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Process Safety and Environmental Protection 123 (2019) 206–214

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Process Safety and Environmental Protection


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

Photocatalytic degradation of an artificial sweetener (Acesulfame-K)


from synthetic wastewater under UV-LED controlled illumination
Zhao Wang ∗ , Giang Nguyen Song Thuy Thuy, Varsha Srivastava, Indu Ambat,
Mika Sillanpää
Department of Green Chemistry, School of Engineering Science, Lappeenranta University of Technology, Sammonkatu 12, FI-50130, Mikkeli, Finland

a r t i c l e i n f o a b s t r a c t

Article history: The photocatalytic degradation of an artificial sweetener, acesulfame-K (ACE) was investigated using an
Received 12 November 2018 ultraviolet light emitting diode (UV-LED) based irradiation in presence of titanium dioxide (TiO2 ), zinc
Received in revised form 15 January 2019 oxide (ZnO), hydrogen peroxide (H2 O2 ), peroxomonosulfate (PMS, HSO5 − ) and peroxodisulfate (PDS,
Accepted 16 January 2019
S2 O8 2− ). The pH of ACE solution showed significant effect on the degradation of ACE. It was observed that
Available online 22 January 2019
low pH value enhanced the ACE degradation rate. After 120 min by UV-LED/TiO2 treatment, the degra-
dation of ACE reached up to 90%, while in UV-LED/ZnO, UV-LED/H2 O2 , UV-LED/PMS, and UV-LED/PDS
Keywords:
degradation rate were found to be 63%, 87%, 76% and 86% respectively. PMS and PDS both oxidant
Acesulfame-K
Artificial sweetener showed good results without the generation of any secondary sludge like other heterogeneous catalysts.
Photocatalytic The present study showed that in presence of catalysts and oxidants, UV-LED illumination significantly
UV-LED enhanced the degradation rate of ACE in comparison to direct photolysis by UV-LED. Possible degradation
pathway of ACE was determined by gas chromatography-mass spectrometry (GC–MS) which confirmed
the ACE degradation by generation of three byproducts.
© 2019 Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.

1. Introduction river, and 2.6 ␮g/L ACE concentration was detected in the tap water
sample(Buerge et al., 2009; Lange et al., 2012; Liu et al., 2014;
The artificial sweeteners can provide sweetness of sugar with- Loos et al., 2013; Müller et al., 2011). ACE has been reported as
out the calories, but does not have any nutritional value(Manfred the most persistent sweeteners with removal rates as low as 40%
et al., 2006; Sharma et al., 2014; Subedi and Kannan, 2014). Arti- (Scheurer et al., 2009). Due to the increasing use of ACE, the con-
ficial sweeteners have been used in personal care products, such centration of ACE in water and wastewater streams is continuously
as dental cream and pharmaceuticals. ACE also exists in food and increasing and it is necessary to develop an efficient technology
beverage(Toth et al., 2012). The most commonly used artificial for the proper treatment of persistent sweeteners. Artificial sweet-
sweetener is acesulfame-K (ACE). Fig. 1 presents the chemical struc- ener pollutant cannot be removed by common mechanical and
ture of ACE. It is widely used artificial sweeteners in all over the secondary microbial digestion. According to Criegee mechanism
world. The sweetness of ACE is 200 times higher than sugar. (Sang (Criegee, 1975), ozone can attack C C double bond easily, ACE also
et al., 2014; Zoulias et al., 2000; Zygler et al., 2009). can be oxidized by ozonation, but the ratio between the ACE and
Utilization of artificial sweeteners is continuously increasing ozone is more restrictive. ACE has the highest octanol-water par-
due to increasing health awareness but the artificial sweeteners tition coefficients, therefore it is not a good choice to use granular
may pose a potential health risk. (Bandyopadhyay et al., 2008; activated carbon filtration method for the removal of ACE in drink-
Polyák et al., 2010). The artificial sweeteners exposure can enhance ing water treatment plants (Lange et al., 2012). Further, artificial
the deoxyribonucleic acid (DNA) in the bone marrow cells because sweeteners have low soil adsorption ability and good water solu-
of the sweetener-induced DNA strand breaks. The concentration of bility, so the adsorption process cannot give a good performance
artificial sweeteners may vary in the different water system and for the removal the artificial sweeteners (Soh et al., 2011). Ultravi-
the ranges from 2.2 to 65 ␮g/L for ACE was in the influent. In the olet photolysis is widely used for the removal of organic pollutants
groundwater sample, 4.7 ␮g/L concentration of ACE, 6.9 ␮g/L in the (Levchuk et al., 2015; Nasseri et al., 2018; Yi et al., 2018b, 2018a).
Its efficiency can be enhanced when irradiation is combined with
hydrogen peroxide, as its photocatalytic dissociation yield hydroxyl

