Separation and Purification Technology 235 (2020) 116226

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Separation and Purification Technology

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Degradation of trans-ferulic acid in aqueous solution by a water falling film T

DBD reactor: Degradation performance, response surface methodology,
reactive species analysis and toxicity evaluation
⁎
Jingyu Rena,c, Jie Lia,b,c, , Nan Jianga,b,c, Kefeng Shanga,b,c, Na Lua,b,c, Yan Wua,b,c
a
Key Laboratory of Industrial Ecology and Environmental Engineering, MOE, Dalian University of Technology, Dalian 116024, China
b
School of Electrical Engineering, Dalian University of Technology, Dalian 116024, China
c
School of Environmental Science & Technology, Dalian University of Technology, Dalian, China

A R T I C LE I N FO A B S T R A C T

Keywords: In this study, a water falling film dielectric barrier discharge (DBD) reactor was used to degrade trans-ferulic acid
Dielectric barrier discharge plasma (FA) in water. The results show that 98.4% of FA was degraded by 10 min treatment with the discharge voltage
Response surface methodology of 19 kV. The reactor displayed an excellent energy efficiency, which could reach to 13.4 g/kWh for FA de-
Trans-ferulic acid gradation. Degradation characteristics of the water falling film DBD for FA was studied by single factor ex-
Advanced oxidation processes
periments and response surface methodology. The optimal operating condition and a quadratic polynomial
equation for predicting FA degradation efficiency were obtained by the response surface model. The reactive
species analysis unveils that the peroxone reaction between H2O2 and O3 generated by DBD could promote the
formation of %OH, causing a synergistic effect for FA degradation. Hydrated electron (eaq−) converted into %H in
FA solution. In the present reaction system, %H preferred to react with FA rather than merge with %OH, and %H
showed a well ability to degrade FA. FA solution toxicity was weakened after DBD treatment.

1. Introduction more attention as a promising alternative to the conventional advanced

Olive mill wastewater (OMW) is classified as a hardly degradable
waste because it contains a large number of phenolics [1]. The dis-
charge of OMW into environment has caused serious environmental
problems, including eutrophication, odour and aesthetic deterioration
of the ecosystems [2–4]. The phenolics in OMW are identified to be able
to damage the liver and kidney cell membranes of animals and hinder
the feeding of phytophagous animals [1–4]. In the OMW, trans-ferulic
acid (FA) is the most common phenolic [5]. Researchers have at-
tempted several technologies to treat FA wastewater such as photo-
catalysis [6], electrochemical oxidation [7], Fenton-like [8], catalytic
wet oxidation [9]. Although good treatment effect has been achieved,
there are some disadvantages still need to be solved for these processes.
Fenton-like and photocatalysis suffer the problems of catalyst in-
activation and leak. Catalytic wet oxidation requires high equipment
costs, and the equipment corrosion is inevitable in the operation en-
vironment of high temperature and pressure. Electrochemical oxidation
is sensitive to solution conductivity, and the electrode consumption is
quick. Hence, it is urgent to develop an effective method to treat OWM.
In present years, electrical discharge plasma has received more and
oxidation processes [10–13]. During the electrical discharge, energetic
electrons are produced, and they can collide with background mole-
cular such as O2 and H2O to form reactive species including %OH, %O
and %H etc. [14–17]. These species have quite high reactivity, being
able to quickly degrade pollutants [18]. Compared with other AOPs,
electrical discharge plasma technology is clean and environmentally
friendly because it requires no extra chemicals and thus will not bring
secondary pollution. Moreover, a variety of strong reactive species in
the electrical discharge process make it has an excellent performance
for pollutant degradation [19]. Among the various electrical discharge
modes, dielectric barrier discharge (DBD) is one of the most commonly
used discharge mode [15,20], which has the uniform discharge and can
be operated under high solution conductivity and complicated water
quality conditions [21–23]. Therefore, DBD is more suitable for prac-
tical application in comparison to most of discharge modes. Although,
electrical discharge plasma process owns many incomparable ad-
vantages, the energy efficiency of the technology is often unsatisfactory
because part of reactive species generated by electrical discharge is
unable to be sufficiently utilized to degrade pollutants in conventional
reactor configurations, posing the waste of energy. To overcome the

⁎
Corresponding author at: Key Laboratory of Industrial Ecology and Environmental Engineering, MOE, Dalian University of Technology, Dalian 116024, China.
E-mail address: lijie@dlut.edu.cn (J. Li).

