Nguyen, Huong Thi Giang Duong, Hien Quoc Nguyen,
Yi-Ching Chen, Hiep Nghia Bui, Thi-Dieu-Hien Vo, Van-Truc Nguyen,
Ha Manh Bui

PII: S2352-1864(20)31615-1
DOI: https://doi.org/10.1016/j.eti.2020.101315
Reference: ETI 101315

To appear in: Environmental Technology & Innovation

Received date : 19 September 2020

Revised date : 9 December 2020
Accepted date : 12 December 2020

Please cite this article as: D.N. Nguyen, H.T. Nguyen, T.-L. Pham et al., Degradation of
tricyclazole from aqueous solution and real wastewater by electron-beam irradiation.
Environmental Technology & Innovation (2020), doi: https://doi.org/10.1016/j.eti.2020.101315.

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DEGRADATION OF TRICYCLAZOLE FROM

AQUEOUS SOLUTION AND REAL
WASTEWATER BY ELECTRON-BEAM

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IRRADIATION
Duy Ngoc Nguyen1,2, Hieu Trung Nguyen3, Thanh-Luu Pham4,5, Cong Tien
Nguyen6, Huong Thi Giang Duong7, Hien Quoc Nguyen2, Yi-Ching Chen8,

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Hiep Nghia Bui8, Thi-Dieu-Hien Vo9, Van-Truc Nguyen7, Ha Manh Bui7*
1
Ho Chi Minh City University of Technology (HUTECH), 475A Dien Bien Phu
Street, Ward 25, Binh Thanh District, Ho Chi Minh City 700000, Vietnam
2
Research and Development Center for Radiation Technology, Vietnam Atomic
Energy Institute, 202A Street 11, Thu Duc District, Ho Chi Minh City 700000,
Vietnam
3
Institute of Applied Technology, Thu Dau Mot University, 06 Tran Van On
4
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Street, Phu Hoa Ward, Thu Dau Mot City, Binh Duong Province 75000, Vietnam
Graduate University of Science and Technology, Vietnam Academy of Science
and Technology (VAST), 18 Hoang Quoc Viet Street, Cau Giay District 100000,
Vietnam
5
Institute of Tropical Biology, Vietnam Academy of Science and Technology
(VAST), 85 Tran Quoc Toan Street, District 3, Ho Chi Minh City 700000,
Vietnam
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6
Faculty of Chemistry, Ho Chi Minh City University of Education, 280 An Duong
Vuong Street, District 5, Ho Chi Minh City 700000, Vietnam
7
Department of Environmental Sciences, Saigon University, 273 An Duong Vuong
Street, District 5, Ho Chi Minh City 700000, Vietnam
8
Department of Environmental Engineering, Dayeh University, No.168 University
Street., Dacun, Changhua 51591, Taiwan
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9
Faculty of Environmental and Food Engineering, Nguyen Tat Thanh University,
Ho Chi Minh City, 300A Nguyen Tat Thanh St., District 4, Ho Chi Minh City
700000, Vietnam

*Email: manhhakg@yahoo.com.vn

Abstract: In this study, electron-beam (EB) irradiation was employed for the
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degradation of tricyclazole (TC) in an aqueous solution and real pesticide industry

wastewater (RPW). Acute toxicity tests revealed that TC exhibits low toxicity
against Daphnia magna, with LC50 values of 52.81 mg/L, 32.68 mg/L, 24.35 mg/L
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and 14.56 mg/L for TC at 24 h, 48 h, 72 h and 96 h, respectively. In contrast, RPW

exhibited high toxicity against D. magna, with LC50 values of 0.194%, 0.157%,
0.141% and 0.136% at 24 h, 48 h, 72 h and 96 h, respectively. Results revealed
that the high-efficiency removal of TC in an aqueous solution and RPW are
achieved by employing EB. Approximately 96.5% of TC in the solution was
decomposed under the optimum conditions of an absorbed dose of 3.5 kGy, a pH
of 7.0, and an initial TC concentration of 4 mg/L and a H2O2 concentration of 4

of
mM with an operating cost of ~0.92 $/m3, while 99.2% TC and 82.8% TOC from
real wastewater was eliminated at an absorbed dose of 4 kGy, and a H2O2
concentration of 5 mM, with an operating cost of 1.13 $/m3. The degradation of
EB apparently followed first-order kinetics, with an R2 of ~0.998. In real
wastewater, the central composite design was employed to optimize the absorbed

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dose and H2O2 concentration and predict the TC and TOC removal efficiencies.
Good regression coefficients (R2TC = 0.775 and R2TOC = 0.783) of the model
revealed fitted correlation between observed and predicted values. In addition, the
major degradation pathways of TC were suggested by density functional theory
and natural bond orbital calculations.

Keywords: Tricyclazole; fungicide; electron beam; hydrogen peroxide.

Introduction
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Pesticide residue contamination of the water environment originates
not only from agricultural fields but also from agricultural industries. In
recent decades, the use of pesticides in agricultural production has rapidly
increased worldwide, and it has enormously increased in Vietnam in
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particular (Nishimoto 2019). According to inventory data from the Plant

Protection Department in Vietnam, there were over 200 pesticide factories.
About 100 pesticide producing factories had a production capacity from
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30,000 to 40,000 tons/year, including more than 1,804 active ingredients

and 4,021 trade products in the entire country in 2019 (Salazar & Rand
2020). However, extensive use of pesticides become a current worldwide
public health issue due to persistence environmental degradation as well as
elevated threats on human health (Liao et al. 2020). Therefore, pesticide-
containing wastewater must be strictly controlled and treated before
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discharge into the environment.