radicals ( OH) (Al-Hamdi et al., 2015; Gao et al., 2017; Sillanpää
∗ Corresponding author. et al., 2018; Yi et al., 2019, 2017). On UV/H2 O2 affect the chemi-
E-mail address: Zhao.Wang@lut.fi (Z. Wang).

https://doi.org/10.1016/j.psep.2019.01.018
0957-5820/© 2019 Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.
Z. Wang et al. / Process Safety and Environmental Protection 123 (2019) 206–214 207

Fig. 1. Chemical structure of Acesulfame-K (Scheurer et al., 2012).

Fig. 2. Schematic representation of the experimental set-up for the UV-LED illumi-
cal bonds in various hence different degradation by products can nation of ACE solution.
be produced in the degradation process (Rantalankila et al., 2016).
Among the different types of light source, ultraviolet light emitting tor (Stellarnet CR2) was used to monitor Ultraviolet irradiance. The
diodes (UV-LED) has high efficiency, lack of warm-up time, low UV-LED light source was with an internal diameter of 55 mm of
cost and disposal problem (Hammouda et al., 2017; Rantalankila 11 LED components and a height of 400 mm into which, a quartz
et al., 2016; Verma and Sillanpää, 2015; Vilhunen et al., 2009). sleeve with a diameter of 45 mm was longitudinally inserted at
UV-LED based catalytic degradation have been used for the treat- the axial center. During the whole experiment, the solutions were
ment of many. Titanium dioxide (TiO2 ) and zinc oxide (ZnO) were properly agitated by using a magnetic stirrer at 500 rpm agitation
widely used for photocatalytic degradation of organic pollutants speed for homogeneous exposure of UV irradiation and proper mix-
(Ansari et al., 2015; Zinatloo-Ajabshir and Salavati-Niasari, 2016; ing of the catalyst during the whole reaction. After degradation, the
Safajou et al., 2017; Salavati-Niasari et al., 2016; Zinatloo-Ajabshir samples were filtered by using the 0.2 ␮m regeneration cellulose
et al., 2017, 2016, 2015). However, the degradation of ACE arti- (RC) membrane.
ficial sweetener by UV-LED based system is not well explored.
Further, the application of sulphate radical producing compounds 2.3. Preparation of ACE solution
such as peroxomonosulphate (PMS, HSO5 − ) and peroxodisulfate
(PDS, S2 O8 2− ) have not been investigated for the ACE degradation. To investigate the effect of ACE concentration, the concentration

Application of SO4 − radical mediated degradation of organic pol- of 20 ␮M/L and 30 ␮M/L ACE solution were prepared in deionized

lutants has many advantages over other catalysts as SO4 − radical water for the degradation process. The pH of ACE solutions was

has a longer lifetime compared to OH radical and less influenced maintained from 2.0 to 7.0 by using 1 M HCL/NaOH for pH studies
by the dissolved organic matter (DOM) (Ghiyasiyan-Arani et al., and measured by using a pH meter (VWR® pH1000). For degra-
2016; Mahdiani et al., 2018; Soofivand et al., 2013; Wang et al., dation, the ACE solution was poured into a quartz petri dish and
2018; Zinatloo-Ajabshir and Salavati-Niasari, 2016,2015). Further, illuminated with the UV-LED source for 120 min and during reac-

the reactivity of SO4 − is pH independent and can be used for a wide tion ACE solutions was continuously stirred using magnetic stirrer.

pH range in comparison to OH radical, which is highly pH depen- The sample was taken after every10 min interval of degradation
dent (Ayati et al., 2016; Carp et al., 2004; Qi et al., 2016; Sampath reaction and the remaining ACE concentration in sample was mea-
et al., 2016). The aim of the present study is to apply UV-LED illu- sured to investigate the effect of different degradation time. Effect
mination in for the degradation of ACE in synthetic wastewater. of H2 O2 , TiO2 , ZnO, PDS, and PMS on ACE degradation was investi-

Role of SO4 − radical in ACE degradation was studied by using UV- gated by adding an appropriate concentration into ACE solution.