https://doi.org/10.1016/j.seppur.2019.116226
Received 30 July 2019; Received in revised form 10 October 2019; Accepted 17 October 2019
Available online 19 October 2019
1383-5866/ © 2019 Published by Elsevier B.V.
J. Ren, et al.
problem, we propose using a water falling film DBD reactor to improve
the energy efficiency of electrical discharge process. In this reactor,
high voltage electrode is covered up by a dielectric and the dielectric is
placed in the center of a cylindrical ground electrode. 12 pores are
punched in the ground electrode to make the water film evenly dis-
tributes on the inner surface of ground electrode. The uniformity of
water film is a crucial factor for the energy utilization because the water
film is easy to cluster, causing that lots of plasma can’t contact the
wastewater. In addition, O3 generated in gas phase within the water
falling film DBD reactor can be bubbled into the treated solution to
improve the energy efficiency. O3 is a strong oxidant, which can react
with pollutant directly or transform into %OH to degrade pollutants.
Previous studies have proved that O3 and electrical discharge plasma
have a synergistic effect for pollutant degradation [24].
In this study, FA was employed as the representative of phenolics of
OMW. The degradation characteristics of the water falling film DBD
reactor for FA was investigated by single factor experiments with dif-
ferent variations. Response surface methodology was employed to build
a model to predict FA degradation efficiency and further reveal the
interaction of the variations. It should be emphasized that although
oxidizing species is the most important reactive species, reduction re-
actions can also take place in electrical discharge plasma; however,
reductive species are always neglected in most of studies. Hence, the
evolution of reactive species including oxidizing and reductive species
and their effect on FA degradation were studied in this work. FA toxi-
city was evaluated by seed germination experiments.
2. Materials and methods
2.1. Materials
FA (99%) were purchased from Aladdin Industrial Corporation,
China. All of the reagents used in this study were analytical grade and
no further purification required.
2.2. Experimental setup
The experimental system is shown in Fig. 1a. The water falling film
DBD reactor was mainly consisted by a high voltage electrode, ground
electrode, dielectric and Teflon holders. The length, outer diameter and
inner diameter of the ground electrode were 200, 22 and 20 mm, re-
spectively, while those parameters of dielectric were 300, 12 and
10 mm, respectively. The length and diameter of high voltage were 350
and 10 mm. 12 pores with diameter of 2 mm was punched in the ground
electrode to evenly distribute the water film. FA solution in the vessel
was injected into the DBD reactor by a peristaltic pump (Longer pump,
BT00-300T). The O3 generated in the gas phase in the reactor was
bubbled into the vessel by a gas pump. A magnetic stirring apparatus
was used to promote the mass transfer of O3. A 50 Hz of AC power
(special power source factory of DUT, AC-50) was used as the power
supply.
The discharge power is different with and without water film. In
order to investigate sole O3 treatment and keep the discharge char-
acteristics the same, a sealed vessel (vessel A) with FA solution was
recycled into DBD reactor, while the O3 was blown into another vessel
(vessel B) through the vessel A. The solution in vessel B was sampled.
The experimental system is shown in Fig. 1b.
2.3. Analysis methods
A high performance liquid chromatograph (HPLC) (Shimadu LC-
10Avp) was used to measure FA concentration. The detection wave-
length was 320 nm. Methyl alcohol and 0.3% glacial acetic acid aqu-
eous solution were the mobile liquid (40:60 V/V). The flow rate of the
mobile phase was 0.8 mL/min.
Lissajous figure was employed to calculate the discharge power,
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Separation and Purification Technology 235 (2020) 116226
obtained by an oscilloscope (Tektronix, TDS2024) equipped with a high
voltage probe (Tektronix, P6015) and a low voltage probe (Tektronix,
TPP0101) across a 1 μF capacitor.
The energy efficiency was evaluated by G50, given as Eq. (1)
0.5m
G50 =
P × t50 (1)
where m (g) was FA initial mass, P (kW) was the discharge power, and
t50 (h) was the time when 50% of FA was degraded
The synergistic effect between plasma and O3 was evaluated by
synergistic factor, calculated by Eq. (2)
k plasma/O3 − (kplasma + k O3)
Synergistic factor = × 100%
k plasma + kO3 (2)
−1
where kplasma/O3, kplasma and kO3 (min ) were the apparent pseudo-
first order reaction rate constants of FA degradation for plasma/O3,
DBD plasma and ozonation.
Dissolved ozone concentration was measured using the indigo
spectrophotometry, and the detection wavelength was 610 nm [25].
H2O2 concentration was also measured by a spectrophotometer (INESA,
752N) using titanium sulfate as the chromogenic agent, and the de-