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Wastewater originating from pesticide producing factories comprises

a mixture of several inorganic and organic components and various active
ingredients, and it is characterized by a specific odor of pesticides. This type
of wastewater contains a high organic content, with a biological oxygen

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demand (BOD5)/ chemical oxygen demand (COD) ratio of less than ~0.3; it
can be unsuitable for the application of biological treatment methods.
Chavan et al. (2016) reported high concentrations of sulfur and oil/grease in

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as well as the presence of organochlorine pesticides which is toxic to
aquatic animals in pesticide production wastewater. Tricyclazole (TC) is
active fungicide ingredients that is commonly produced under various trade
name in Vietnam (Chau et al. 2018; Sattler et al. 2018; Stadlinger et al.
2018). TC is relatively stable in the environment, but undergo rapid
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degradation under alkaline conditions. TC can bioaccumulate, harm aquatic
organisms and ecosystems, or exert adverse effects to the environment (Liao
et al. 2020). Therefore, in the absence of suitable mechanisms to manage
such pesticide wastewater, it could directly affect the health of workers in
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pesticide producing factories, surrounding communities, and the
environment. Although TC is one of the most common fungicides used to
control fungus in rice fields, marginal information of its toxic effects on
aquatic microcrustaceans is available.
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Electrocoagulation, microwave catalysis, biological methods,

adsorption and chemical oxidation method were employed for the removal
of pesticide contaminants in wastewater (Salleh et al. 2011; Kuan et al.
2013). However, these conventional methods require expensive or large
land areas that are threatened by urbanization or the lack of space. For
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example, biological methods take a long time and cannot degrade pesticides
due to the presence of compounds that can inhibit microorganisms
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(Pirkarami & Olya 2017; Mani et al. 2019). On the other hand, absorbents
cannot be efficiently reused (Salleh et al. 2011; Yuan & Ha 2015), and a
considerable amount of toxic sludge is released by coagulation (Ha 2018).
Oxidation methods, including the use of chlorine, ozone and oxygen, slowly

of
react with contaminants and require expensive contain or transfort materials
(Chen et al. 2001). In addition, these methods are not sufficient due to the
chemical complexity of the wastewater (Pirkarami & Olya 2017).

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Advanced oxidation processes (AOPs), such as Fenton, electrochemical
oxidation and H2O2, etc., which release hydroxyl radicals (OH), are
typically expensive (Bilińska et al. 2016). Hence, to eliminate pesticide
wastewater, methods in which appropriate quantities of chemicals and
resources are consumed, with more effective outputs that meet effluent
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requirements, should be developed.
Recently, the application of electron-beam (EB) irradiation—an
AOP technique—has attracted increasing attention due to its advantages of
facile operation, low initial cost, high performance, no sludge residues and
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no requirement of chemicals. Researchers reported that EB can eliminate
organic pollutants from petroleum waste (Wojnárovits et al. 2018), urban
wastewater (Kurucz et al. 1995), textile wastewater (Duy et al. 2019),
slaughterhouse wastewater (Kim et al. 2009; Cho 2010). Estimation of EB
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treatment costs relative to those of conventional methods revealed that EB

treatment is more expensive than chlorine treatment and less expensive than
activated sludge treatment (Kurucz et al. 1995).
Although there has been a significant increase in the number of
studies on the EB process for degrading recalcitrant organic compounds,
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there is a lack of knowledge regarding the fate and intermediates or

transformed products generated during EB irradiation (Kim et al. 2009; Cho
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2010; Duy et al. 2019). Recently, some researchers reported theoretical

calculations to explain the pollutant degradation pathways by AOPs (Han et
al. 2014; Nazari & Setayesh 2019). These studies were based on density
functional theory (DFT), representing one of the most commonly used and

of
effective theoretical calculation methods for optimizing geometric structures
and calculating electronic structures of a molecule by the application of
natural bond orbital (NBO) calculations (Nazari & Setayesh 2019). For

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example, OH released in AOPs are expected to ideally attack sites with
large partial negative charges, or the lowest unoccupied molecular orbital
(LUMO) of OH interacts with the highest occupied molecular orbital
(HOMO) of the organic molecule in the environment. Therefore, the charge
distribution and energy level of the localized highest occupied orbitals need
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to be considered. Several studies have correlated the relationship between
these two factors to the decomposition of organic compounds in the
presence of OH (Han et al. 2014; Changotra et al. 2019). The calculation
can determine the active centres on molecules that are preferentially
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attacked by OH, which typically exhibit a high electron density as well as a
large partial negative charge. Moreover, the degradation mechanism was
entirely investigated by the combination of DFT with liquid
chromatography–tandem mass spectrometry (LC/MS/MS).
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Even though numerous studies have been conducted to examine the

effect of EB on the degradation of recalcitrant organic compounds (Kim et
al. 2009; Cho 2010; Duy et al. 2019), not much information is available on
the degradation on tricylazole (TC) by EB, the synergistic effect (SE) of
H2O2 and EB, and the mechanism of the EB process. Therefore, for the first
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time, in this study, the effect of EB on the degradation of TC in solution and

real wastewater is investigated by factors such as the initial TC
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concentration, initial pH, H2O2 concentration and absorbed dose. In

addition, the degradation mechanism is examined on the basis of kinetics
studies, theoretical calculations, LC/MS analysis, toxicity of TC solution
and RPW on Daphnia magna and operating costs.

of
Experimental

Synthetic solutions
Stock (100 mg/L) solutions contaminated with TC were prepared

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using 100 mg of standard TC (Sigma-Aldrich) in water purified using a
Millipore reverse osmosis purification system. Serial solutions with
deionized water were prepared to obtain TC working solutions (2.0 to 8.0
mg/L). Analytical-grade solvents and other chemicals were used. The
chemicals and solutions were kept in the dark and stored at 4°C.
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Real wastewater (RPW)
Pesticide production wastewater was obtained from an equalization
tank at a wastewater treatment plant in Longan Province, Vietnam.
Wastewater was collected in a glass container and preserved at 4 °C for
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treatment by EB. Raw wastewater exhibited the following properties: pH of
4.97–6.82, COD of 930–1248 mg/L, BOD5 of 526–725 mg/L, total organic
carbon (TOC) of 530–1048 mg/L, Total suspended solids of 116–136 mg/L,
total nitrogen of 112–245 mg/L, coliform of 200–300 MPN/100 mL and TC
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of 2.1–8.2 mg/L.

Acute toxicity assay

D. magna cultures, obtained from MicroBioTest Inc., Belgium, were

maintained in 1-L glass beakers containing ISO medium. The animals were
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daily fed a mixture of Scenedesmus sp. and Chlorella sp. All cultures were

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renewed every 3 days and maintained at 25 ± 1°C and a photoperiod of

12:12 h light:dark cycles.
The acute toxicity assay was conducted according to the acute
immobilization test of the Organization for the Economic Cooperation and

of
Development (OECD 2004). Dissolved oxygen and water pH were
measured before and after exposure. Real pesticide wastewater (RPW) and
TC were used for the acute toxicity assay. For RPW, serial dilutions of

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0.05%, 0.0625%, 0.125%, 0.25%, 0.5% and 1%, as well as the blank
control, were used for the acute toxicity test. For TC, a series of different
TC concentrations (1, 2, 5, 10, 20, 40, 60, 80 and 100 mg/L) were used. All
test concentrations were prepared in triplicate in 50-mL glass beakers
containing 40 mL of ISO medium combined with RPW or TC. Ten neonates
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(<24 h old) were placed in each beaker. Exposure was conducted for 96 h at
a stable pH and temperature of 7–8 and 25±1°C, respectively. The
observation was recorded at 24 h, 48 h, 72 h and 96 h. All daphnids were
not fed, and the medium was not renewed during the acute toxicity test. At
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the end of the toxicity tests, the median lethal concentrations (LC50) at 24 h,
48 h, 72 h and 96 h were calculated by using Probit analysis.