LED illumination in presence of PDS and PMS, while the role of OH
in ACE degradation was investigated by using TiO2 , ZnO, and H2 O2 2.4. Analysis of ACE concentration in treated sample
under UV-LED illumination. Different parameters such as pH of ACE
solution, catalyst dose, initial concentration of ACE, and UV-LED High performance liquid chromatography (HPLC, SHIMADZU® )
illumination time were optimized for higher degradation of ACE was used for measuring the concentration of ACE in treated solu-
in synthetic wastewater. Further, degradation by-products were tion. The Phenomenex® C18 column (5 ␮m, 150 mm*4.6 mm) was
identified to propose possible degradation pathway of ACE. used with 230 nm wavelength of UV detector. The ratio of buffer
solution was 95:5 mixture of ammonium acetate and methanol.
2. Materials and method The flow rate of mobile phase was maintained at 1 mL/min. The
percentage of ACE solution degradation was calculated by following
2.1. Chemicals Eq. 1:
(C0 − Ct )
Acesulfame-K (ACE), Titanium dioxide (TiO2 ), Hydroxyl perox- ACE degradation (%) = *100 (1)
ide (H2 O2 , 30%), Zinc oxide (ZnO), Potassium peroxodisulfate (PDS), C0
Potassium peroxomonosulfate (PMS), Potassium phosphoric acid, Where C0 and Ct represent the concentration of ACE solution before
methanol and ammonium acetate of HPLC grade were procured and after the UV illumination respectively. The pseudo-first-order
from Sigma-Aldrich. Deionized water (18.2 M) produced from a model was used to analyze the kinetic data of ACE degradation (Eq.
Milli-Q water purification system (Millipore) was used for solution 2) (Coiffard et al., 1999).
preparation. C 
t
ln = −k1 t (2)
C0
2.2. Experimental setup for ACE degradation
The ACE solution before and after degradation treatment rep-
As shown in Fig.2, UV-LED light (AlInGanN) source was used resent to Ct and C0 respectively, and the reaction rate constant of
for the irradiation. The emission wavelength was 265 nm. The pseudo-first order refer to k1 . The determination coefficient (R2 )
spectroradiometer (Stellarnet Black Comet) with a cosine recep- value was used to investigate the goodness of the model fitness. The
208 Z. Wang et al. / Process Safety and Environmental Protection 123 (2019) 206–214

Fig. 3. Effect of UV-LED illumination time and ACE concentration on ACE degrada- Fig. 4. Effect of pH on the degradation of ACE (UV-LED illumination time, 120 min,
tion. ACE concentration: 30␮M/L).

byproducts generated during the degradation process were deter- The anomalous behavior of ACE in alkaline range revealed the
mined by Gas chromatography-mass spectrometry (GC–MS). The instability of ACE at higher pH range. At higher pH range, a higher
GC–MS (Agilent-GC 6890 N, MS 5975) was using Agilent DB-5MS amount of hydroxyl ions (OH− ) are available in solution, which
GC column dimensions 30 m, 0.25 mm, 0.25 ␮m. Splitless mode was interacts with ACE species in a different manner resulting differ-
used with 250 ◦ C inlet temperature and the injection volume was ent degradation rate on exposure to UV light based on the ACE-OH
1.0 ␮L. The program of oven temperature was 65 ◦ C for 2 min and site more exposed to UV light. On the basis of the pH study (Coiffard
then the heating rate was adjusted 30 ◦ C/min to achieve 180 0 C and et al., 1999), the effect of pH on the shelf-life of ACE is significant
kept at this temperature for 1 min. Further, the heating rate was at pH 3.0. Further experiments were conducted at pH 3.0. The rela-
maintained at 7 ◦ C /min to raise the temperature up to 280 ◦ C for tionship between pH and photostability has been found for many
1 min, which was followed by a further increment in temperature organic molecules (Le et al., 1996). As shown in Fig.4, the significant
to be 300 ◦ C by maintaining heating rate 40 ◦ C/min for 3 min. The degradation rate changes were observed with pH variation.
stepwise increment of the column temperature provides a proper
temperature condition for the analyst. 3.3. ACE degradation by UV-LED/H2 O2