tection wavelength was 410 nm [26]. %OH yield was monitored by
HPLC using salicylic acid as the molecular probe. The mobile phase was
composed of 10% (V/V) acetonitrile, 10% (V/V) methanol, 0.3 mol/L
acetic acid, 0.03 mol/L citric acid and ultra-pure water. The detection
wavelength was 296 nm [27].
The specific experimental methods of seed germination experiments
are described in text S1 in SI.
3. Results and discussion
3.1. Effect of discharge voltage on FA degradation
The FA degradation efficiency by plasma combined ozone (model
1), single plasma (model 2) and single O3 (model 3) treatment at dif-
ferent voltage was investigated. Turning off the air pump can achieve
the purpose of treating FA by plasma alone, and turning on the air
pump can co-treat FA with plasma and ozone. The operation of in-
dividual ozone treatment is discussed in detail in Fig. 1b. The effect of
discharge voltage on FA degradation is shown in Fig. 2. The results
unveil that FA degradation efficiency increased with the increase of
discharge voltage. When the discharge voltages were 15 kV, 17 kV and
19 kV, the degradation efficiency of FA by model 1 was 74.3%, 92.7%
and 98.4%, respectively. In Fig. 2, it can also be found that FA de-
gradation efficiency by plasma alone (model 2) treatment was higher
than that by sole ozone (model 3) treatment. For example, FA de-
gradation efficiency after 10 min model 2 and model 3 treatment was
68.3% and 62%, respectively when the discharge voltage was 17 kV.
The synergistic factors between plasma and ozone were 18.6%,
20.1% and 20.3% at 15, 17 and 19 kV, respectively, indicating the
plasma and ozone had a synergistic effect for degrading FA but it did
not change obviously with the increase of discharge voltage. This can
be attributed to the fact that FA degradation rate constants by model 1,
model 2 and model 3 enhanced simultaneously with increasing dis-
charge voltage, causing the change of synergistic factors was not ob-
vious.
It can be seen from Table 1 that the introduction of ozone generated
in gas phase into FA solution is an effective strategy to enhance energy
utilization. Taking 17 kV as an example, the energy efficiency of FA
degradation by model 2 and model 3 was 6.1 and 5.1 g/kWh, respec-
tively, while the energy efficiency of the model 1 reached to 13.4 g/
kWh. Table 1 also indicates that energy efficiency of the three methods
was improved when the discharge voltage increased from 15 kV to
17 kV, implying the increase of discharge voltage enabled to degrade
more FA with specific energy consumption. However, the energy
J. Ren, et al.
Fig. 1. (a) Schematic diagram of the experimental system; (b) schematic diagram of sole O3 treatment method.
efficiency of the model 1 was 12.1 g/kWh at the discharge voltage of
19 kV, which was lower than that of 17 kV (13.4 g/kWh). This is be-
cause plasma combined with O3 (model 1) had a high treatment effect
on FA at 17 kV, and further increasing the discharge voltage couldn’t
significantly increase the degradation efficiency, resulting in a waste of
energy. At the same time, the energy efficiency of model 2 and model 3
still increased with the increase of discharge voltage because lots of FA
has not been degraded by the two methods, and there was still room for
energy efficiency to be improved. According to the above, 17 kV had
the highest energy efficiency for the DBD reactor (model 1). Then, TOC
removal with 17 kV was investigated to evaluate the mineralization of
FA by the reactor. About 20.9% of TOC was removed by model 1, while
about 10% of TOC could be removed by plasma alone. Only 3.4% of
TOC was removed by ozone alone. Ozone is selective in the degradation
of pollutants and cannot effectively remove organic small molecular
acids in water, and thus its mineralization effect of pollutants is usually
limited [24]. The higher removal efficiency of TOC in the model 1 also
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Separation and Purification Technology 235 (2020) 116226
shows the synergistic effect between plasma and ozone.
Table 2 compares FA degradation results under different treatment
methods. Fenton-like treatment requires 50 min to completely degrade
FA with the initial concentration of 4 mg/L [8]. Photocatalysis and bio/
photocatalysis need at least 180 min to obtain the degradation effi-
ciency higher than 80%, and the energy efficiency is less than 0.16 g/
kWh [6,28,29]. Our previous study shows that the energy efficiency of
the most common plate DBD reactor can be enhanced by combining
with extra ozone generator, nevertheless the energy utilization is only
0.608 g/kWh with the same power supply with this study [30]. Ac-
cording to the above, it can be concluded that the reactor used in this
study has an excellent performance for FA degradation, and its energy
efficiency is two to three orders of magnitude higher than that of the
common DBD reactor and other conventional advanced oxidation
processes.
J. Ren, et al. Separation and Purification Technology 235 (2020) 116226