Irradiation procedures
EB irradiation experiments were reported in our previous study (Duy
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et al. 2020). In short, 1000 mL of TC solutions or real wastewater with or

without H2O2 in a plastic box (solution thickness of 2.5 cm) was irradiated
at absorbed doses of 0.5 to 5.0 kGy by using an electron accelerator UERL–
10–15S2 (10 MeV, 7.5 kW), running on a conveyor (0-24 m/min) at the
Research and Development Center for Radiation Technology, Vietnam
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Atomic Energy Institute, Ho Chi Minh City (Duy et al. 2020). Dichromate
dosimetry (ASTM International 2004) was employed to measure absorbed
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doses at H2O2 dosages ranging from 1.0 to 6.0 mM. The pH of the initial
sample was adjusted from 3 to 9.

TC degradation kinetics
TC degradation kinetics were expressed by equations 1–3, where A0

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is the concentration of the initial TC solution, A is the concentration of the
TC solution at time t and k is the rate constant of TC degradation.

First-order reaction: Ln kt (1)

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Second-order reaction: kt (2)

Third-order reaction: 2kt (3)

Experimental design re-

The central composite design (CCD) was employed to establish the
optimum concentration ranges of H2O2 and absorbed dose required to
achieve the optimum reduction of TOC and TC in wastewater. Twenty-two
experimental runs were performed with three centre points and two
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randomized replicates, with a rotatability α of +1.414. The nonlinear
behaviour shown in terms of the TOC and TC removal efficiencies was
explained by Equation 4 (Bui 2017).
Y = β0 + β1X1 + β2X2 + β11X12 + β22X22 + β12X1X2 (4)
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Letters Y and X in the equation represent the response and factors,

respectively; βo is the constant coefficient; βj and βjj are the linear and
quadratic interaction coefficients, respectively. H2O2 dosages of 3 mM (low
level) and 5 mM (high level) were randomized with absorbed doses of 3.0
kGy (low level) and 4.0 kGy (high level) in the CCD study. Table 1 lists the
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selected H2O2 dosages and absorbed doses for the optimization study of the
TOC and TC removal.
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Table 1. Experimental range of independent parameters for wastewater treatment

Levels
Parameters
-1.414 -1 0 1 1.414

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Absorbed dose (kGy) X1 2.5 3.0 3.5 4.0 4.5
H2O2 concentration (mg/L) X2 1.5 3.0 4.0 5.0 6.5

Theoretical calculations

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Geometrical and electronic structures of the TC molecule and
predicted products were optimized by DFT at the B3LYP/6-311++G(d, p)
level of theory in a water solvent. In addition, NBO analysis was conducted
using the same software (Gaussian 09W) as that used for DFT calculations.
The polarizable continuum model was utilized as the water solvent model.
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Analysis method
LC-tandem MS equipped with a turbo spray electrospray (ESI) interface
(Agilent Technologies, Palo Alto, CA and MS/MS, 4000 QTRAP, Applied
Biosystems, USA) was utilized to monitor m/z transitions 190 → 136 for
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TC quantification. The initial solution pH values were determined using an
Inolab 740 pH meter. Results were expressed as the mean of triple
determinations, and statistical analyses were performed using Microsoft
Excel software release 2010 (Microsoft Corp., USA) and Minitab version
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18.0.0.

Results and Discussion

Prepared TC solution
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Effect of absorbed dose

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In the EB process, the absorbed dose determines the OH production rate
that could augment the TC removal capacity (equation 5) (Duy et al. 2020).

H2O ~~~→ 2.8OH + 2.7e-aq +0.6H +0.72H2O2 +2.7H3O+ + 0.48H2 (5)

In this serial experiment, the effect of the absorbed dose on the EB

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process from 0.5 to 5.0 kGy corresponding to 0.15 and 1.50 second was
investigated. Figure 1 shows the degradation and kinetic order results.

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Figure 1. Effect of different absorbed doses and reaction kinetic order
on TC degradation with a [TC]0 of 4 mg/L at pH 7 without H2O2
Figure 1 shows the effect of the variation in the absorbed dose on the
TC removal efficiencies. With the increase in the absorbed dose from 0.5
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(23.5%) to 3.5 kGy (89.6%), the degradation efficiency sharply increases,

and with the further increase in the absorbed dose, the removal efficiency
slowly increased. The increase in the rapid and slow degradation of TC with
the increase in the absorbed dose can be explained by the reaction between
•
OH and TC. At a constant TC concentration, the increase absorbed dose
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can accelerate •OH formation, leading to a rapid reaction with the TC

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contaminant. However, under saturated •OH conditions (absorbed dose of

greater than 3.5 kGy), •OH can react with other radicals or intermediate
compounds; therefore, the TC removal efficiency slowly increases. This
trend also can be confirmed in some previous studies (Shin et al. 2002; Duy

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et al. 2020). The reaction followed first-order kinetics, with an R2 of 0.9989
and a rate constant (k) of ~0.0022 1/m or 0.66 1/kGy. The first-order
reaction kinetics corresponding to the time required for the decomposition

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of 50% of the TC concentration are shown in equation 6.
𝐿𝑛 𝐿𝑛 𝐿𝑛2 0.0022. 𝑡 (6)
.

Therefore, the t50 value is 315.1 ms or the number of absorbed dose

(D50) is 0.350 kGy. Other kinetic orders, such as second and third, were not
fitted as the first-order reaction (Table S1). The maximum TC degradation
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(96.0%) was observed at an absorbed dose of 5.0 kGy. However, to reduce
the treatment cost of EB as well as optimize other parameters, a suitable
absorbed dose of 3.5 kGy was selected for further experiments.

