Oxidative Decoloration of Dyes by Pulsed Discharge Plasma in Water

J. /ov. Dx|o. Tecnno|. vo|. 8, ho.
2, 2005
- 1 -
Oxidative Decoloration of Dyes by
Pulsed Discharge Plasma in Water

Anto Tri Sugiarto
a
, Shunsuke Ito
a
, Takayuki Ohshima
a
, Masayuki Sato
a
and Jan D. Skalny
b

a
Department of Biological and Chemical Engineering, Gunma University,
1-5-1 Tenjin-cho, Kiryu-shi, Gunma 376-8515, Japan

b
Department of Plasma Physics, Comenius University
Bratislava 84215, Slovakia

Abstract
Degradation of organic dyes by the pulsed discharge plasma between needle-to-plane
electrodes in contaminated water has been investigated in three discharge modes: (i) streamer,
(ii) spark, (iii) spark-streamer mixed mode. The process of the decoloration has been found to
be most effective if the discharge operates in the spark-streamer mixed mode in dye solutions.
The decoloration rate during the pulsed discharge plasma treatment was depended on the initial
pH values. The decoloration rate was increased when more acidic condition was used,
especially in the case of streamer discharge mode. The decoloration rate at the pH value of 3.5
was found to be approximately three times higher than that at the pH value of 10.3. A small
effect of initial pH during the decoloration process by spark and spark-streamer discharge
mode means that the physical effects, such as shock-wave and ultraviolet radiation, may play
an important role in the oxidation process. It was found that the decoloration rates in the case of
spark and spark-streamer mixed discharge modes, which are characterized by high intensity
ultraviolet radiation, were found to be much higher than that in the case of streamer discharge
that is characterized by low intensity ultraviolet radiation. In addition, the considerable
increase in the decoloration efficiency of H
2
O
2
containing solutions can be attributed to the
increase in hydroxyl radicals concentration. These are produced by ultraviolet light
photo-dissociation of H
2
O
2
molecules in water surrounding the plasma channel.

J. /ov. Dx|o. Tecnno|. vo|. 8, ho. 2, 2005
- 2 -
Keywords: Pulsed Discharge Plasma; Advanced Oxidation Process; Ultraviolet radiation; Dye
Decoloration

1. Introduction
A variety of new synthetic organic dyes are frequently used by modern textile technologies.
Therefore, the removal of these dyes from effluents becomes the major environmental problem
of the textile industry, not only because of the potential toxicity of certain dyes, but often due to
their visibility in wastewater. Although the dye concentration in wastewater is usually lower
than that of many other chemical compounds, these dyes are visible even at very low
concentrations. In general, dye-containing wastewater can be treated in two ways: (i) by
chemical or physical process and (ii) by biodegradation process. Due to the variety of different
organic compounds, containing various substituted aromatic nuclei, there is no universal
chemical method for a removal of dye from wastewater.
Recent experimental investigations have revealed that reactive dyes can be decolorized by
advanced oxidation processes (AOPs). For example, the ultraviolet light induced degradation
combined with H
2
O
2
/O
3
or Fenton process alone was utilized for such processing [1-5].More
recently, among the AOPs, the pulsed discharge plasma in water is considered to be an
applicable method for removal of organic pollutants from wastewater [6,7]. Pulsed discharge
plasma in water is efficient in the formation of chemically active species such as OH, H, O, O
3
,
H
2
O
2
, etc [8,9]. Most of these species are among the strongest oxidizing agents. The major
active species involved in the degradation of organic pollutants are hydroxyl radical and
hydrogen peroxide [8]. The hydroxyl radicals can directly attack organic pollutants contained
in water due to their high oxidation potential, and the hydrogen peroxide can effectively be
decomposed by ultraviolet radiation into hydroxyl radical [10]. In addition, depending upon
the solution conductivity and the magnitude of the discharge energy, shock-waves and
ultraviolet light may also be formed [11]. These effects also play an important role in
- 3 -
destroying harmful organic pollutants in wastewater [11].
The pulsed discharge in water has several modes such as streamer, spark, and spark-streamer
mixed mode. It has been reported earlier that the pulsed discharge mode can affect the removal
efficiency of phenol in water solutions [12]. The differences in removal efficiency were
considered to be caused by the differences in the physical and chemical processes of each
pulsed discharge mode in the water.
The objective of this paper is to present the experimental data on the oxidative decoloration
of dyes in water using three pulsed discharge modes. The effect of the initial pH, the emission
intensity of ultraviolet light from the pulsed discharge plasma, and the effect of hydrogen
peroxide additives on the decoloration efficiency were also examined.