80 (a) 100 (b)

Model 1 Model 1

Degradation efficiency (%)

Degradation efficiency (%)

70
Model 2 Model 2
60 80
Model 3 Model 3
50
60
40
30 40
20
10 20
0
0 2 4 6 8 10 0
0 2 4 6 8 10
Treatment time (min) Treatment time (min)

100 (c)
Degradation efficiency (%)

80

60

40
Model 1
20 Model 2
Model 3
0
0 2 4 6 8 10
Treatment time (min)
Fig. 2. Effect of discharge voltage on FA degradation (discharge frequency 50 Hz, FA concentration 60 mg/L, air flow rate 100 mL/min, pH 5, dielectric thickness
1 mm).

Table 1
100
Degradation efficiency (%)

Energy efficiency for FA degradation under different discharge voltage.

Discharge voltage (kV) Model 1 (g/ Model 2 (g/ Model 3 (g/kWh) 80
kWh) kWh)
60
15 11 5.5 4.1
17 13.4 6.1 5.1 40 60 mL/min
19 12.1 8.7 5.6 100 mL/min
20 140 mL/min
180 mL/min
3.2. Effect of air flow rate on FA degradation 0
0 2 4 6 8 10
Air flow rates will affect the mass transfer efficiency and residence Treatment time (min)
time of ozone in the liquid phase, which is an important working
parameter. FA degradation efficiency under different air flow rates Fig. 3. Effect of air flow rate on FA degradation (treatment method model 1,
discharge voltage 17 kV, discharge frequency 50 Hz, FA concentration 60 mg/L,
were investigated. As shown in Fig. 3, the degradation efficiency in-
pH 5, dielectric thickness 1 mm).
creased from 82.9% to 92.7% with the increase of air flow rates from
60 mL/min to 100 mL/min with 10 min treatment of model 1. However,
with the further increase of air flow rates, the FA degradation efficiency ozone can’t effectively participate in the degradation of FA [31].
decreased gradually. It decreased to 87.1% at the same treatment time Moreover, many generated fine bubbles will be merged into coarse
when the air flow rate was 180 mL/min. bubbles, causing the decline of gas-liquid mass transfer for the ozone
Increasing air flow rates allow more gas molecules to pass through [31]. The similar trend was observed in removal of antibiotic by pulse
the discharge area to produce more ozone. However, excessive air flow discharge plasma combine with graphene oxide/TiO2 [32]. The FA
rates will shorten the residence time of ozone in water, resulting in degradation efficiency reached to the max when the air flow rate was

Table 2
Comparison on FA elimination by various techniques.
Treatment methods Initial concentration (mg/L) Solution volume (mL) Degradation efficiency (%) Treatment Time (min) Energy efficiency (g/kWh) References

Fenton-like 4 750 100 50 – [8]

Bio/photocatalysis 194 250 80 180 0.043 [28]
UV/TiO2 97 150 80–100 240 0.036 [6]
UV/WO3/TiO2 97 150 49.3 180 0.159 [29]
Plate DBD/ozonation 20 150 92.6 40 0.608 [30]
Water falling film DBD 60 150 92.7 10 13.4 This study

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J. Ren, et al. Separation and Purification Technology 235 (2020) 116226

100 100 1.0 mm

Degradation efficiency (%)

Degradation efficiency (%) 80 80
1.5 mm
2.0 mm
60 60
2
40 5 40
8
20 20
11
0 0
0 2 4 6 8 10 0 2 4 6 8 10
Treatment time (min)
Treatment time (min)
Fig. 4. Effect of pH on FA degradation (treatment method model 1, discharge
Fig. 5. Effect of dielectric thickness on FA degradation (treatment method
voltage 17 kV, discharge frequency 50 Hz, FA concentration 60 mg/L, air flow
model 1, discharge voltage 17 kV, discharge frequency 50 Hz, FA concentration
rate 100 mL/min, dielectric thickness 1 mm).
60 mg/L, air flow rate 100 mL/min, pH 5).