Effect of TC concentration
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The effect of the TC concentration on the degradation efficiency by

EB was investigated by irradiating TC solutions with different
concentrations from 2.0 to 8.0 mg/L at a fixed absorbed dose (3.5 kGy) and
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initial pH (7) without the addition of H2O2.

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of
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Figure 2. Effect of different TC concentrations on the TC degradation
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efficiency at an absorbed dose of 3.5 kGy and pH of 3.5 without H2O2
At a low initial TC concentration from 2.0 to 4.0 mg/L, the TC
degradation rate increased more rapidly (Figure 2). However, at TC
concentrations of greater than 4.0 mg/L, the degradation efficiency sharply
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reduced from 89.6 (4 mg/L) to 47.1% (8 mg/L). This sharp reduction was
possibly related to fixed •OH formation could inadequate react with the
increasing number of TC. Moreover, at increasing TC initial concentration,
the number of intermediate products increases and these intermediate
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products acting as competitors with TC that lead degradation efficiency

decreases (Jia-Tong et al. 2017). At TC concentration of 4 mg/L, the
degradation efficienty start to switch state therefore this value is used in
subsequent experiments.
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Effect of initial pH

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The pH of the TC solution significantly contributes to the degradation

efficiency. The pH affected the generation of •OH and oxidation efficiency.
Effects of the initial pH on the removal of TC by EB were investigated in a
pH range from 3 to 9. TC concentrations and absorbed dose were

of
maintained constant at 4.0 mg/L and 3.5 kGy, respectively, for all batch
experiments, without the addition of H2O2. Figure 3 shows the effect of the
variation in pH on the degradation of TC by EB.

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With the increase in pH, the degradation efficiency of TC slightly
decreased. These results may be related to the complex mechanism during
the EB process, as shown in reaction 5. Because of no significant difference
in the removal efficiency of the pH values and the natural pH of 4 mg/L of
TC is ~7.0 (89.6%), indicating that there are no costs for additionally
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adjusting pH chemicals (NaOH or HCl); hence, the EB process is
economical. Therefore, a pH of 7 is selected to examine the SE of H2O2 and
EB.
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Figure 3. Effect of different pH values on the TC degradation with an

absorbed dose of 3.5 kGy and a [TC]0 of 4 mg/L without H2O2

Effect of hydrogen peroxide concentration

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Previously, several studies reported that H2O2 can accelerate •OH
formation and then enhance the removal of organics in some types of
wastewater (Kurucz et al. 1995; Duy et al. 2020). Figure 4 shows the results

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obtained for the effect of the variation in the H2O2 concentrations from 1.0
to 6.0 mM while maintaining the initial pH, absorbed dose and TC
concentration constant.

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Figure 4. Effect of different H2O2 concentrations on the TC degradation

efficiency at an absorbed dose of 3.5 kGy and a [TC]0 of 4 mg/L at pH 7
The use of H2O2 alone led to the slight increase in the degradation
efficiency (5.5% at 6 mM), while the use of EB coupled with H2O2 led to
the significant increase in the removal efficiency from 89.6 (EB alone) to
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91.4% (EB/1 mM H2O2) and 98.3% (EB/6 mM H2O2). The combined effect
of H2O2 and EB was considerably better than that of either component or
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the sum of the individual effect. These results revealed an interesting SE

between EB and the H2O2 concentration, which can be calculated by
equation 9 (Hien et al. 2012):
SE % Degradation efficiency / Degradation efficiency Degradation efficiency 9

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The higher the SE, the stronger the SE. This effect was calculated in
Figure S1.
With an increase in the H2O2 concentrations from 1 to 4, the SE

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increased, and after that, it decreased. These observations may be attributed
to the fact that under EB, H2O2 was easily converted into •OH , according to
equations 7 and 8 (Duy et al. 2020).
e-aq + H2O2 → OH+ OH− (7)
H + H2O2 → OH+ H2O (8)
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As a result, the SE was accelerated (increase from 0.6% at 1 mM to
3.6% at 4 mM). Moreover, with the increase in the H2O2 concentrations
from 4 to 6 mM (3.2%), SE decreased due to the scavenging effects of OH
at higher H2O2 concentrations, which induce a strong reaction with OH to
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produce weak oxidative substances (such as HO2• or O2) according to the
reactions 10 and 11 shown below.
H2O2 + OH → HO2 + H2O (10)
HO2 + OH → H2O + O2
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(11)
The results again demonstrated that H2O2 not only activates EB and
produces an increased number of OH but also interferes with the radicals in
water; these results are in good agreement with those reported previously
(Kurucz et al. 1995; Duy et al. 2020). The maximum SE of 3.6% was
observed for the combination of EB and H2O2, which was obtained under
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conditions of an absorbed dose of 3.5 kGy, a H2O2 of 4 mM and a TC of 4

mg/L at pH 7.

TC degradation mechanism by EB

Previous studies reported that the irradiation of EB on an aqueous

of
solution can lead to the formation of strong oxidizing agents such as OH
(Kurucz et al. 1995; Kim et al. 2009; Cho 2010; Wojnárovits et al. 2018;
Changotra et al. 2019). OH is a powerful oxidizing agent that is essentially

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an electrophile or an electron acceptor. Hence, the partial negative charge of
the atoms and the HOMO need to be considered. NBO analysis permits the
investigation of the interactions between molecules as well as charge
transfer. The interaction between the NBO electron donor and NBO electron
acceptor with similar energies is stabilized; hence, a chemical reaction
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occurs. If we consider the partial negative charges of the atoms in the TC
molecule, OH preferentially attack sites with a high electron density or
large negative charges. Therefore, to predict the TC decomposition by the
OH generated from EB, the quantitative charge of the atoms in the TC
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molecule must be determined, which can be solved on the basis of
theoretical quantum chemical calculation models. In this study, the
molecular geometry of the structures of TC and predicted products was
optimized by DFT, and their charge distribution was estimated by NBO
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calculations. Natural population analysis charges were used as the primary

basis for predicting the products that are obtained from TC decomposition.
The TC molecule structure was optimized in an aqueous solution by the
NBO charge distribution shown in Figure S2a. As can be observed in this
figure, the carbon C[13] position exhibited the highest partial negative
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charge in the TC molecule; hence, this position is first attacked by the

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hydroxyl radical. Next, as positions with high partial negative charges,

