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International Journal of Plasma Environmental Science and TechnologyVol.3, No.1, MARCH 2009

Degradation of organic contaminants in water by plasma

M. Sato
Professor Emeritus, Gunma University, Japan

AbstractAtmospheric pressure plasma in water or in gaseous media is applicable to decompose organic materials in environmental water and kill bacteria in waste water. Plasma has a characteristic feature that all kinds of organic materials including recalcitrant matter are decomposed due to active species produced by plasma. The plasma is generated by pulsed discharge in water, on the water surface, and in the bubbles in water. For applying to industrial use, the energy efficiency for generating plasma will be the most important factor. To increase the total energy efficiency (decomposed molecules / input energy), a hybrid system such as plasma-biotechnology or plasma-chemical reaction would be one of the solutions. Keywordsunderwater plasma, water surface plasma, contaminant degradation, water purification

I. INTRODUCTION Recently, contamination of environmental water becomes a big problem. Groundwater, river, and lakes are polluted by human activities and industrial wastes. Chemical and/or biological treatments have been widely used to purify the water, but there are no suitable technologies to decompose recalcitrant organic matter. The hydroxyl radical is the most powerful oxidant to decompose organic materials, and is produced easily due to underwater discharge plasma or gaseous plasma. Underwater plasma is produced due to the electrical breakdown of water, when the electric field concentrates to the needle tip [1]. Many kinds of active species were detected from the streamer discharge by emission spectrum [2,3]. The active species decompose organic materials in water, finally into carbon dioxide and water through intermediate materials. Formation mechanism of the underwater plasma was considered that the initial discharge could start in a small bubble on the needle electrode surface, and then could propagate into water phase. Introducing gas bubbles into the plasma region could decrease discharge voltage [4]. Energy efficiency to decompose organic materials is depended on the reactor design, i.e., (a) gas bubbling through metal tube electrode [5], (b) gas bubbling through porous ceramic tube [6,7], (c) discharge through pinhole [8,9], (d) water surface plasma and wetted-wall plasma reactor [10,11], or hybrid type reactor [12], and so on [13]. Electrical breakdown or disruption of a biological cell by pulsed electric field (PEF) is well understood to occur by electromechanical compression of the cell membrane, which results in inactivation of microorganisms. The effective sterilization by using PEF-induced irreversible disruption of biological membranes was investigated and reported. The treatment temperature, growth temperature, and the shape of the reactor were found to have a great Corresponding author: Masayuki Sato e-mail address: mxsato@nifty.com
Accepted; March 25, 2009

effect on PEF sterilization. The PEF-induced reversible disruption of the membrane could be utilized for selective release of intracellular proteins from a certain gene-engineered E. coli. The secretion of periplasmic protein from E. coli was achieved during cultivation. In addition to the cell inactivation, chromosomal DNA and RNA molecules were decomposed, and activation and inactivation of enzymes would be possible by PEF treatment. The outlines of some environmental applications using high voltage pulsed plasma in water or in gas phase are mentioned briefly in the present paper.

II. PURIFICATION OF ENVIRONMENTAL WATER BY

PLASMA

A. Underwater plasma Using underwater electrical discharges in point-toplane electrode geometry, magenta colored streamer was observed. The streamer length was varied with varying electrical conductivity of water, having a plateau at about 0.01 mS/cm of the water conductivity. The streamer length increased as the pulse width increased. When the streamer touched to the ground electrode, the discharge mode changed to spark discharge. Emission spectra from H, OH, O radicals were detected as shown in Fig. 1. Fig. 2 shows time profile of voltage and current in the case of

Fig. 1. Emission spectrum from pulsed discharge in water with point-to-plane electrode configuration [5].

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Fig. 4. Illustration of three discharge modes in water, where (a) streamer (electrode distance L: 45 mm), (b) spark with streamer combined (L: 15 mm), (c) spark (L: 6 mm) [18]. Fig. 2. Wave patterns of voltage and current in the case of spark discharge in water using point-to-plane electrode configuration [19].