3 L/min, and it slightly decreased with the further increase of air flow
rates.
3.4. Effect of dielectric thickness on FA degradation
3.3. Effect of initial pH on FA degradation
The effect of dielectric thickness on the FA degradation is shown in
Fig. 5. The results indicate that increasing the dielectric thickness was
Solution pH is an important index of water quality, influencing the
not conducive to the FA degradation with the same discharge voltage.
existing forms of reactive species in water [33]. Therefore, the effect of
When the thickness of quartz dielectric increased from 1 mm to 2 mm,
solution pH on FA degradation was investigated, and the results are
the FA degradation efficiency decreased by 39% at the treatment time
demonstrated in Fig. 4. FA degradation efficiency increased as the so-
of 10 min. As an indispensable material in DBD, the dielectric thickness
lution pH increased from 2 to 8. For instance, 78.7% of FA was de-
is an important parameter of reactor structure. On the one hand, the
graded after 10 min treatment of model 1 with solution pH of 2. It
initial discharge voltage will be increased when the dielectric becomes
enhanced to 100% when the solution pH was 8 at the same treatment
thicker, which is not conducive to the occurrence of discharge. On the
time. However, the degradation efficiency reduced to 80.9% after
other hand, it is easy to cause breakdown and damage of the dielectric if
10 min treatment when the solution enhanced to 11.
the dielectric thickness is too thin. Hence, to obtain a satisfied de-
O3 can react with OH– to form %OH (Eqs. (3)–(4)) [19,33], thus
gradation performance and a stable DBD system, it is necessary to de-
increasing the solution pH is beneficial to the conversion of O3 to %OH.
termine a proper dielectric thickness. According to the experimental
On the other hand, H2O2 mainly exists as the HO2– in the alkaline
results, quartz dielectric with 1 mm thickness in this study was able to
condition [34]. It is well accepted that the conversion of H2O2 to HO2–
achieve a well FA degradation efficiency and stable work without da-
is the initial process for the peroxone reaction (Eqs. (5)–(10)), and
maging the dielectric.
therefore the peroxone process has a higher reaction rate under a higher
pH values, as unveiled by Eq. (11) [34]. Moreover, the pKa of FA is 4.6,
indicating that FA will existed as the ionic state when the pH is higher 3.5. Response surface methodology
than 4.6 [35]. It is well known that organics with the ionic state is
easier to be degraded in comparison to the molecular state [36]. 3.5.1. Model establishment and regression analysis
However, in extreme alkaline conditions, the OH– will capture %OH (Eq. Box-Behnken design (BBD) was employed to study the FA de-
(12)) [19], hindering the reaction between %OH and FA. This can ex- gradation by response surface methodology. According to the results of
plain the reduction of FA degradation efficiency when the solution pH single factor experiments, three levels of BBD for four factors were es-
was 11. tablished and analyzed by Design-Expert software. The independent
variables were (A) discharge voltage, (B) air flow rate, (C) pH and (D)
O3 + OH− → HO−2 + O2 (3) dielectric thickness. All the design consisted of 29 experiments.
In terms of the fitting of 29 sets of experimental data, the quadratic
polynomial equation for predicting FA degradation efficiency was ob-
O3 + HO2− → %OH + %O2− + O2 (4)
tained as follow.
H2 O2 ↔ H+ + HO−2 (5)
Degradation efficiency
= 84.46 + 10.83A + 5.21B − 6.34C − 18.82D − 2.5AB − 0.3AC + 1.6
HO2− + O3 → HO2% + O3%− (6)
AD − 0.57BC − 0.5BD − 0.85CD − 6.73A2 − 6.41B2 − 14.39
HO2% ↔ O2%− + H +
(7) C2 − 3.3D2 (13)
%−
O2 + O3 → O2 + O3%− (8) Table 3 lists the analysis of variance (ANOVA), which can analyze
%− %
the single variation source in the mode by subdividing the total varia-
O3 + H → HO3
+
(9) tions. The correlation coefficient of the fitting regression equation (R2adj)
HO3% %
→ OH + O2 (10) was 0.9566, which of the model (R2) was 0.9783. The R2 was only
0.012 higher than R2adj, signifying a good fitting degree. The R2pred was
k app = kHO−2 ,O3 × 10(pH − pKa) (11) higher than 0.9, indicating a well match between the predicted values
and experimental values. The p-values of A, C and D were less than
where kapp is the the apparent second order rate constant for the re-
0.0001, implying that discharge voltage, solution pH and dielectric
action of H2O2 with O3, and kHO2− 6
,O3 = 9.6 × 10 M
−1 −1
s , pKa of
thickness could very significantly influence FA degradation, while the
H2O2 = 11.8.
p-value of variation B was 0.0002, indicating that the effect of air flow
OH− + OH → O%− + H2O (12) rate on FA degradation efficiency was not as significant as that of

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J. Ren, et al. Separation and Purification Technology 235 (2020) 116226

Table 3
ANOVA results of response surface quadratic model for FA removal efficiency.
Source Sum of squares DF Mean of square F Value p-value

Model 8022.76 14 573.05 45.08 < 0.0001

A 1408.33 1 1408.33 110.80 < 0.0001
B 325.52 1 325.52 25.61 0.0002
C 482.60 1 482.60 37.97 < 0.0001
D 4248.80 1 4248.80 334.26 < 0.0001
AB 25.00 1 25.00 1.97 0.1826
AC 0.36 1 0.36 0.028 0.8688
AD 10.24 1 10.24 0.81 0.3846
BC 1.32 1 1.32 0.10 0.7518
BD 1.00 1 1.00 0.079 0.7832
CD 2.89 1 2.89 0.23 0.6408
A2 293.43 1 293.43 23.08 0.0003
B2 266.79 1 266.79 20.99 0.0004
C2 1342.86 1 1342.86 105.65 < 0.0001
D2 70.67 1 70.67 5.56 0.0335
Residual 177.95 14 12.71
Lack of fit 96.38 10 9.64 0.47 0.8466
Pure error 81.57 4 20.39
Corrected total 8200.71 28
R2 = 0.9783 R2adj = 0.9566 R2pred = 0.9168

Fig. 6. Correlation of actual and predicted degradation efficiency for FA.