N[8](0.416), N[12](0.380) and N[11](0.337) were attacked one after
another. The product obtained by the attack of hydroxyl on C[13] was
denoted as TC-OH (Figure S2b). However, due to the association with the -

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OH group at position C[13], the charges of N[8], N[12] and N[11] were
slightly changed, but the order of magnitude of charge remained the same.
Further decomposition of TC-OH possibly occurred by two routes: 1)

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Considering the charge on the three N atoms in the TC molecule, the
reaction could occur by the attack of OH radicals on N[8], which exhibited
the highest negative charge; 2) however, the N[8] position was apparently
stereoscopically hindered; hence, as the second path, the reaction could
occur by the attack on the N[12] position, which exhibited the second-
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largest negative charge. K and L molecules were produced by the attack of
OH on the N[11] and N[12] positions, respectively. Similarly, the M
molecule was produced by the attack of OH on the N[8] position because
N[11] and N[12] atoms already formed covalent double bonds with oxygen
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also as a result of the same attack. The N molecule was produced by the
removal of NO3, CO2 and water from the M molecule. Similarly, the P
molecule was produced by the removal of SO42, CO2 and water of the O
molecule (Feng et al. 2019). Moreover, molecules B1, C, D, E and F were
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produced by the attack of OH on molecules A, B2, C, D and E,

respectively, in the order of the electrical charge magnitude at the positions
of the atoms that were the most negative. The G molecule was produced by
the removal of SO42, NO3, CO2 and H2O from the F molecule. Figure 5a
shows the major decomposition pathways of the TC molecule under the
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mechanism of partial negative charges.

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(a

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(b

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Figure 5. The possible major pathways by the partial negative charge
mechanism (a) and by the attack of OH on the highest occupied NBOs (b)
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However, considering the highest bonding and lone pair NBO
energy levels of the TC molecule and the predicted products, the major
degradation pathways of this molecule possibly differed from those when
considering partial negative charges. The C[2]–C[3] bond corresponding to
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the bonding NBO of the TC molecule exhibited the highest energy (7.20
eV) in a water environment; hence, in the obtained product (denoted as R),
the -OH group is attached to the C[2] position as a covalent bond is already
formed between the C[3] and C[13] atoms. Similarly, the C[1]–C[6] bond
corresponding to the bonding NBO of molecule R exhibited the highest
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energy (7.40 eV); hence, the -OH group is attached to the C[6] position

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(para position, denoted as S) because the -OH group is attached to the C[2]
or ortho position. The C[2]–C[3] bond corresponding to the bonding NBO
of the S molecule exhibited the highest energy (7.36 eV); hence, the C[2]
atom continues to be oxidized to a higher oxidation number of +2 to form

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covalent double bonds with oxygen. By the same calculations and inference,
Table S2 lists the following results for the energy level of bonding/lone-pair
NBOs, and Figure 5b shows the major pathways under this mechanism.

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Real pesticide wastewater

According to the primary experiment on TC solutions, the central point

of two main factors, i.e. the absorbed dose (3.5 kGy) and H2O2
concentration (4 mM), respectively, was selected at the optimal condition in
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the previous EB experiment. Table 2 also lists the range of values of
operational variables, percentage removal and predicted efficiencies of the
examined responses.
Table 2. Relationship between the absorbed dose and H2O2 concentration for
the EB process
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TC removal efficiency TOC removal efficiency
Experimental design
(%) (%)
Run
Absorbed dose
H2O2 (X2) Experiment Prediction Experiment Prediction
(X1)
1 3 5 89.3 89.8 71.9 71.3
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2 3.5 1.5 69.0 56.0 50.6 37.9

3 4 3 93.8 94.0 75.4 75.4
4 3.5 6.5 83.1 92.0 64.7 73.0
5 3.5 4 88.8 86.1 70.4 68.0
6 2.5 4 56.4 47.1 38.0 29.3
7 3.5 4 87.1 86.1 68.7 68.0
8 3 3 32.6 49.7 18.2 32.3
9 4 5 98.8 82.7 80.4 64.5
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10 3 5 88.6 89.8 70.2 71.3

11 4.5 4 76.4 84.3 58.0 65.7

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12 3.5 4 85.2 86.1 66.8 68.0

13 3.5 4 88.3 86.1 69.9 68.0
14 4 5 99.2 82.7 80.8 64.5
15 3 3 30.7 49.7 12.3 32.3
16 3.5 1.5 57.4 56.0 39.0 37.9
17 2.5 4 55.7 47.1 37.3 29.3

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18 3.5 4 86.4 86.1 68.0 68.0
19 3.5 6.5 87.6 92.0 68.2 73.0
20 4 3 92.4 94.0 74.0 75.4
21 3.5 4 85.0 86.1 66.6 68.0

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22 4.5 4 76.0 84.3 57.6 65.7

Table 3 lists the results from the analysis of variance (ANOVA) for the
quadratic regression model obtained from CCD used for the removal of TC
and TOC from pesticide wastewater.
Table 3. ANOVA results for the percentage TC removal and TOC reduction
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Source DF Adj SS Adj MS F- value P-value
TC removal
Model 5 6175.2 1235.04 11.18 0.000
X1 1 2080.9 2080.90 18.84 0.001
X2 1 1702.8 1702.77 15.42 0.001
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X12 1 1017.7 1017.71 9.21 0.008
X22 1 367.2 367.21 3.32 0.087
X1 X2 1 1318.8 1318.78 11.94 0.003
Residual error 16 1767.3 110.45
Pure error 13 94.1 7.24
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Total 21 7942.5
TOC reduction
Model 5 5951.2 1190.25 11.53 0.000
X1 1 1988.8 1988.83 19.27 0.000
X2 1 1624.7 1624.68 15.74 0.001
X12 1 1029.3 1029.32 9.97 0.006
X22 1 394.3 394.31 3.82 0.068
X1 X2 1 1242.9 1242.87 12.04 0.003
Residual error 16 1651.7 103.23
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Pure error 13 107.0 8.23

Total 21 7602.9
R2TC= 0.7775 and R2TOC= 0.7828
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From ANOVA, the factors with p-values of less than 0.05 were
distinguished to be significant. Low P values (<0.05) for the factors of X1,
X2, X12 and X1X2 (TC removal) and X1, X2, X22 and X1X2 indicated that all
linear, square and interactions should be included in the final model.

