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Degradation of Nitenpyram Pesticide in Aqueous Solution by Low-Temperature Plasma
Degradation of Nitenpyram Pesticide in Aqueous Solution by Low-Temperature Plasma
Degradation of Nitenpyram Pesticide in Aqueous Solution by Low-Temperature Plasma
Environmental Technology
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To cite this article: S. P. Li , Y. Y. Jiang , X. H. Cao , Y. W. Dong , M. Dong & J. Xu (2013) Degradation of nitenpyram
pesticide in aqueous solution by low-temperature plasma, Environmental Technology, 34:12, 1609-1616, DOI:
10.1080/09593330.2013.765914
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Environmental Technology, 2013
Vol. 34, No. 12, 1609–1616, http://dx.doi.org/10.1080/09593330.2013.765914
In order to study the new technique of plasma wastewater treatment, the degradation behaviour of nitenpyram (NTP) pesticide
was investigated in a low-temperature plasma formed during a dielectric barrier discharge process. The reactor was a radial
flow sedimentation tank centred around the water inlet. We studied the effect of pesticide concentration and input power of the
dielectric barrier discharge, together with the effect of external factors on the degradation of nitenpyram pesticide wastewater
such as conductivity and the use of various of catalysts, and the reaction products were analyzed by high-performance liquid
chromatography mass spectrometry (HPLC–MS). The results showed that NTP could be effectively removed from aqueous
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solution by low-temperature plasma. Increasing the input power could improve the efficiency of degradation, conforming to
a first-order kinetic model. Use of a suitable catalyst clearly improved the degradation process, as also did low conductivity.
The pH of NTP was reduced with discharge time.
Keywords: low-temperature plasma; nitenpyram; degradation; reaction products; HPLC–MS
2.1. Experimental apparatus charge time was 180 min and the removal efficiency was
Figure 1 shows a schematic diagram of the experimental determined at initial NTP concentrations of 50, 100 and
system used in the present investigation. It consists of the 200 mg L−1 .
reaction system and a power supply (CTP–2000K) able to It is seen from Figure 2 that initial concentration
provide a steady high voltage up to 250 V and current in had a significant effect on the efficiency of removal of
the range 0–4 A. In the study the optimum voltage used NTP. When the initial NTP concentration was 50 mg L−1 ,
was found to be 80 V at a current of 1–2.5 A. The reac- NTP degradation efficiency was 79.1% after 180 min dis-
tor had a structure of a radial flow sedimentation tank charge. However, when the initial concentrations were
(height 100 mm, inner diameter 100 mm and outer diameter 100 or 200 mg L−1 , removal efficiencies of 82.7% and
150 mm). The total volume of the tank was 7.85 × 10−4 m3 . 70.1%, respectively, were achieved over the same treat-
DBD is a discharge system in which one or two electrodes ment time. This meant that too low or too high an initial
cover the isolation medium in the reactor. We used quartz concentration would reduce the NTP degradation rate. This
glass (diameter 90 mm) as isolation medium, and the high phenomenon can be explained as follows. If the initial con-
voltage electrode was located above the quartz glass. The centration is below 100 mg L−1 , some solute molecules are
ground electrode was placed in the centre of the reactor. not immediately able to make contact with • OH and are not
The distance between the barrier and the solution surface therefore degraded by the low-temperature plasma, result-
was about 8 mm. The solution was circulated continuously ing in a lower removal rate than at concentrations above
by means of a pump (BT100–1L) connected in the inlet. 100 mg L−1 . On the other hand, if the initial concentra-
tion is too high, the number of molecules increases to the
point at which the quantity of active species (• OH) available
2.2. Chemicals and reagents are insufficient to react completely with the excess of NTP
NaOH, HCl, FeSO4 and KCl used in the study were ana-
lytical grade. NTP was obtained from Tianjin Chemical 100
Reagent Company at 95% purity. The analytical eluents
were all of HPLC grade.