discharge voltage, solution pH and dielectric thickness. A higher F value
means that the variation has a more significant influence on FA de-
gradation. The order of the F value was (D) dielectric thickness > (A)
discharge voltage > (C) pH > (B) air flow rate, which was identical
with the results of single factor experiments. Fig. 6 shows that the
predicted values and the actual values were closed to the same line,
unveiling a good consistency of them.
The optimal operating condition predicted by the model was: dis-
charge voltage 18.24 kV, air flow rate 112, pH 9.3 and dielectric
thickness 1 mm. The desirability of the solution was 0.805, and the
predicted degradation efficiency was 98.5%.
3.5.2. Interaction of two parameter study
The 3D response surface and the 2D contour curves were employed
to establish the interactions between the parameters and their effect on
FA degradation efficiency. Each plot has two variations while other two
variations keep constant in their coded values. The results are shown in
Fig. 7. The effects of the factors on FA degradation efficiency were
clearly demonstrated on these plots. For example, as shown in Fig. 7a–c,
FA degradation efficiency monotonic increasing with increasing the
discharge voltage and decreasing the dielectric thickness, while the
degradation efficiency had a inflection point during the change of pH
and air flow rate. The contour curves is the projection of 3D response
surface in 2D. It can be found that the contour curves in Fig. 7d has the
maximum curvature, and this resulted from the inflection point of the
degradation efficiency caused by solution pH and air flow rate. The
colours of contour curves changed from dark blue to red in Fig. 7c and
F. The massive change is due to the fact that the dielectric thickness had
a strongest influence on FA degradation efficiency, which has been
proved by F values, and dielectric thickness was the variation in Fig. 7c
and F. It is needed to point out that the colur only changed from light
blue to red in Fig. 7e, although dielectric thickness was also the the
variation in the plot. The less change in Fig. 7e could be attributed to
the effect of anthor variation, air flow rate, which had the least influ-
ence on FA degradation efficiency, proved by F values.

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J. Ren, et al. Separation and Purification Technology 235 (2020) 116226

Fig. 7. Response surface plots for degradation of FA showing interaction between process parameters.

3.6. Investigation of reactive species different treatment modes. The dissolved ozone concentration after
10 min plasma (model 2) treatment was only 0.07 mg/L, indicating that
3.6.1. Measurement of O3, H2O2 and %OH sole plasma was not able to produce dissolved ozone in water. The
Fig. 8(a) shows the change of dissolved ozone concentration under concentration of dissolved ozone by sole O3 (model 3) treatment in

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J. Ren, et al. Separation and Purification Technology 235 (2020) 116226

Aqueous O3 concentration (mg/L)

0.6 (a) 8
Model 1 (b)

H2O2 concentration (mg/L)

0.5 Model 2
Model 3 6
0.4
0.3 4
0.2 Model 1
2 Model 2
0.1
Model 3
0.0
0 2 4 6 8 10 0
0 2 4 6 8 10
Treatment time (min) Treatment time (min)

•OH concentration ( mmol/L) 40 (c)

Model 1
Model 2
30 Model 3

20

10

0
0 2 4 6 8 10
Treatment time (min)
Fig. 8. Evolution of (a) O3, (b) H2O2 and (c) %OH concentration under different treatment methods (discharge voltage 17 kV, discharge frequency 50 Hz, FA
concentration 60 mg/L, air flow rate 100 mL/min, pH 5, dielectric thickness 1 mm).

water was the highest, reaching to 0.59 mg/L at 10 min treatment time. (5)–(10)) occurred when plasma and ozone were combined.
However, the concentration of dissolved ozone was reduced to
O2 + e → 2O (14)
0.17 mg/L after the plasma combined with ozone (model 1) at the same
treatment time. This phenomenon indicates that the ozone in water and O + H2 O → H2 O2 (15)
was decomposed by plasma. It is worthy to mention that there is an
inflection point in the variation of dissolved ozone concentration with H2 O + e → H2 O+ + 2e (16)
treatment time in many researches that use high frequency power
supply, because the electrical discharge can heat up water temperature
in these cases, which is adverse to the dissolution of O3 in water. H2O+ + H2O → %OH + H3O+ (17)
Nevertheless, we used a duty frequency power supply (50 Hz) in this %
OH + OH → H2O2 %
(18)
study, whose input energy was not high enough to heat up the treated
%
solution significantly. Therefore, O3 concentration did not show the OH is the most important reactive species in advanced oxidation
inflection point in all the three models. technologies. Therefore, the yield of %OH was investigated. Fig. 8(c)
Fig. 8(b) depicts the change of H2O2 under different treatment illustrates the yield of %OH under different treatment methods. Due to
modes. The results showed that sole ozone (model 3) could not effec- the low conversion efficiency from O3 to %OH, the concentration of %OH
tively produce H2O2 in water. The formation of H2O2 by O3 mainly via produced by ozone alone (model 3) in water was the lowest, which was
the combination of %OH. However, the yield of %OH by O3 in water 6.2 μmol/L after 10 min treatment. The plasma alone (model 2) could
under acidic and neutral conditions is very low so that the H2O2 are not produce 26.4 μmol/L %OH in water at the same time. The higher con-
effectively produced by ozone alone. 7.3 mg/L H2O2 was produced in centration of %OH also explains the higher FA degradation efficiency by
water after plasma (model 2) treatment for 10 min. Plasma produces plasma alone than ozone alone. The yield of %OH increased significantly
H2O2 in two ways: (1) energetic electrons impact oxygen molecules to after combining plasma and ozone (model 1), and the concentration
produce oxygen atoms, and oxygen atoms react with water to form reached to 41.6 μmol/L at the same treatment time. The %OH yield in
H2O2 (Eqs. (14)–(15)) [37]; (2) the water molecules are electrolyzed model 1 system was higher than the sum of model 2 and model 3, and
and dissociated to form %OH, and two %OH combine to produce a H2O2 the synergistic effect for generating %OH between plasma and O3 can be
(Eqs. (16)–(18)). DBD can produce a large number of energetic elec- attributed to the peroxone reaction (Eqs. (5)–(10)), which also resulted
trons to hit water molecules and produce %OH in water, and hence its in the synergistic effect for FA degradation in plasma/O3 process.
ability to produce H2O2 is much higher than that of ozone alone. It can
also be found from Fig. 8(b) that the concentration of H2O2 produced by 3.6.2. Effect of hydrated electron on FA degradation
plasma combined with O3 (model 1) is lower than that produced by the Hydrated electron (eaq−) is a strong reductant with a standard re-
plasma alone, and the concentration is 6.4 mg/L after 10 min treatment. duction potential of −2.9 V, which can react with a variety of pollu-
In the study of 2, 4-dichlorophenoxyacetic acid degradation by plasma- tants through a single electron transfer process [38]. In recent years,
ozonation [24], Bradu et al. also found that the H2O2 yield in water by more and more attention has been paid to the advanced reduction
plasma combined with ozone was significantly less than that in plasma technology based on the eaq− [38], and great treatment results have
alone. According to the variation of dissolved O3 and H2O2 con- been achieved. Previous studies have observed that discharge plasma
centration, it can be concluded that the peroxone reaction (Eqs. can produce eaq− in water. Therefore, it is significant to investigate the