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Therefore, the model for predicting the removal of TC and TOC by using
EB is reconstructed to filter out the non-significant factors and predicted
models, as expressed by Equations 12 and 13, respectively:

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YTC = 264.4X1 + 112.6X2 –20.44X12 – 25.68X1X2 – 649 (12)
YTOC= 261.8X1 + 110.3X2 –2.01X22– 24.93X1X2 – 657 (13)
The model F values of 11.18 and 11.53 for the TC and TOC removal,
respectively, indicated that the model is sufficiently significant for the
regression analysis between response and variable effects. The fit of the
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model was verified by determining the regression coefficient (R2). The R2TC
and R2TOC values of 0.775 and 0.7828 indicated that the models cannot
explain the 21.72–22.25% variation of the mean or that the models exhibit
satisfactory adjustment of the quadratic models to the experimental data
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(Montgomery 2013). Moreover, some investigations revealed that an R2 of
greater than 0.70 is considered to be suitable for model fitting (Granato &
Masson 2010).

At an absorbed dose of 4 kGy and a H2O2 concentration of 5 mM,

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optimum TOC and TC removal efficiencies were 80.8 and 99.2%,

respectively (Figure 6). With the further increase in the H2O2 concentration,

the TC and TOC removal efficiencies increased slightly. Hence, a H2O2

concentration of 5 mM is optimized at an absorbed dose of 4 kGy to attain
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the highest removal efficiencies.

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(a
6
90
Hydrogen peroxide (mM)

5
70

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4

50 80
90
3

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40

2
80
60
2.5 3.0 3.5 4.0 4.5
Absorbed dose (kGy)

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(b 70
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Hydrogent peroxide (mM)

70 80
5
50

4
60
30 70
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3
20

2
40
60
2.5 3.0 3.5 4.0 4.5
Absorbed dose (kGy)
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Figure 6. Two-dimensional contour of a) TC and b) TOC removal efficiencies

Toxicity evaluation

Table 4 lists the lethal concentration (LC) values of TC and RPW

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against D. magna at different times intervals. The results indicated that TC

exhibits low toxicity against D. magna. LC50 values of TC against D. magna

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were 52.81 mg/L, 32.68 mg/L, 24.35 mg/L and 14.56 mg/L at 24 h, 48 h, 72
h and 96 h, respectively. Xueming and Daoyi (1993) reported an amphibian
mortality of Rana limnocharis after exposure to TC, with a CL50 value of
19,425 μg/L. In addition, CL50 values of TC were reported for the fish

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Lepomis macrochirus (1,609–3,880) μg/L) and Oncorhynchus mykiss
(1,500–2,200 μg/L) (USEPA 2013). Our results are in agreement with those
reported previously: TC exhibits low toxicity against invertebrates (USEPA

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2013). Our results agree with previously reported that TC showed low
toxicity on invertebrates (Xueming & Daoyi 1993; Rossaro & Cortesi
2013). However, the results indicated that the RPW exhibits high toxicity
against D. magna with LC50 values of 0.194%, 0.157%, 0.141% and 0.136%
at 24 h, 48 h, 72 h and 96 h, respectively. Probably, the RPW contained
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toxic compounds other than TC that contributed to toxic effects. Further
study is required to understand the toxic effects of unknown compounds in
RPW on aquatic organisms.
Table 4. Lethal dose LC50 of the TC solution and RPW on Daphnia magna
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Chemical Time (h) 24h 48h 72h 96h
LC10 22.322 12.637 7.713 4.300
TC (mg/L) LC50 52.810 31.680 24.350 14.560
LC90 84.354 52.492 42.932 25.925
LC10 0.082 0.058 0.042 0.035
RPW (%) LC50 0.194 0.157 0.141 0.136
LC90 0.306 0.257 0.242 0.234
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Cost comparison analysis

Besides treatment efficiency, operating cost is one of the essential

factors for determining treatment selection. The critical aspect of EB is the
energy consumption and H2O2 costs to achieve the maximum removal of
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TC at the lowest consumption amount as well as low operating costs.

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The energy consumption (Econ) of EB is related to absorbed dose (D)

and radiation energy utilization efficiency (f), which are typically 0.5 for
UELR-10-15S2 electro accelerator (Diem et al. 2017). Econ can be
calculated by Equation 14 as follows:

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𝐸 (14)
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With suitable absorbed doses of 3.5 and 4.0 for solution and
wastewater, respectively, the energy consumption in solution and real

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wastewater were 1.94 and 2.22 kWh/m3h, respectively. Given the
Vietnamese market in November 2020, the electrical energy price is 0.065
US$/kWh and H2O2 -50% price 2.0 US$/ liter.
Table S3 summarizes the costs originating from the optimal treatment
conditions. As shown in this table, the operating cost of the treated solution
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and real wastewater by EB under the optimum condition were 0.92 and 1.13
$/m3, respectively, for each cubic meter of the treated water. Under these
conditions, a majority of the TC or TOC was removed. This operating cost
was confirmed by Han et al. (2012). In their study, EB was employed for
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the purification of real textile wastewater, and the EB process was reported
to cost ~0.94 $/m3, which was cheaper than the existing process (1.1 to 1.2
$/m3).
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Conclusions

In this study, the electron beam process coupled with H2O2 was
employed for the treatment of tricyclazole (TC) in aqueous and real
pesticide production wastewater (RPW). In addition, the acute toxicity of
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this contaminant was evaluated. Results revealed that TC exhibits low

toxicity against D. magna. However, the RPW exhibited high toxicity
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against D. magna. TC treatment experiments were conducted at different

TC concentrations, absorbed doses, H2O2 dosages and initial pH values. At
optimum values of variables (absorbed dose of 3.5 kGy, TC of 4 mg/L, pH
of 7 and H2O2 concentration of 4 mM), almost all of the TC was eliminated

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(96.5%). The degradation of TC by EB apparently followed first-order
kinetics, with R2 and D50 of ~0.9989 and 1.050, respectively. Besides, the
major degradation pathways of TC under EB irradiation were elucidated by

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DFT theoretical calculations including NBO analysis. The central composite
design was applied, with two factors of absorbed dose and H2O2
concentration, respectively, for predicting the removal of TC and TOC in
RPW by the EB process. The R2TC = 0.775 and R2TOC = 0.7828 values for the
obtained quadratic model revealed a good correlation between observed and
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predicted values by using the mathematical model. At an absorbed dose of 4
kGy and a H2O2 concentration of 5 mM, the optimum TOC and TC removal
efficiencies were 82.8 and 99.2%, respectively. The EB operating costs
were ~0.92 and 1.13 $/m3 for the solution and real pesticide wastewater
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treatment, respectively, under this optimum condition. Results revealed that
EB radiation demonstrates promise for the degradation of organic pollutants
in aqueous solutions.
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Acknowledgments

This work was supported by the National Foundation for Science and Technology
Development (NAFOSTED) under Project No. 105.08-2019.17. The authors are thankful to
VINAGAMMA center for providing necessary conditions during the implementation of
this project.
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References
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 Journal Pre-proof

Bilińska L., Gmurek M. and Ledakowicz S. (2016). Comparison between

industrial and simulated textile wastewater treatment by AOPs –
Biodegradability, toxicity and cost assessment. Chemical
Engineering Journal 306, 550-9.