2. Experimental apparatus and method
The schematic diagram of experimental apparatus is shown in Fig. 1. The pulsed electric
discharge was generated in the electrode system of the needle-to-plane electrode geometry
located in the centre of plexiglas cylinder (50 mm inner diameter) reactor having the volume
100 cm
3
. Stainless steel tube needle (0.5 mm inner and 1.5 outer diameter) protruded 1 mm
from silicone insulator and was placed on axis of the reactor opposite to the stainless steel plane
electrode (diameter of 30 mm). Three distances between the needle and plane electrodes were
fixed at: 30 mm for the streamer, 15 mm for the spark-streamer mixed, and 7 mm for the spark
discharge mode [12], respectively. In experiment the spark-streamer mixed mode was in the
time course with the mixing degree was 50:50.
The pulse power supply with a rotating spark-gap switch was used to generate high voltage
pulse. The pulse voltage amplitude, pulse frequency, and the capacitance of the storage
capacitor: 20 kV, 25 Hz, and 6 nF, respectively, were kept constant in all experiments.
The total volume of 300 mL of solution was circulated through the reactor and temperature
controller by peristaltic pump at the solution flow rate of100 mL/min. Rhodamine B (basic dye),
- 4 -
Methyl Orange (acid dye), and Chicago Sky Blue (direct dye) were treated in experiments.
Their concentrations were 0.01 g/L and 0.05 g/L. The conductivity of the solution was changed
by adding KCl and was adjusted to 100 S/cm. Since the conductivity greatly affect the
formation of plasma discharge in water, the initial conductivity should be kept constant in all
experiment. Therefore, the initial solution pH was adjusted by added a little amount of HCl
and/or KOH into the solution until the conductivity becomes 100 S/cm.
Spectrophotometer (Shimadzu, UV-1200) was used for measuring dye absorption. The
decoloration factor F
D
was calculated by the following formula.
( ) ( )
( ) initial absorption
treated absoption initial absorption
F
D
= (1)
The temporal development of F
D
factor was measured.
In order to investigate the emission intensity of ultraviolet light produced by pulsed
discharge plasma, the light emitted from the discharge was collected by the optical fiber and
transmitted to the entrance slit of a monochromator (McPherson 2035) equipped with a
photomultiplier tube (Hamamatsu R764). The end of the optical cable was located 10 mm from
the point electrode and 10 mm from the axis of the discharge gap. The temporal variation of the
light emission in the wavelength of ultraviolet region (200 < < 300 nm) was recorded on
oscilloscope (Tektronix TDS3032). Ten peak values of successive light pulses were averaged
with fluctuation less than 20% of the average value.

3. Results and discussion
3.1 Decoloration of dyes
Due to differences in the chemical composition of dyes, there is no universally applicable
chemical technology for a removal of dyes from wastewater. Therefore, it is necessary to find a
nonselective method in order to simplify the decoloration process. Using the pulsed discharge
plasma in water, decoloration of several kinds of dyes was tested. Results obtained in the
spark-streamer mixed mode of discharge are shown in Fig. 2. The decoloration factor reached
- 5 -
the value of 95% after approximately 100 minutes of treatment if the initial concentration of all
three substances was 0.01 g/L. The rate of decoloration was considerably affected by initial
concentration of dye in solution. The decrease in the rate of decoloration for Rhodamine B is
evident from Fig. 2.
It can be easily surmised from the presented results that the pulsed discharge plasma in water
is an effective method for the decoloration of dyes from water solutions. The process of
decoloration is complex including more mechanisms that act simultaneously. Among them,
the break-up of chromosphores bounds, due to the activity of hydroxyl radicals, is the dominant
process in the dye solution.