Fig. 5. Decoloration of aqueous Rhodamine B solution by three discharge modes with and without addition of hydrogen peroxide, where concentration of Rhodamine B and hydrogen peroxide: 0.01 g/L and 8.8x10-3 mol/L [26]. Fig. 3. Varying hydrogen peroxide concentration by applied pulse energy with and without catalase addition, where pulse voltage: 19 kV, in distilled water [14].

spark discharge. The streamer discharge started after the fast rising pulse voltage was applied to the electrode, showing a small current. When the streamer channel approached to the opposite ground electrode, the spark discharge occurred, where the discharge current increased rapidly up to 320 A. After that the current became zero, because the pulse power source was a capacitor discharge type. Hydrogen peroxide was produced by the streamer discharge in water [2,14-17]. Variation of hydrogen peroxide concentration due to the streamer discharge in distilled water with and without addition of catalase is shown in Fig. 3. In this measurement, the total amount of oxidizing agents, such as ozone, hydrogen peroxide, and others was measured after pulse treatment by a biochemical test method using enzymes. Discharge mode changed with changing the distance between point-to-plane electrode; with 6 mm for spark discharge, 15 mm for spark with streamer discharge combined, and 45 mm for streamer discharge [18]. The applied voltage was 20 kV with a frequency of 50 Hz. A little KCl was added into the solution in order to change the liquid conductivity. Illustrations of three discharge modes are shown in Fig. 4. In the case of streamer discharge (a), there are many magenta colored plasma

channels formed in the liquid. In the case of spark discharge (c), a single plasma channel is formed in the liquid, and their energy is very strong, which seems to be a high intensity ultraviolet light source without any wall to interrupt the penetration into the water. During the formation of plasma channels, a strong shock wave is generated in liquid. The high energy electrons in the plasma channels, strong ultraviolet radiation and shock waves are very effective in exciting and ionizing the water molecules, and therefore, more radicals are formed in the spark discharge compared to the streamer discharge. On the other hand, in the case of spark with streamer discharge mode, there are many plasma channels produced. Their energy seems to be strong, and the channels are more stretched than in the other cases. Since the distribution of active species occurred mainly around the plasma channels [19], a large number of channels with a strong energy would be very effective to generate a large number of active species. As shown in Fig. 5, decoloration of Rhodamine B was very effective in the case of streamer with spark discharge mode than the other cases. In the spark mode, the addition of hydrogen peroxide is effective to raise energy efficiency of decoloration. The electrical energy of 360 J/mL was necessary for 80 % decoloration without hydrogen peroxide addition, but the energy efficiency was improved to 70 to 80 J/mL with the addition of hydrogen peroxide. In the presence of hydrogen peroxide, the decomposition rate of phenol was very high in the case of

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International Journal of Plasma Environmental Science and TechnologyVol.3, No.1, MARCH 2009

spark discharge. This is because the spark discharge radiates very strong ultraviolet light compared to the other discharge modes. Approximately 30 % of the plasma energy is radiated in the UV spectrum according to Robinson [20], and then a large number of hydroxyl radicals can be produced in the reactor (Eq. 1). H2O2 + h = OH + OH (1) Phenol decomposition was the same tendency in reaction rate of the decoloration. B. Simultaneous discharge in gas bubbles and in water As shown in Fig. 6, pulsed discharge plasma was generated in the gas phase, and the produced plasma was permeated into the water phase through the pinhole [6]. Water (upper) and gas (lower) were separated by an insulating plate with a pinhole, through which gas was bubbled into the water phase. In the gas phase, the highvoltage pulse was applied between the needle electrode and the ground electrode (immersed in the water phase). The pulsed discharge plasma was generated in the gas phase; simultaneously, the plasma channels were permeated into the water phase accompanied by the gas bubbles. Fig. 7 shows an example of simultaneous discharge in liquid phase at 20 kV applying pulse voltage when oxygen gas was bubbled through the pinhole at the rate of 100 mL/min. The streamer channels are stretched
ground

into the water phase accompanying with the gas bubbles. To increase the processing fluid volume, a porous ceramic tube (average pore size: 15 m, wall thickness: 4 mm) was used as a gas disperser instead of a pinhole as shown in Fig. 8. The discharges spread over the ceramic tube surface and formed many streamers in the water phase. The streamer and the active species decompose organic materials. The aqueous Chicago sky blue solution with 10 ppm initial concentration was decolored by about 95 % in 10 min treatment (using pinhole system). The decoloration rate increased with increasing electrical conductivity of the solution. The decoloration rate became higher with increasing applied voltage, because the discharge intensity was getting stronger with the higher voltage. However, as shown in Fig. 9, the energy efficiency for decoloration in each applied voltage (plots of decoration rate versus pulse energy) falls on almost the same line. The effect of electrical conductivity of the solution to the decoloration rate is shown in Fig. 10, where the oxygen gas was bubbled with 150 mL/min, applied pulsed voltage was 15 kV, and initial dye concentration was 10 ppm. As shown clearly in the figure, the decoloration rate increased with increasing conductivity of the aqueous dye solution. It was reported in the previous papers, in the case of producing pulsed

stainless steel mesh porous ceramic tube ground

gas and water mixture

water inlet
PVC thin plate

to HVP gas inlet

HV pulse

Fig. 8. Porous ceramic tube reactor, where treatment cell: 60 mm height, 50 mm inside diameter; average pore size: 15 m, wall thickness of ceramic tube: 4 mm.
100