80
NTP Removal (%)
2.3. Analysis 60
Measurement of discharge power was by the instantaneous
power method, in which a voltage and a current probe are
40 50mg/L
used directly to obtain the working voltage and current
100mg/L
waveform (signals), then converting them to an instan- 200mg/L
taneous power curve by means of digital oscilloscopes. 20
The distance between the dielectric barrier and wastewa-
ter was adjusted to 8 mm and the parameters of the power
0
supply were adjusted correspondingly. The discharge time 0 20 40 60 80 100 120 140 160 180 200
was 180 min and samples were taken every 20 min. After Time (min)
180 min, the NTP concentration was determined using
a TU1810PC–UV spectrophotometer at a wavelength of Figure 2. NTP degradation at different concentrations.
Environmental Technology 1611
Removal (%)
Time (min) 60
Figure 3. NTP degradation at different input power levels.
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40
100 9
90
8
80
7
70
6
NTP Removal (%)
60
5
pH
50
40
pH = 3.0 4
pH = 8.2
30 pH = 11.0 3
20 2
10 1
0
0 20 40 60 80 100 120 140 160 180 200
0
0 20 40 60 80 100 120 140 160 180 200
Time (min)
Time (min)
Figure 5. The effect of pH on NTP degradation. Figure 6. pH changes in NTP solution due to low-temperature
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plasma.
attack at high points of electric density and the reaction
time is thus shortened. Although the addition of Fe2+ had
an obvious effect on removal rate, higher concentrations during the decomposition of ozone at high pH [24,25]. This
offered no additional advantage. Excessive concentrations presumes that ozone will react with H2 O to form hydrogen
of Fe2+ would increase the reaction between Fe2+ and • OH, peroxide, which at high pH decomposes to give hydroxyl
so more Fe3+ and OH− would be produced, which would radicals, whereas the ozone molecules remain unchanged
in turn decrease the • OH concentration and thus reduce at low pH.
the degradation rate. This incidentally confirms that • OH As shown in Figure 6, the pH decreased as the discharge
is the species responsible for the degradation of NTP in time increased, due to the formation of acidic substances
wastewater. in the degradation process, showing that the degradation
efficiency of NTP wastewater decreases with decreasing
pH. When the pH is higher, more hydroxyl radicals are
3.4. Effect of the initial pH on NTP degradation by produced and the degradation of NTP increases.
low-temperature plasma
It is well known that oxidation processes are sensitive to pH.
3.5. Effect of initial solution conductivity on NTP
It has for example been reported that the degradation of phe-
degradation by low-temperature plasma
nol in aqueous solution using pulsed high-voltage discharge
plasma is more effective at high rather than low pH [23]. In the present study the variation in degradation rate
Similarly, pH is an important factor in NTP degradation. was measured at initial solution electrical conductivities
In order to study the effect of pH on NTP degradation, the adjusted to 10, 50, 100, 200 and 400μS cm−1 using KCl
pH was adjusted using HCl or NaOH (0.01 mol L−1 ). The (0.01 mol L−1 ). The results are illustrated in Figure 7.
pH of NTP wastewater was 8.2. Figure 5 shows the effect The trend of the curve in Figure 7 indicates that the
of initial pH value on NTP degradation by low-temperature degradation rate decreases with increasing initial solution
plasma. conductivity, giving a greater concentration of charged
As shown in Figure 5, the NTP degradation process was ions and a decreasing rate constant. The possible reason
more effective at an initial pH value of 11, giving 85.4% is that the charged ions react with active species gener-
NTP removal over at a discharge time of 180 min. For this ating complex products, and as a result there are fewer
discharge time the degradation efficiency was higher at ini- hydroxyl radicals available for reaction with NTP. In addi-
tial pH 8.2 rather than at pH 3, and it was lower at initial pH tion, more ions present in the aqueous solution would
8 than at pH 11. These results indicated that the degradation change the charge space, and may further decrease the for-
of an organic pollutant by oxidation was more efficient at mation of hydroxyl radicals [26]. The total effect is that the
higher pH. removal of NTP wastewater is low when the initial solution
Since NTP has a pyridine-type structure, and the car- conductivity is high.