Bui H. M. (2017). Optimization of electrocoagulation of instant coffee

of
production wastewater using the response surface methodology.
Polish Journal of Chemical Technology 19(2), 67-71.

Changotra R., Guin J. P., Khader S. A., Varshney L. and Dhir A. (2019).

pro
Electron beam induced degradation of ofloxacin in aqueous solution:
kinetics, removal mechanism and cytotoxicity assessment. Chemical
Engineering Journal 356, 973-84.

Chau H. T. C., Kadokami K., Duong H. T., Kong L., Nguyen T. T., Nguyen
T. Q. and Ito Y. (2018). Occurrence of 1153 organic micropollutants
in the aquatic environment of Vietnam. Environmental Science and
re-
Pollution Research 25(8), 7147-56.

Chavan M., Thacker N. P. and Tarar J. L. (2016). Toxicity evaluation of

pesticide industry wastewater through fish bioassay. International
Journal of Applied Sciences 3(3), 331-9.
lP
Chen C. M., Shih M. L., Lee S. Z. and Wang J. S. (2001). Increased toxicity
of textile effluents by a chlorination process using sodium
hypochlorite. Water Science and Technology 43(2), 1-8.

Cho J.-Y. (2010). Evaluation of Degradation of Antibiotic Tetracycline in

rna

Pig Manure by Electron Beam Irradiation. Bulletin of Environmental

Contamination and Toxicology 84(4), 450-3.

Diem P. H. N., Thao D. T. T., Phu D. V., Duy N. N., Quy H. T. D., Hoa T.
T. and Hien N. Q. (2017). Synthesis of gold nanoparticles stabilized
in dextran solution by gamma Co-60 ray irradiation and preparation
of gold nanoparticles/dextran powder. Journal of Chemistry 2017.
Jou

Duy N. N., Hieu T. N., Thanh-Luu P., Xuan-Thanh B., Thuy T. D., Jiang J.-
J., Perng Y.-S., Boujelbane F. and Ha M. B. (2020). Removal of
27
 Journal Pre-proof

leucomalachite green in an aqueous solution by the electron beam

process. Journal of Water Process Engineering, 101781.

Duy N. N., Van Phu D., Lan N. T. K., Duoc N. T., Hien N. Q., Hiep B. N.,
Han B. N. and Ha B. M. (2019). Treatment of Real Textile
Wastewater Using Electron Beam Irradiation. Acta Chemica Iasi

of
27(2), 303-16.

Feng J., Sun J., Liu X., Zhu J., Xiong Y. and Tian S. (2019). Enhancement
and mechanism of nano-BaTiO3 piezocatalytic degradation of

pro
tricyclazole by co-loading Pt and RuO2. Environmental Science:
Nano 6(7), 2241-52.

Granato D. and Masson M. L. (2010). Instrumental color and sensory

acceptance of soy-based emulsions: a response surface approach.
Food Science and Technology 30(4), 1090-6.
re-
Ha B. M. (2018). Decolorization of Suncion Red P-2B Solution by Gamma
Co-60 Irradiation in the Presence of Hydrogen Peroxide. Journal of
Advanced Oxidation Technologies 21(1), 118-26.

Han B., Kim J. K., Kim Y., Choi J. S. and Jeong K. Y. (2012). Operation of
industrial-scale electron beam wastewater treatment plant. Radiation
lP
Physics and Chemistry 81(9), 1475-8.

Han W., Zhong C., Liang L., Sun Y., Guan Y., Wang L., Sun X. and Li J.
(2014). Electrochemical degradation of triazole fungicides in
aqueous solution using TiO2-NTs/SnO2-Sb/PbO2 anode:
rna

experimental and DFT studies. Electrochimica Acta 130, 179-86.

Hien N. Q., Van Phu D., Duy N. N. and Lan N. T. K. (2012). Degradation
of chitosan in solution by gamma irradiation in the presence of
hydrogen peroxide. Carbohydrate polymers 87(1), 935-8.

Jia-Tong L., Yong-Sheng L., Qing S., Da-Qian H., Dan Z. and Wen-Bao J.
Jou

(2017). The treatment of aniline in aqueous solutions by gamma

irradiation. Journal of Advanced Oxidation Technologies 20(1).

28
 Journal Pre-proof

Kim T. H., Nam Y. K. and Lee M. J. (2009). Electron-Beam Irradiation of

Livestock Wastewater in the Presence of Natural Zeolite. Journal of
the Korean Physical Society 54(5), 2109-14.

Kuan W.-H., Chen C.-Y., Hu C.-Y. and Tzou Y.-M. (2013). Kinetic
modeling for microwave-enhanced degradation of methylene blue

of
using manganese oxide. International Journal of Photoenergy 2013.

Kurucz C. N., Waite T. D. and Cooper W. J. (1995). The Miami Electron

Beam Research Facility: a large scale wastewater treatment

pro
application. Radiation Physics and Chemistry 45(2), 299-308.

Liao J.-Y., Fan C., Huang Y.-Z. and Pei K. J.-C. (2020). Distribution of
residual agricultural pesticides and their impact assessment on the
survival of an endangered species. Journal of Hazardous Materials
389, 121871.
re-
Mani S., Chowdhary P. and Bharagava R. N. (2019). Textile wastewater
dyes: toxicity profile and treatment approaches. In: Emerging and
Eco-Friendly Approaches for Waste Management Bharagava RN
and Chowdhary P (eds). 1st edn, Springer Nature, Singapore, pp.
219-44.
lP
Montgomery D. C. (2013). Design and Analysis of Experiments. John Wiley
& Sons, Inc., United States.