3.2 Effect of various pulsed discharge modes

The efficiency of the decoloration process is affected by the mode of the pulsed discharge as
it follows from plots shown in Fig. 3. The differences in decoloration rate of Rhodamine B by
various pulsed discharge modes are remarkable. The spark-streamer mixed mode was found to
be the most effective for the decoloration of dye in water solutions. The mentioned regime is
characterized by great amount of plasma channels distributed bush like in great volume of the
discharge gap and also by relatively high discharge currents.
Processes acting in the plasma channel determine the differences in the decoloration rate. In
the case of the spark discharge, a single plasma channel is formed in the liquid, but the channel
has the high peak current of several hundred amperes compared to the streamer discharge
characterized by peak currents below of 100 A [13]. The concentration of electrons producing
the hydroxyl radicals by electron impact dissociation of water molecules and the gas
temperature in the plasma channel of the spark mode, are higher than that of corresponding
parameters in the streamer mode. Therefore, more radicals are formed in the spark mode
compared to the streamer mode. For these reasonsthe decoloration rate becomes higher in the
case of the spark mode than in the case of the streamer mode. Moreover, dyes can be
- 6 -
decolorized even directly by ultraviolet light. It can be considered that the intense radiation of
ultraviolet light emitted from the spark plasma channel is active in radical reaction of the dye
decoloration.
The spark-streamer mixed discharge mode is characterised by an appearance of many
plasma channels [12]. The conditions are favourable for the generation of hydroxyl radicals by
electron impact dissociation in the channels distributed over a large water volume that can
explain the highest efficiency of such mode in decoloration of dyes. Moreover the direct
photo-dissociation of dyes can be also active.

3.3 Effect of pH
It is well known that the oxidation processes are very sensitive to the pH of the aqueous
solutions. It was reported that the decoloration of dyes using photolysis process is more
effective at low pH values than high pH values [14]. Kang et al. [15] reported that the optimum
pH for both the formation of hydroxyl radicals and dye removal in photo Fenton process ranges
from 3 to 5.
Using various pulsed discharge plasma modes, the efficiency of decoloration of aqueous
Chicago Sky Blue with different initial pH was tested. The obtained results after 30 minutes
treatment are shown in Fig. 4. The initial pH of each plasma discharge mode was 3.5, 7.5 and
10.3. The initial conductivity of each plasma discharge was 100 S/cm. The decoloration rates
of Chicago Sky Blue were different for various modes, and depended on the initial pH of dye
solutions. It was found that pH and conductivity after plasma treatment was different for each
plasma discharge mode, e.g. in the case of streamer discharge, the pH was changed from 7.5 to
6.2, and conductivity was changed from 100 to 120 S/cm after 30 minutes treatment. In the
case of spark discharge, the pH was changed from 7.5 to 5.5, and conductivity was changed
from 100 to 155 S/cm after 30 minutes treatment. These results are in accordance with
decoloration of dye using ozonation process [14], which shows that the dye molecules
decompose into organic acids, aldehydes, resulting in a decrease in pH values and increase in
- 7 -
water conductivity. The decoloration rates were increased when more acidic conditions were
used, especially when the streamer discharge mode was used. The decoloration rate at the initial
pH of 3.5 is approximately three times faster than that at the initial pH of 10.3.
Joshi et al [8] reported that the major active species involved in the degradation of organic
pollutants using pulsed streamer corona discharge are hydroxyl radicals and hydrogen peroxide.
However, in the case of pH values higher than 7, the hydroxyl radicals are unselective and react
readily with the carbonate ions, substantially reducing the efficiency of the oxidation process
[16]. Carbonates are generated through the breakdown of the organic materials during the
oxidation processes. For these reasons, it can be considered that the decoloration by hydroxyl
radical is the dominant process during the streamer discharge mode treatment.
On the other hand, in the case of spark and spark-streamer mixed modes, the effect of initial
pH on the decoloration rate was small. It means that the other physical effects such as shock
wave and ultraviolet radiation play an important role in the decoloration process during the
spark and spark-streamer mixed mode of the discharge treatment.