3. Results and discussion Photocatalytic degradation of any pollutant species can be


enhanced by the combination of H2 O2 with UV-LED illumina-

For optimization of the degradation process of ACE with UV-LED, tion, as in presence of UV light, H2 O2 provide OH radicals,
various important parameters (effect of concentration of ACE solu- which can play a significant role in degradation of pollutant
tion, irradiation time, pH of ACE solution, concentration of H2 O2 , species (Rosenfeldt et al., 2006). To optimize the degradation rate
TiO2 , ZnO, PMS, and PDS) were investigated. of ACE by using UV-LED/H2 O2 , different concentration of H2 O2
(6.4 × 10−3 −1.92 × 10−3 M) were added into ACE solution. Fig. 5
depicts ACE degradation percentage at different H2 O2 concentra-
3.1. Effect of UV-LED illumination time and ACE concentration on tions. Generation of hydroxyl radicals on UV irradiation and their
degradation interaction with ACE can be explained by following equations:

Two different concentrations 20␮M/L and 30␮M/L of ACE solu- H2 O2 +h␯ → 2HO (3)
tion were illuminated with UV-LED source for different time • •
H2 O2 +HO → HO2 +H2 O (4)
interval up to 120 min to investigate the effect of ACE concentra-
• •
tion on degradation. Higher degradation of ACE was observed by H2 O2 +HO2 → HO +H2 O + O2 (5)
increasing irradiation time and within 120 min of UV-LED illumi- • •
nation; the degradation rate was 43.7% and 41.9% for 20␮M/L and ACE + HO → ACE +H2 O (6)
30␮M/L respectively (Fig.3). •
2HO → H2 O2 (7)

3.2. Effect of pH on ACE degradation 2HO2 → H2 O2 +O2 (8)
• •
HO +HO2 → H2 O + O2 (9)
The pH of solution plays a major role in the degradation of any
pollutant species as pH can strongly affect the pollutant species On irradiation with UV light, hydrogen peroxide generates two

in solution. To investigate the effect of pH on degradation of ACE, OH radicals, which is a powerful oxidant (Tsukamoto et al., 2012).

the pH value of the ACE solutions was adjusted from 2.0 to 7.0. It On UV irradiation, OH radical, attack on the ACE molecule and
was observed that the degradation of ACE increased by increasing degrade ACE in different byproducts.
pH of ACE solution from 2.0 to 3.0. When pH was increased above Higher degradation rate was observed in presence of higher con-
3.0, decreased degradation of ACE was observed. With the increase centration of H2 O2 due to the availability of higher concentration

in solution pH, decreased degradation of ACE was observed. The of OH radicals in the solution and hence a higher number of ACE

higher degradation of ACE was obtained at pH 3, this was same as can be targeted by OH radical resulting in higher degradation of
the earlier reported study (Coiffard et al., 1999). ACE. The significant increase in degradation rate was observed by
Z. Wang et al. / Process Safety and Environmental Protection 123 (2019) 206–214 209

Fig. 6. Effect of TiO2 concentration on the ACE degradation at pH 3.0 (UV-LED illu-
mination time: 120 min, ACE concentration: 30␮M/L).
Fig. 5. Effect of H2 O2 concentration on the ACE degradation at pH 3.0 (UV-LED
illumination time: 120 min, ACE concentration: 30␮M/L).

using UV-LED/H2 O2 in comparison to the degradation rate, which


was obtained in absence of H2 O2 .

3.4. ACE degradation by UV-LED/TiO2

The TiO2 has been reported as an efficient photocatalyst for


the degradation of variety of pollutant species but its applications
with UV-LED for the removal of artificial sweeteners and especially
for ACE are rarely available. The TiO2 generate conduction-band
electrons (eCB − ) and valence-band holes (hVB + ) under the UV-LED
irradiation. These charge carriers either stay inside the crystal or
migrate to the surface to react with the available adsorbate, such
as OH− and H2 O (Turchi and Ollis, 1990).