Decoloration rate [%]

Fig. 6. Extended view of the treatment cell of simultaneous discharge in gas bubbles and in water, where treatment cell: 60 mm height, 50 mm inside diameter; PVC thin plate: 2 mm thickness with 0.5 mm diameter pinhole [6].

80 60 40 20 0 0 100 200 300 400 500 600 +10 kV +25 kV +15 kV +20 kV +8 kV

Energy [J/mL]
Fig. 7 Photograph of discharge state in water phase with oxygen gas bubbling, where gas flow rate: 100 mL/min, applied voltage: +20kV. Fig. 9 Percentage decoloration of Chicago sky blue with varying input pulse energy and applied voltage (100 mL/min oxygen bubbling).

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100

Decoloration rate [%]

80 60 40 20 0 0 10 20 30 40 50 60 S/cm 1000 500 100 10

Fig. 11. Illustration of water surface plasma.

Treatment time [min]

Fig. 10 The effect of electrical conductivity of aqueous dye solution, where initial concentration of Chicago sky blue: 0.01 g/L, applied voltage: 15 kV, oxygen gas bubbling with 150 mL/min.

discharge directly in water using needle-plate electrode configuration, the electrical current flowing through the electrode increased greatly with increasing the conductivity of water [5]. The streamer length decreased with increasing conductivity, which resulted in the decoloration rate decreased. From the figure, the decoloration rate reached to almost 100 % at 20 minutes treatment in the case of 500 - 1000 S/cm of the solution conductivity. Therefore, when we apply to treat tap water or sewage water having conductivity of 200 to 2000 S/cm, this system is considered to have a characteristic feature to raise energy efficiency for degradation of organic contaminants in water. C. Water surface plasma For decomposition of organic contaminants in water, the gas phase corona or streamer discharge on the water surface have been reported [11,21]. The corona discharge on the water surface produces some kinds of active species that effectively react with organic materials in water. The streamer discharge on the water surface is also effective for decomposing organic materials in water due to their active species and UV light, and high-energy electrons hit the water surface. As illustrated in Fig. 11 and shown photo in Fig. 12, filamentary discharge from the needle tip in the gas phase on the water surface was observed. Ozone and active species produced by the discharge may dissolve into water through the water surface, and then they were decomposed to some kinds of radicals or hydrogen peroxide. High-energy electrons may dissociate water molecules then produce radicals. Many chemical reactions may occur by water surface plasma, which may decompose organic contaminants in water. When electrode distance between the needle tip and the water surface was adjusted to 5 mm, the water surface plasma discharge could be obtained in both argon and oxygen gases. In argon gas, bright blue colored discharge streamers were seen and were accompanied by popping sounds. On the other hand, rather weak water surface plasma was obtained in oxygen gas. The percent

Fig. 12. Discharge state (Argon: 1 L/min, Pulse voltage: +25 kV, distance between needle tip and water surface: 8 mm).

decomposition increased with increasing treatment time and was higher for oxygen than for air, because the electrical discharge produced much more ozone in oxygen than in air. The generated ozone probably dissolves in the water through the surface layer and then reacts with the phenol by hydroxyl radicals or other active species converted from the dissolved ozone. Among the various discharge modes for decomposing phenol in water, Fig. 13(a) shows the percent phenol decomposition using oxygen as a function of elapsed treatment time for three different discharge modes obtained by changing the electrode distance: 1) water surface plasma (WSP), 2) streamer, and 3) corona discharge. The phenol decomposition increased with increasing treatment time, particularly in the water surface plasma mode. On the other hand, when the decomposition was plotted against the consumed energy, as shown in Fig. 13(b), the points for the three modes were all on the same curve. Each discharge mode such as corona, streamer, and water surface plasma may have different decomposition mechanisms. The corona and streamer discharge modes can decompose organic materials with low energy, but a long treatment time is required. On the other hand, in the water surface plasma mode, the decomposition rate is higher than the other discharge modes, but it requires more energy for water treatment. The water surface plasma on the horizontal water surface was applied to the vertical water film in wettedwall reactor [10]. As shown in Fig. 14, it is expected that the reaction area could be larger, liquid volume for treatment could be larger, and the processing time could be shorter in the wetted-wall reactor. The pulsed discharge plasma occurred between the center electrode and ground electrode, where the positive pulsed high voltage was applied to the center electrode. The sample