3.4 Ultraviolet radiation
One of the physical effects produced by pulsed discharge plasma in water is ultraviolet
radiation. In the case of the pulsed arc discharge reactor, the temperature in the plasma channel,
which forms during an electrohydraulic discharge, can reach values of 14.000 15.000 K and
thus functions as a blackbody radiation source. A maximum of emittance of such source is in
the vacuum ultraviolet (VUV) region of the spectrum (=75-185 nm) [14]. The vacuum
ultraviolet light emitted from the hot plasma is absorbed immediately in the water layer
surrounding the plasma channel [11], and the ultraviolet light with >185 nm penetrates into the
bulk of the solution.
The emission intensity of ultraviolet light produced by three pulsed discharge plasma
modes in distilled water is shown in Fig. 5. The intensity of ultraviolet light radiation in the
- 8 -
case of spark discharge was much higher than that of the other discharge modes. In the case of
spark discharge, a single plasma channel is formed in the liquid. The plasma channel has the
high peak current of several hundred amperes, and according to Brmann et al. [17] the electron
density in the propagated leader channel is high, close to the values typical for a thermal arc.
This condition makes the plasma channel that becomes a source of light with high intensity of
ultraviolet radiation.
However, the intensity of ultraviolet light in the case of streamer discharge was found to be
very low. This is because streamer discharge in the distilled water is characterised with the
bush like-streamer discharge channel, and a moderate amount of bubbles. Therefore, the
plasma channels emit very low intensity of ultraviolet light as shown in Fig. 5. It should be
noted that an increase in the solution conductivity might increase the emission intensity of
ultraviolet light of the pulsed discharge plasma in water [18].

3.5 Effect of hydrogen peroxide

The use of chemical additives for enhancement of the energy efficiency of the depletion of
dyes is one of the recommended methods. In this study, the effect of hydrogen peroxide on the
removal of Rhodamine B by various pulsed discharge modes has been investigated. Results are
shown in Fig. 6. The initial concentration of hydrogen peroxide of 8.810
-3
mol/L was used for
all experiments. The initial pH of each plasma discharge mode was 7.5. The increase by
addition of hydrogen peroxide in the rate and in F
D
values is apparent for all three modes of the
discharge.
The dramatic increase of decoloration rate most likely appears due to the reactions of dyes
with hydroxyl radicals formed by photo-dissociation of hydrogen peroxide in the gap
surrounding discharge channels. The low threshold energy for photo-dissociation of H
2
O
2
in
comparison with water makes this process strictly dependent on the light intensity. The spark
discharge mode is characterised with high light intensity as shown in Fig. 5. Therefore, the
- 9 -
process of dye removal from water is most effective in the case of spark discharge mode. The
production of hydroxyl radicals by electron impact dissociation, which normally dominates in
streamer or spark-streamer mixed modes, becomes less important. The changes in the
dominant mechanism of hydroxyl radical production can be explained by the high efficiency of
the single spark mode of the discharge. The intensity of UV radiation from spark-streamer
mixed mode of discharge and especially pure streamer mode are evidently lower.

3.6 Mechanism and intermediates
Decoloration process using plasma discharge in water is complex including more
mechanisms that act simultaneously. Our experimental results showed that hydroxyl radical
and ultraviolet radiation were dominant on decoloration process during plasma discharge. This
process is similar like in photooxidation of dye using combination of ultraviolet radiation and
hydrogen peroxide. As reported by several authors, the schematic mechanism of
photooxidation on decoloration process are proposed as follows [14, 19],
RH + h R
+ H (2)
H
2
O
2
+ h OH + OH (3)
OH + RH R
+ H
2
O (4)
R
+ O
2
RO
2
(5)
A direct photooxidation of dye with ultraviolet light alone can lead to the decoloration of dye.
However, direct photooxidation of dye in water is very limited since water absorbs significantly
in the vacuum UV region. Therefore, ultraviolet light is practically used in combination with
oxidant (e.g. hydrogen peroxide) or catalysts (e.g. titanium oxides). The combination of
ultraviolet and hydrogen peroxide can form hydroxyl radicals. The hydroxyl radicals react with
dye (RH) to form dye
+
(R
), and then dye