TiO2 (e) + O2 → O2− · (10)

H +
+ O2− · ↔ HO2· (11)

HO2· + HO2· → O2 + H2 O2 (12)

O2− · + e− + 2H + → H2 O2 (13)

H2 O2 + e− → OH · + OH − (14)

 ·
 Fig. 7. Effect of ZnO concentration on the ACE degradation in pH 3.0 (UV-LED illu-
ACE + O2 O2− · or OH → degradation products (15) mination time: 120 min, ACE concentration: 30␮M/L).

Different concentrations of TiO2 (0.63 × 10−4 M, 1.25 × 10−4 M, ACE solution was illuminated with UV-LED source for 120 min. It
and 1.88 × 10−4 M) were added in ACE solution at pH 3.0 to inves- was observed that 62.7% degradation could be achieved by using
tigate the effect of UV-LED/TiO2 on ACE degradation. Fig. 6 shows 1.88 × 10−4 M ZnO in ACE solution within 120 min of irradiation
that the degradation rate increased from 70.8 to 90.4% by increas- (Fig. 7).
ing TiO2 dose. In absence of TiO2 catalyst, < 40% degradation rate Similar to TiO2 , on UV-LED irradiation, ZnO catalyst gener-
was achieved in 120 min of UV-LED illumination. It is reported ates the electrons (e–) and holes (h+ ) in the conduction band

that OH radicals are the primary oxidative species to initiate and valence band respectively. The holes generate hydroxyl rad-
the degradation reaction in the photocatalysis of various organic icals while electron is trapped by oxygen and gives superoxide
substrates(Ceresa et al., 1983). The TiO2 can easily degrade ACE as ion (Eq.16). Hydroxyl radical attack on ACE and give degradation

it can produce OH radicals on UV irradiation. byproduct by bond breakage of ACE molecule (Eq. 16–22).

3.5. ACE degradation by UV-LED/ZnO ZnO + h␯ → ecb − +h+ (16)


+ − •
h +HO → HO (17)
ZnO has been proved a promising candidate in photocatalytic •
+ +
degradation of several organic pollutants, but the study on appli- h +H2 O → H +HO (18)
cation of ZnO for ACE degradation is rather scanty. Effect of ZnO
e − + O2 → O2− · (19)
for UV-LED degradation of ACE was also investigated. For this pur-
+ +
pose, different ZnO concentrations were added in ACE solution and h +ACE → ACE (20)
210 Z. Wang et al. / Process Safety and Environmental Protection 123 (2019) 206–214

Fig. 8. Effect of PMS concentration on the ACE degradation (UV-LED illumination


time: 120 min, ACE concentration: 30␮M/L pH = 3).

ACE+ +O2 → DegradationProduct (21)


+
HO• + ACE → DegradationProduct (22)

By using different amount of ZnO catalyst viz. 0.63 × 10−4 M,


1.25 × 10−4 M, and 1.88 × 10−4 M, the degradation rate was found
Fig. 9. Effect of PDS concentration on the ACE degradation (UV-LED illumination
to be 54.8%, 61.7%, and 62.7% respectively. time: 120 min, ACE concentration: 30␮M/L, pH = 3).

3.6. ACE degradation by UV-LED/PMS

PMS(HSO5 −) is asymmetric around the peroxide bond(-O-O-)



and generate one SO4− · and one OH radical on UV radiations (Wang
and Chu, 2012). It is reported that UV–vis absorption spectra of per-
oxymonosulfate radical is ␭SO5 = 260 nm with ␧so5 = 1030M−1 cm−1
(Antoniou et al., 2010). The energy of excitation for one mole is
461.5 kJ/mole at 260 nm (Verma et al., 2016). For ACE solution
degradation, 461.5 kJ/mole energy is sufficent for PMS vibration in
the peroxide bond and to generate sulfate and hydroxyl radicals.
The UV-LED source of 265 nm is sufficient for the generation of sul-
phate and hydroxyl radicles from PMS which can take part in the
degradation of ACE. The degradation of ACE was carried out using
the various PMS concentrations. Fig. 8 shows the degradation of
ACE at different concentration of PMS. The degradation rate was
found to be 40.4%, 69.5% and 76.9% at 0.63 × 10−4 M, 1.25 × 10−4 M
Fig. 10. Comparison of ACE degradation by different UV-LED/catalytic treatment.
and 1.88 × 10−4 M concentration of PMS respectively.