8
J. Ren, et al.
100 0 mmol/L
Degradation efficiency (%)
1 mmol/L
80 2 mmol/L
4 mmol/L
60
40
20
0 0
0 2 4 6
Treatment time (min)
Fig. 9. Effect of NO3– on FA degradation (treatment method model 1, discharge
voltage 17 kV, discharge frequency 50 Hz, FA concentration 60 mg/L, air flow
rate 100 mL/min, pH 5, dielectric thickness 1 mm).
effect of eaq− on FA degradation. NO3– is a common eaq− scavenger.
The reaction rate constant between NO3– and eaq− is 1.4 × 108 M−1
s−1. Fig. 9 displays the effect of NO3– on FA degradation. It is clear that
NO3– hardly affected FA degradation by model 1.
Previous studies have proved that eaq- can decompose of H2O2 and
O3 to produce %OH (Eqs. (19)–(22)) [39-41]. Therefore, the addition of
NO3– may inhibit the degradation of FA by plasma/O3 treatment.
However, according to Eq. (23), eaq− can be converted to %H and H2O in
water, and its pKa is 9.6 [42]. Base on the high pKa, eaq− mainly exists
as its form of conjugate acid, i.e. %H, in weakly acidic FA solution.
Therefore, eaq− scavenger couldn’t exert a significant influence on FA
degradation. It is necessary to point out that the addition of NO3– could
increase the solution conductivity. In the conventional liquid discharge
process, the pollutant degradation efficiency is significantly influenced
by the solution conductivity, because the electrical discharge takes
place in the liquid and the conductivity will influence the discharge
intensity. However; during the gas-liquid two phases discharge, the
electrical discharge mainly takes place in the air. As a result, the so-
lution conductivity hardly affects the discharge process [43,44]. The
results of the addition of NO3– also proves the conclusion.
eaq− + H2O2 → %OH + OH−
eaq− + O3 → O3%−
%− % vironment, because FA can inhibit the growth and absorption moisture
O3 + H → HO3
+
HO3% %
→ OH + O2
%
H + H2O ↔ eaq− + +
H pKa = 9.6
3.6.3. Effect of %H on FA degradation
In the DBD process, high energy electrons attacking water molecules
can produce %H (Eq. (24)) [45]. %H is a kind of reductant with high
chemical activity. In addition, %H can combine with %OH to produce
H2O (Eq. (25)). CCl4 is a commonly used %H scavenger, which can
quickly capture %H in water (Eq. (26)) [46], but can’t react with %OH
[47]. The effect of CCl4 on the degradation of FA is demonstrated in
Fig. 10. When the dosage of CCl4 was 5 mmol/L, FA degradation effi-
ciency decreased to 80.7% from 92.7% after 10 min model 1 treatment,
and it further reduced to 52.8% when 10 mmol/L of CCl4 was added.
e− + H2O → %OH + %H + e−
% %
H + OH → H2O
% %
CCl4 + H → CCl3 + HCl 7
k = 3.8 × 10 mol L
Wang et al. [47] found that the degradation efficiency of p-ni-
trophenol by ultrasonic treatment was drastically enhanced with the
addition of CCl4. Okitsu et al. [48] also found that the degradation of
methyl orange was increased by 14 times by adding 250 mg/L of CCl4.
Separation and Purification Technology 235 (2020) 116226
100 0 mmol/L
Degradation efficiency (%)
5 mmol/L
80 10 mmol/L
60
40
20
8 10 0 2 4 6 8 10
Treatment time (min)
Fig. 10. Effect of CCl4 on FA degradation (treatment method model 1, dis-
charge voltage 17 kV, discharge frequency 50 Hz, FA concentration 60 mg/L,
air flow rate 100 mL/min, pH 5, dielectric thickness 1 mm).
This is because CCl4 suppresses the combination of %OH and improves
the utilization of %OH. However, in this study, CCl4 didn’t promote FA
degradation; on the contrary, it showed a significant inhibitory effect.
The results imply that %H preferred to take place reduction reaction
with FA rather than merge with %OH during plasma/O3 treatment.
Oxidation reactions are the main degradation pathway for pollutants
under electrical discharge plasma, thus reduction reactions are gen-
erally overlooked in most of researches, and only a few studies show
that reductive species such as HO2− and O2− are capable to contribute
to the pollutant degradation in the electrical discharge plasma process
[49,50]. To our knowledge, this is the first report that %H can degrade
pollutant in electrical discharge plasma process. Last section unveiled
that the eaq− produced by DBD could not participate in the degradation
of FA, and it was speculated that eaq− was transformed into %H and H2O
in FA solution. This section also supports the speculation.
3.7. Toxicity analysis
Toxicity evaluation is important for degradation of organic pollu-
tants by advanced oxidation processes because the intermediates that
(19) are more toxic than the parent pollutants may be produced.
Microorganisms are generally used to detect the toxicity of pollutants.
(20) However, the phytotoxicity of FA is a more spectacular threat for en-
(21)
of root system and reduce the hydrolytic enzyme activities of seeds
(22) [51,52]. Seed germination assay is a simple and rapid method to
evaluate the phytotoxicity of polluted liquid samples [53,54]. Plant
(23)
phenols including FA have been proved having the inhibitory effect on
wheat germination [55]. Herein, wheat seed germination tests were
used to evaluate the toxicity of FA samples with and with no treatment.
The wheat seed germination characteristics in different solutions are
demonstrated in Fig. 11a. The germination rate in deionized water (CK)
was 70%, and it only was 52% in FA solution without treatment (T-0).
However, the germination rate increased to 62% in the FA solution with
10 min’s DBD treatment (T-10). Additionally, germination index in T-0
was only 44.7, which was 55.5 in CK. Nevertheless, the germination
index increased to 49 in T-10. Vigor index and root length of the wheat
seeds showed the similar trend. As represented in Fig. 11b, root length
and vigor index increased by 11% and 20.9%, respectively, in T-10
compared with T-0. These results clearly revealed that FA solution in-
hibited the wheat seed germination and growth, but DBD treatment
(24) could weaken FA toxicity. The growth photographs of wheat seeds
germinated in the deionized water and FA solution are shown in
(25)
Fig. 12.
−1 −1
s (26)
4. Conclusions
In this study, FA was degraded by a water falling film DBD reactor.
The reactor demonstrated a well FA degradation efficiency, and the
9
J. Ren, et al. Separation and Purification Technology 235 (2020) 116226