Nazari P. and Setayesh S. R. (2019). Effective degradation of Reactive Red

195 via heterogeneous electro-Fenton treatment: theoretical study
rna

and optimization. International Journal of Environmental Science

and Technology 16(10), 6329-46.

Nishimoto R. (2019). Global trends in the crop protection industry. Journal

of pesticide science, D19-101.

OECD (2004). Daphnia sp. acute immobilization test: OECD Guideline for
Jou

Testing of Chemicals. Organization for the Economical Cooperation

and Development, Paris, France.

29
 Journal Pre-proof

Pirkarami A. and Olya M. E. (2017). Removal of dye from industrial

wastewater with an emphasis on improving economic efficiency and
degradation mechanism. Journal of Saudi Chemical Society 21,
S179-S86.

Rossaro B. and Cortesi P. (2013). The effects of tricyclazole treatment on

of
aquatic macroinvertebrates in the field and in laboratory. Journal of
Entomological and Acarological Research 45(23), 128-36.

Salazar C. and Rand J. (2020). Pesticide use, production risk and shocks.

pro
The case of rice producers in Vietnam. Journal of environmental
management 253, 109705.

Salleh M. A. M., Mahmoud D. K., Karim W. A. W. A. and Idris A. (2011).

Cationic and anionic dye adsorption by agricultural solid wastes: A
comprehensive review. Desalination 280(1), 1–13.
re-
Sattler C., Schrader J., Farkas V. M., Settele J. and Franzén M. (2018).
Pesticide diversity in rice growing areas of Northern Vietnam.
Paddy and Water Environment 16(2), 339-52.

Shin H. S., Kim Y. R., Han B., Makarov I. E., Ponomarev A. V. and Pikaev
A. K. (2002). Application of electron beam to treatment of
lP
wastewater from papermill. Radiation Physics and Chemistry 65(4),
539-47.

Stadlinger N., Berg H., Van den Brink P. J., Tam N. T. and Gunnarsson J.
S. (2018). Comparison of predicted aquatic risks of pesticides used
rna

under different rice-farming strategies in the Mekong Delta,

Vietnam. Environmental Science and Pollution Research 25(14),
13322-34.

USEPA E. P. A. a. O. o. P. P. (2013). Pesticide Ecotoxicity Database

(Formerly: Environmental Effects Database (EEDB). In,
Environmental Fate and Effects Division, U.S. EPA., Washington,
D.C, USA.
Jou

30
 Journal Pre-proof

Wojnárovits L., Takács E. and Szabó L. (2018). Gamma-ray and Electron

beam based AOPs. In: Advanced oxidation processes for wastewater
treatment Stefan M (ed.). 1st edn, IWA publishing, London, UK, pp.
241-96.

Xueming P. and Daoyi L. (1993). Safety study of pesticides on bog frog, a

of
predatory natural enemy of pest in paddy field. Journal of Hunan
Agricultural College 19(1), 47-54.

Yuan P. S. and Ha B. M. (2015). The feasibility of cassia fistula gum with

pro
polyaluminium chloride for decolorization of reactive dyeing
wastewater. Journal of the Serbian Chemical Society 80(1), 115–25.

re-
lP
rna
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Highlights

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 Electron beam (EB) were employed to remove tricylazole (TC) in solution and real
wastewater
 LC50 values of D. Magna in wastewater seem more toxic than these value in TC’s

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solution
 TC degradation mechanism was also evaluated by kinetic studies and density functional
theory
 CCD were ultilized on absorbed dose and H2O2 to predict the TC and TOC removal
efficiencies re-
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AUTHORSHIP STATEMENT

Manuscript title: DEGRADATION OF TRICYCLAZOLE FROM AQUEOUS SOLUTION AND REAL

WASTEWATER BY ELECTRON-BEAM IRRADIATION

All persons who meet authorship criteria are listed as authors, and all authors certify that they have

of
participated sufficiently in the work to take public responsibility for the content, including participation in
the concept, design, analysis, writing, or revision of the manuscript. Furthermore, each author certifies that
this material or similar material has not been and will not be submitted to or published in any other
publication before its appearance in the Environmental Technology & Innovation.

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Authorship contributions
Please indicate the specific contributions made by each author (list the authors’ initials followed by their
surnames, e.g., Y.L. Cheung). The name of each author must appear at least once in each of the three
categories below.

Category 1 re-
Conception and design of study: B.M. Ha, N. Q. Hien, N.N. Duy;

acquisition of data: N.T. Hieu, N. T. Cong, D.T.G. Huong, B.N. Hiep;

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analysis and/or interpretation of data: T. L. Pham, Y.C. Cheng, V.T.D. Hien, N.V. Truc.

Category 2
Drafting the manuscript: B.M. Ha, N.N. Duy;
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revising the manuscript critically for important intellectual content: B.M. Ha, N.T. Hieu, N. Q. Hien, T. L.
Pham

Category 3
Approval of the version of the manuscript to be published (the names of all authors must be listed):
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B.M. Ha, N.T. Hieu, N. Q. Hien, T. L. Pham, N.N. Duy, N. T. Cong, D.T.G. Huong, B.N. Hiep, Y.C. Cheng,
V.T.D. Hien, N.V. Truc.

Acknowledgements
All persons who have made substantial contributions to the work reported in the manuscript (e.g., technical
help, writing and editing assistance, general support), but who do not meet the criteria for authorship, are
named in the Acknowledgements and have given us their written permission to be named. If we have not
included an Acknowledgements, then that indicates that we have not received substantial contributions from
non-authors.
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This statement is signed by all the authors (a photocopy of this form may be used if there are more than 10 authors):

Author’s name (typed) Author’s signature Date

Duy Ngoc Nguyen 09/ 12/ 2020

Hieu Trung Nguyen 09/ 12/ 2020

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Thanh-Luu Pham 09/ 12/ 2020

Cong Tien Nguyen 09/ 12/ 2020

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Huong Thi Giang Duong 09/ 12/ 2020

Hien Quoc Nguyen 09/ 12/ 2020

Yi-Ching Cheng 09/ 12/ 2020

Hiep Nghia Bui

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Thi-Dieu-Hien Vo 09/ 12/ 2020

Van-Truc Nguyen 09/ 12/ 2020

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Ha Manh Bui 09/ 12/ 2020
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Declaration of interests

☒ 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.

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☒The authors declare the following financial interests/personal relationships which may be considered
as potential competing interests:

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Ha Manh Bui

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