3.7. ACE degradation by UV-LED/PDS to the availability of higher concentration of SO4− · radicals in ACE
solution, which facilitated the higher degradation of ACE.
PDS (S2 O8 2− ) is asymmetric around the peroxide bond ( O O )
and generates two sulfate radicals (O4− · ) on UV irradiation, which 3.8. Comparative studies of UV-LED, UV-LED/TiO2 , UV-LED/ZnO,
takes part in the degradation of pollutants. UV-LED/H2 O2 , UV-LED/PDS and UV-LED/PMS system

S2 O82− → hv 2SO4− · (23)


The time-dependent degradation of ACE by UV-LED, UV-

The H radicals can also react with PDS and produce more SO4− · LED/TiO2 , UV-LED/ZnO, UV-LED/H2 O2 , UV-LED/PDS, and UV-
radicals as shown in reactions. LED/PMS system at the same chemical molar dosage and at pH 3.0
is shown in Fig. 10. Only 41.9% of ACE was degraded after 120 min
S2 O82− + H . → HSO4− + SO4− · + 1⁄2O2 (24) by UV-LED direct photolysis, while TiO2 and ZnO nanoparticles
gave 90.4% and 62.7% degradation respectively within 120 min of
S2 O82− + H · → HSO4− + SO4− · (25)
UV irradiation. The degradation rate 86.7%, 76.9% and 85.6% was
The presence of higher concentration of SO4− ·
radicals can lead obtained for H2 O2 , PMS, and PDS respectively. The degradation of
to higher degradation of organic pollutant species. In this study, ACE followed the pseudo-first order kinetics. The coefficient value
the effect of PDS concentration for ACE degradation was studied k1 for different concentraion of TiO2 , ZnO, PMS, PDS, and H2 O2 in
by varying PDS concentration (0.63 × 10−4 M, 1.25 × 10−4 M, and ACE solution is given in Table 1.
1.88 × 10−4 M) in ACE solution. It was observed that at the low- Soh et al., (Soh et al., 2011) reported 35% degradation of ACE
est dose of PDS, degradation percentage was 56.0% (Fig. 9). The under the UV light exposure, which suggested that UV light could
maximum degradation of ACE (85.56%) was achieved by using be used for ACE degradation but degradation rate was not promis-
1.87 × 10−4 M of PDS. Higher degradation at higher PDS dose is due ing. An incubation experiment to degrade ACE in soils was studied
Z. Wang et al. / Process Safety and Environmental Protection 123 (2019) 206–214 211

Table 1 Table 2
The kinetics of different catalysts/oxidants with different concentration. ACE degradation byproducts detected by GC–MS analysis.

Concentration of k1 (min−1 ) Time Product ID MS m/z Proposed structure


catalysts/oxidants used (M)
ZnO TiO2 PDS PMS H2 O2

0.63 × 10−4 0.007 0.017 0.007 0.004 0.008


1.25 × 10−4 0.007 0.010 0.007 0.010 0.012 15min 1 182.8
1.88 × 10−4 0.008 0.019 0.021 0.012 0.017

and it was reported that ACE cannot be degraded even after 6.1 days
(Buerge et al., 2011). Yin et al.(2017) used permanganate for the
oxidative transformation of acesulfame (Yin et al., 2017).Further,
in another study, TiO2 was used for ACE degradation in presence 15min 2 148.9