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International Journal of Plasma Environmental Science and TechnologyVol.3, No.1, MARCH 2009

100 Phenol decomposition [%]

Oxygen : 1 [L/min]

80 60 40 20 0
: WSP : Streamer : Corona

(a)

(b)

Fig. 15. Two types of wetted wall reactor.

10 20 30 40 50 Treatment time [min]

60

100 Phenol decomposition [%]

Oxygen : 1 [L/min]

80 60 40 20 0 0.1

: WSP : Streamer : Corona

Fig. 16. Variation of phenol decomposition rate with some wetted wall reactor types and gas phase.

1 10 100 Input energy [J/mL]

Fig. 13. Percent phenol decomposition for three kinds of discharge modes with an oxygen gas flow, where oxygen gas flow rate: 1 L/min, pulse frequency: 100 Hz for water surface plasma (WSP) and 600 Hz for streamer and corona discharges, electrode distance: 7.5 mm for WSP, 15 mm for streamer, and 20 mm for corona.
High voltage pulse

Gas in Water in

Wetted-wall

Gas and water out

Fig. 14. Illustration of wetted-wall plasma reactor [10].

liquid was circulated by peristaltic pump, in which the water fell down along with the inner surface of the cylinder forming wetted-wall. Gas was introduced from the upper part of the reactor and out from the bottom as gas-water mixture. Typical types of reactors are shown in Fig. 15(a) and (b). Reactor (a) is made of aluminum cylinder and center electrode with 1 x 1 mm tungsten square wire. Inner surface of the cylinder was treated by corona discharge before starting the experiment to increase contact angle between aluminum and water. In reactor (d), the disk

electrode is set at the middle of the cylinder to make plasma easier in the oxygen gas, and grounded electrodes are glued at the top and the bottom of the Plexiglas cylinder. Reactor (a) shows the basic structure of our study, in which square wire are allocated at the center of cylindrical ground electrode. Using a reactor (a), when the gas content was varied, discharge mode changed as: (1) in the case of argon, streamer-like discharge occurred from the center wire electrode to the water surface, and decomposition rate of phenol was high (85 % decomposition at 60 min treatment). However, the streamer mode easily shifted to sparking mode, because the streamer discharge paths could touch to the surface of the aluminum cylinder through the thin water film. (2) in the case of air or oxygen, the discharge mode was corona, and the decomposition rate in the case of oxygen was a little less than the above case (1). Using a disk plate with sharp edge as a discharge electrode (d), it was possible to keep streamer mode even in the case of air, oxygen, and argon gases. In the streamer mode, the decomposition rate of phenol was higher in argon (40 % after 60 min) than the case of oxygen (25 %). It was because the discharge channels strike the water surface and produce active species by direct dissociation of water molecules. In order to check the effect of electrical conductivity of the liquid on the decomposition of phenol, the conductivity was varied with adding NaCl to the liquid. Effective decomposition of dissolved phenol could be achieved independently with the solution conductivity, so that the present wetted-wall reactor is applicable to treat tap or wastewaters. Fig. 16 shows comparison of decomposition efficiency of phenol with varying reactor types (a) to (d) in the case of argon and oxygen, respectively. Discharge modes were corona (oxygen gas in reactor (a)) and streamer (other cases). In the case of reactor (a), the

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decomposition rates in argon and oxygen were almost the same, though the strength of plasma was quite different between corona in oxygen and streamer in argon. Corona discharge in oxygen would generate ozone efficiently, and the ozone seemed to contribute the decomposition of phenol in water. Reactor (a) was most effective for phenol decomposition in the cases of argon and oxygen as the environmental gases. These systems can be utilized to not only the water treatment but also simultaneous treatment of water and gas at the same time.

inactivated under normal temperature by pulsed electric field, which is applicable to fresh liquid food sterilization. The energy efficiency to decompose organic materials in water is still not high, but it will be much better in the near future. The author proposes a combination of plasma and other methods i.e., biological or chemical methods, where the organic molecules are decomposed into an intermediate state due to plasma and then degraded into carbon dioxide and water by bacteria as an environment-friendly technology.