90
80 Gemination rate (a) 60 400 25000
Root length (b)
Gemination rate (%) 70 Gemination index 350
Vigor index

Gemination index
20000
60 300

Root length (cm)

Gemination index
50 40 250 15000
40 200
30 150 10000
20
20 100
5000
10 50
0 0 0 0
CK T-0 T-10 CK T-0 T-10
Fig. 11. Change of (a) germination characteristics of wheat seeds and (b) vigor index and root length of wheat seeds (root length is the total root length of 15
seedlings).

submitted

Appendix A. Supplementary material

Supplementary data to this article can be found online at https://

doi.org/10.1016/j.seppur.2019.116226.

References

Fig. 12. Growth photographs of wheat seeds in different samples.
energy efficiency reached to 13.4 g/kWh. Response surface metho-
dology analysis unveil that the effect degree of the investigated factors
followed the order of dielectric thickness > discharge
voltage > pH > air flow rate, and the quadratic polynomial equation
for predicting FA degradation efficiency and the optimal operating
condition were given. O3 and H2O2 generated by DBD can transform
into %OH, and the plasma and O3 showed a synergistic effect for FA
degradation. eaq- produced by DBD was converted to %H in FA solution,
while %H preferred to react with FA rather than merge with %OH in the
reaction system. FA solution toxicity was weakened after DBD treat-
ment.
Acknowledgements
The authors would like to acknowledge the support given by the
National Natural Science Foundation of China (Nos. 21876070).
Declaration of Competing Interest
We declare that we do not have any commercial or associative in-
terest that represents a conflict of interest in connection with the work
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