+
could hydrolize or react with some oxidizer such as
dissolved oxygen (19).
If the decoloration process by plasma discharge is as same as the photooxidation process by
- 10 -
ultraviolet with hydrogen peroxide, the decoloration of methyl orange occurs due to the break
up of the azo bond (NN) by hydroxyl radicals, generating 4-methylamino aniline, and then
underwent a further opening of phenyl-rings to form small molecular compounds such as oxalic
acid and butenedioic acid [20]. In the case of plasma discharge with strong ultraviolet radiation
(i.e. spark and/or sparkstreamer mixed discharges), ultraviolet radiation will take part in the
break up of the azo bond.

3.7 Energy efficiency
The above investigation was focused on the reaction mechanisms and improvement of the
removal rate. However, in practice, energy efficiency is an important factor. The energy
efficiencies of three pulsed discharge modes for Rhodamine B (see Figure 6) were 25 mg/kWh
for streamer discharge, 80 mg/kWh for spark discharge, and 160 mg/kWh for spark-streamer
mixed discharge modes. When the additive (8.810
-3
mol/L hydrogen peroxide) was injected
into the reactor, the energy efficiency became 320 mg/kWh for spark-streamer mixed
discharge.

4. Conclusions
The process of dye decoloration from water solutions has been investigated using three
pulsed discharge modes in water. The decoloration process was complex and active oxidation
mechanisms were most likely hydroxyl radicals and ultraviolet light radiation. In the case of
streamer discharge, the decoloration rate was dependent on the initial pH solution. Hence, the
oxidation process by hydroxyl radicals is considered to be the dominant dye removal process.
However, a small effect of the initial pH solution on the decoloration rates by spark discharge
and spark-streamer mixed discharge mode mean that the other physical effects such as
shock-waves and ultraviolet radiation play an important role in the decoloration process.
In water solution hydroxyl radical generated mostly in the discharge channel by the electron
- 11 -
impact dissociation of water molecules. Therefore, the spark-streamer mixed discharge mode
was the most effective. In addition, the intensity of ultraviolet light radiation generated by the
plasma channels was high enough for direct photo-dissociation of dyes.
In solutions containing hydrogen peroxide, hydroxyl radicals formed in the water by
ultraviolet light stimulated photolysis of hydrogen peroxide. Therefore the highest efficiency
of spark mode characterised by the highest intensity of emitted light has been found in
experiments.

Acknowledgements

Part of this work was supported by a Grant-in Aid for Scientific Research of the Ministry of
Education, Science, Sport and Culture, Japan, #11555205 and 12895021.

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- 14 -
Figure Captions

Fig. 1 Schematic diagram of the experimental apparatus
Fig. 2 Decoloration of aqueous dye solutions by pulsed discharge treatment
Fig. 3 Decoloration of aqueous Rhodamine B solution by various pulsed discharge
modes
Fig. 4 Decoloration efficiency of aqueous Chicago sky blue solution by various
pulsed discharge modes as a function of initial pH
(Applied voltage = 20 kV, Treatment time = 30 min, Dye concentration = 0.01 g/L)
Fig. 5 Spectrum of ultraviolet emission of various pulsed discharge modes in distilled
water
modes in the presence of hydrogen peroxide

- 15 -

Fig. 1 Schematic diagram of the experimental apparatus

- 16 -

Fig. 2 Decoloration of aqueous dye solutions by pulsed discharge treatment

- 17 -

modes

- 18 -

Fig. 4 Decoloration efficiency of aqueous Chicago sky blue solution by various
pulsed discharge modes as a function of initial pH
(Applied voltage = 20 kV, Treatment time = 30 min, Dye concentration = 0.01 g/L)

- 19 -

Fig. 5 Spectrum of ultraviolet emission of various pulsed discharge modes in distilled
water

- 20 -

modes in the presence of hydrogen peroxide

Oxidative Decoloration of Dyes by Pulsed Discharge Plasma in Water

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), and then dye

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