of solar simulator and decreased degradation was demonstrated


with increasing concentration of ACE (Ghosh et al., 2018). How-
ever, in this study, pH 6.0 was found to be optimum for complete
degradation.TiO2 dosage from 0.8 to 1.0 g/L gave higher degrada-
tion rate for ACE. ACE has been treated by adsorptive removal on
MAF-6-derived carbons (Song et al., 2018). Scheurer et al. (2014) 15min 3 222.2
reported ACE degradation rate constants in the range between
5.4·10− 3 s− 1 and 7.4·10− 3 s− 1 , when degradation study was car-
ried out in presence of UV light and approximately 30% reduction in
ACE concentration was recorded (Scheurer et al., 2014).The present 45min 4 207
study shows that by the combination of UV light source with cat-
alyst, higher degradation of ACE can be achieved. However, TiO2
and ZnO gave significant degradation of ACE solution, but for the
45min 5 207
practical application, the cost and secondary sludge generation in
form of the exhausted catalyst after treatment process limits their
applications. This problem can be overcome by the use of PMS
and PDS because there is not any sludge generation, as well as the 45min 6 207
degradation is rather comparable with TiO2 and ZnO. As both PDS

and PMS gives SO4 − radicals on UV irradiation, and application of
•−
SO4 radical mediated degradation of organic pollutants has many
advantages due to less influence of the dissolved organic matter 45min 7 223.1
(DOM) and pH independence, so it can easily be used for acidic and
alkaline wastewater. PMS and PDS could be good candidates for the
degradation of ACE from water and wastewater.

3.9. Identification of ACE degradation intermediates and 60min 8 148.9


proposed degradation pathways

ACE degradation intermediates by the UV-LED process were


identified by GC–MS. Samples collected at different time intervals
after UV-LED illumination for GC–MS analysis. Molecular structure
was identified according to the National Institute of Standards and
60min 9 149
Technology (NIST) Library match. The detected byproducts at dif-
ferent time interval are shown in Table 2 with their m/z information
and possible structure.
The proposed degradation pathway for ACE degradation by
UV-LED process is shown in Fig. 11. Due to ACE attacked by
hydroxyl radicals, three primary intermediates (compound 1, 2, 120min 10 206.9
and 3) were generated in first step. Compound 1 (Benzoic acid,
2-(1-oxopropyl)-) from the attack of hydroxyl radical, may gen-
erate compound 4 (phthalic acid, hexyl 2-methoxyethyl ester)
compound 5 (phthalic acid, 2-methoxyethyl propyl ester) and
compound 6 (terephthalic acid di (2-methoxyethyl) ester). On
the other hand, compound 2 also may generate compound 120min 11 149.1
6. After UV-LED process, two of the benzene ring was open
from compound 3 and generate compound 12. One of amine
from compound 3 (1-phenoxyphthalazine) combine with com-
pound 2, generate compound 8(3,4-Dimethylbenzamide), attack by
hydroxylaltion generated compound 9(4-ethylbenzamide), finally 120min 12 207
gave the compound 11(methcathinone). The amine from ACE
break by hydration, attached with compound 2, generate com-
pound 8(3,4-Dimethylbenzamide). One of methyl was removed
from compound 8 to generated compound 10(4-ethylbenzamide).
212 Z. Wang et al. / Process Safety and Environmental Protection 123 (2019) 206–214

Fig. 11. Proposed degradation pathways of ACE by UV-LED process.

The thio from ACE combines with compound 2 and generate buty(dimethyl)sily]oxymorphopropan-2-ol and terephthalic acid
compound 7 (2-phenylbutyric acid), when the benzene ring of di (2-methoxyethyl) ester) on UV-LED process in 120 min. Present
compound 7 break by hydroxylation, compound 10 (1-Dyrrol [tert- study showed that the application of different catalyst with UV-
buty(dimethyl)sily]oxymorphopropan-2-ol) would be generated. LED illumination can enhance the degradation of ACE. Due to high
efficiency and simplicity of UV-LED/catalytic and UV-LED/oxidants
AOPs, it can be used in wastewater treatment plant for the degrada-
4. Conclusion
tion of ACE. Further, application of UV-LED/PMS and UV-LED/PDS
source could be an economically viable approach for the degrada-
The degradation of ACE was investigated by the UV-
tion of ACE from wastewater due to their high efficiency for ACE
LED/catalytic and UV-LED/oxidants advanced oxidation process.
degradation.
The degradation of ACE followed pseudo first-order kinetics. The
degradation rate of ACE was affected by operating parameter,
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