bon chain is easily oxidized, such a result is consistent with
that of Yin-Sheng Chen et al., whose research was con-
ducted using a pulsed high-voltage discharge plasma [23]. 3.6. Changes in COD and TOC
One possible explanation is that hydroxyl radical, which COD and TOC are important indicators of water contami-
plays a key role in pulsed discharge degradation, is formed nation. The measured results of chemical oxygen demand
Environmental Technology 1613
+
3H2 O2 + Cr2 O2−
7 + 8H → 3O2 + 2Cr
3+
+ 7H2 O
60 The relationship between the TOC of the NTP solution and
the discharge time is shown in Figure 8(b), and it is seen
50 that the TOC of the solution decreased with treatment time.
40
30
0 100 200 300 400
(a) 140
130
120
110
COD (mg/L)
100
90
80
70
60
50
0 20 40 60 80 100 120 140 160 180 200
Time (min)
(b) 120
100
80
TOC (mg/L)
60
40
20
0
0 20 40 60 80 100 120 140 160 180 200
Time (min)
Figure 8. Change in (a) COD and (b) TOC during the NTP
degradation process.
NH
Main component 271.07 C11 H15 C1N4 O2
NO2
Exact Mass: 270.09
N
Mol. Wt.: 270.72
Cl N
NO2
Intermediate 1 272.15 N C10 H10 C1N3 O4
Exact Mass: 271.04
Mol. Wt.: 271.66
Cl N HOOC
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NH
NH2
NO2
Intermediate 3 237.19 N C8 H17 C1N4 O2
H Exact Mass: 236.10
Mol. Wt.: 236.70
Cl N
H
When the discharge time was 180 min the removal rate of One component and the three main intermediate prod-
the TOC was above 70%. Due to the production of inter- ucts generated during NTP degradation were identified
mediate products, the reduction in TOC was slower than from the HPLC–MS results (Table 2). During the treat-
the NTP degradation rate. As shown in Figure 6, the pH ment process organic acids were formed, leading to the
value decreased with increasing treatment time. This indi- decrease in pH mentioned in Section 2.4. When the dis-
cated that most of the degraded organic carbon would be charge time was sufficiently long, the NTP molecules were
converted into carbon dioxide [23]. eventually converted to inorganic carbon and inorganic
nitrogen in the form of bicarbonate, carbon dioxide and
nitrate. These results are in agreement with the literature
3.7. HPLC–MS analysis of NTP degradation [23,27–30].
In order to easily understand the mechanism of the degrada-
tion of NTP-contaminated wastewater, a high-performance
liquid chromatography mass spectrometry (HPLC–MS) 4. Conclusions
technique was used to identify the intermediates formed in This investigation showed that NTP in wastewater can be
the degradation process. Figure 9 shows HPLC–MS total effectively degraded by low-temperature plasma, bearing in
ion flow during NTP degradation. mind the following factors:
As shown in Figures 9(I) and 9(II), the NTP
molecules (retention time t = 4.93–5.03 min) were grad-
ually degraded and intermediate products (retention time • An initial NTP concentration of 100 mg L−1 gave a
t = 4.60–4.62 min) were generated in the course of the satisfactory removal rate. Too low a concentration
180 min treatment. It can be seen from Figure 9(III) reduced the degree of contact with • OH, and the lim-
that the intermediate products were further degraded as ited quantity of • OH was insufficient to react with the
electrolysis continued, and the chromatographic peaks amount of NTP present.
at retention times t = 4.60–4.62 min and 6.25–6.27 min • An input power of 200 W for 180 min was optimal for
disappeared. the discharge, giving 82.7% decomposition of NTP at
Environmental Technology 1615
an energy efficiency of 2.8487 × 10−10 mol J−1 . The [9] J.B. Zhang, Z. Zheng, Y.N. Zhang, J.W. Feng, and
NTP degradation process fits first-order kinetics. J.H. Li, Low-temperature plasma-induced degradation of
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pp. 506–512.
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