III. BIOTECHNOLOGICAL APPLICATIONS OF HIGH

VOLTAGE PULSE

It is well known that the high voltage pulsed electric field can kill bacteria in liquid by its field effect on the cell membrane disruption. However, energy efficiency of these technologies has been low as aiming for the industrial applications to food industry. The inactivation rate was considerably improved by convergence of electric field. Among some kinds of electrode systems, i.e., plate-plate, insulated plate-plate, needle-plate, ringcylinder, coiled wire-cylinder, and double spiral wire, the double spiral wire was more effective than the others, which was about four orders of magnitude higher than the plate-plate system in the survival ratio reduction [22,23]. Some factors that influence to the pulsed electric field inactivation have been investigated such as: (a) liquid temperature, (b) liquid conductivity, (c) liquid flow rate (flow velocity and residence time), (d) electrode shape and configuration, (e) electric field strength and input pulse energy, (f) additives, and others. The author reported that the intracellular proteins are released from recombinant biological cell selectively by using high voltage electric field [24]. The mechanism of the selective release is a controlled disintegration of the cell membrane by pulsed electric field. Extracellular release of recombinant -amylase from recombinant E. coli was also possible by applying high voltage pulsed electric field during fed-batch cultivation [25]. When the pulsed electric field was applied intermittently (12 kV, 3 Hz, applying 30 min with an interval of 30 min) from the beginning of the stationary phase of cultivation, the amount of -amylase released was about 30 % of the total amount of -amylase produced in the cells. The release ratio and the total amount of -amylase extracted from the periplasm were higher than that of batch cultivation system.

IV. CONCLUSION The pulsed plasma produced in water and/or in gaseous phase to purify environmental water has characteristic feature that organic contaminants are decomposed and finally converted into carbon dioxide and water in a relatively short period. Bacteria are

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International Journal of Plasma Environmental Science and TechnologyVol.3, No.1, MARCH 2009

[16] N. Koprivanac, H. Kusic, D. Vujevic, I. Peternel, and B. R. Locke, Influence of iron on degradation of organic dyes in corona, J. Hazardous Materials, vol. 117, pp. 113-119, 2005. [17] D. R. Grymonpr, A. K. Sharma, W. C. Finney, and B. R. Locke, The role of Fenton's reaction in aqueous phase pulsed streamer corona reactors, Chem. Eng. J., vol. 82, pp. 189-207, 2001. [18] A. T. Sugiarto and M. Sato, Pulsed plasma processing of organic compounds in aqueous solution, Thin Solid Films, vol. 386, pp. 295-299, 2001. [19] B. Sun, M. Sato, A. Harano, and J. S. Clements, Non-uniform pulse discharge induced radical production in distilled water, J. Electrostatics, vol. 43, pp. 115-126, 1998. [20] J. W. Robinison, Finite-difference simulation of an electrical discharge in water, J. Appl. Phys., vol. 44, pp. 76-81, 1973. [21] P. Lukes, Water Treatment by Pulsed Streamer Corona Discharge, Ph.D. Thesis, Institute of Chemical Technology, Prague, Czech Republic, 2001. [22] T. Ohshima, K. Sato, H. Terauchi, and M. Sato, Physical and chemical modifications of high-voltage pulse sterilization, J. Electrostatics, vol. 42, pp. 159-166, 1997. [23] M. Sato, N. M. Ishida, A. T. Sugiarto, T. Ohshima, and H. Taniguchi, High efficiency sterilizer by high voltage pulse using concentrated field electrode system, IEEE Transactions on Industry Applications, vol. 37, pp. 1646-1650, 2001. [24] T. Ohshima, Y. Hama, and M. Sato, Releasing profiles of gene products from recombinant Escherichia coli in a high-voltage pulsed electric field, Biochem. Eng. J., vol. 5, pp. 149-155, 2000. [25] S. Shiina, T. Ohshima, and M. Sato, Extracellular release of recombinant a-amylase from Escherichia coli using pulsed electric field, Biotechnol. Prog., vol. 20, pp. 1528-1533, 2004. [26] A. T. Sugiarto, S. Ito, T. Ohshima, M. Sato, and J. D. Skalny, Oxidative Decoloration of Dyes by Pulsed Discharge Plasma in Water, J. Adv. Oxid. Technol., vol. 8, pp. 1-20, 2005.