22nd International Symposium on Plasma Chemistry July 5-10, 2015; Antwerp, Belgium Application of pulsed Streamer plasma in bacterial disinfection and dye degradation R.K. Singh1, L. Philip1 and S. Ramanujam2 1 2 Department of civil engineering, Indian Institute of Technology, Madras, 600036 Chennai, India Department of electrical engineering, Indian Institute of Technology, Madras, 600036 Chennai, India Abstract: The present study dealt with the application of pulsed streamer plasma for disinfection of water and dye degradation. Different initial cell concentrations were used for the disinfection study. Effect of voltage magnitude, initial dye concentration and volume of contaminated water were also studied. Rate constants for disinfection and dye degradation were different with the variation of concentration, voltage magnitude and reactor volume. Keywords: pulsed, streamer, disinfection, dye degradation, rate constant 1. Introduction With the current water scarcity and waste disposal in water bodies, it is estimated that the 11% of world population are lacking safe drinking water and approximately 3000 children are dying due to water borne diseases [1]. Plethora of microbial diversity and organic pollutants in water leads to many water borne diseases and sometimes are even responsible for death. The organic dye like Methylene blue (MB) is widely being used in textiles industries and it plays the role of a robust staining material in biology and chemistry. Every year around 70,000 – 100000 tons of dye is being released directly as wastewater into the water bodies [2] and these dyes are carcinogenic, allergic and mutagenic in nature and can have significant adverse effect on humans, plants and on aquatic species [3]. To disinfect water many tertiary treatment technologies like chlorination, ozonation and UV treatment are in practise. Along with bacterial disinfection, some disinfection by-products (DBPs) such as trihalomethane and haloacetic acids etc also forms during chlorination [4] and disinfection and these DBPs are carcinogenic in nature [5]. This is one of the biggest demerits of the above said technologies. Also the control of UV dose is difficult and many times bacteria tend to revive back by their DNA repair mechanism [6]. Presently advanced oxidation processes (AOPs) such as fenton, photo-fenton, UV/O 3 , H 2 O 2 /O 3 , sonolysis, photo-catalysis etc. are gaining importance as these processes can produce hydroxyl radicals (OH*). OH*, having a high oxidation potential, gives the biggest advantage of reduction of the volume of the reactor and treatment time, which is not possible with the existing conventional treatment technologies. However most of these processes require high input of energy and high treatment cost [7]. Plasma technology in water purification, one of the latest technologies for water treatment is gaining attention because of its superior potential to kill pathogens without the production of any toxic by-products [9]. Pulsed streamer discharge in air P-III-9-27 and/or water produces different reactive oxygen species like OH*, H 2 O 2 , O 3 and O 2 -* along with UV and intense wave. This synergetic effect results in the effective oxidation of organic pollutants and/ or microbial decontamination. The present study discusses the application of pulsed streamer plasma technology in disinfection of water and dye degradation. By using pulsed high voltage, plasma in the form of streamer was produced in air and propagated to water to form different reactive species and these species in turn were responsible for the ultimate water treatment. 2. Methodology Experimental set up and electrode configuration For the high voltage power supply a 100 kVA transformer was used. A half wave rectifier circuit was designed with the help of a diode rating 140 kV, 20 mA, 100 kΩ, and a capacitor of rating 140 kv and 10000 pF. A rotating spark gap was used as a pulse generator (Fig. 1). In the present study, a self-built reactor was used. The reactor contains a multiple needle type tungsten (Alfa Aesar, India) electrode for generating the high voltage pulsed streamer discharge for a fluid capacity of 100 mL. The reactor was placed in a water jacket and cooling water at 15-20 °C was allowed to flow through the jacket to maintain isothermal conditions in the reactor. The top of the reactor had a sampling port and also a port to insert high voltage electrode into the reactor. Square pulses with a rise time of 0.4 µs and pulse width of 20 ms were used. Bacterial culture and chemicals Pure culture of E. coli bacteria was isolated from Tryptone bile glucuronic agar (Himedia, India) plate, resuspended in Luria Bertani (Himedia, India) liquid media and incubated overnight in an orbital shaker of 120 rpm at room temperature. Culture were centrifuged at 5000 x g for 10 min and washed with physiological saline prior to experiment. Quantification of bacterial concentration was performed using plate count method. 500 mg/L stock 1 a b Fig. 2. Effect of initial E. coli concentration on disinfection rate at 23 kV input voltage. Table 1. Deactivation rate constant at different cell conc. Initial E. coli conc. as log(cfu/mL) 1.00 2.19 3.30 5.60 6.73 Fig. 1. Diagrammatic representation of pulsed streamer discharge system (a) circuit for high voltage source (b) reactor with tungsten electrode. solution of methylene blue was prepared in Millipore water and different concentrations of dye 10 – 50 mg/L, was prepared by using stock solution. Different dye concentrations were quantified by measuring the absorbance at 668 nm wavelength in spectrophotometer (Shimadzu, Japan). Deactivation rate constant (log(cfu/mL)/min) 0.50 0.71 0.74 1.17 1.37 3.2. Dye degradation using pulsed streamer plasma 3.2.1. Effect of voltage magnitude on dye degradation For the MB degradation three input voltage of 17 kV, 20 kV and 23 kV was applied. From the Fig. 3, it can be observed that the dye degradation efficiency increases with the voltage magnitude because the reactive species such as OH*, H 2 O 2 and O 3 increases with voltage magnitude [10]. Total time required to complete decolourization of MB dye was 8 min for 50 mg/L dye concentration at 23 kV. Approximately 60 % of total organic carbon (TOC) removal was obtained at the end of 10 min of treatment. It shows a good agreement with reported value of Wang et al. [11]. 3. Results and discussion For the disinfection and dye degradation, a voltage magnitude of 23 kV and frequency of 25 Hz was applied. 3.1. Effect of initial cell concentration on disinfection Different bacterial cell concentrations in order of 10 cfu/mL, 102 cfu/mL, 103 cfu/mL, 104 cfu/mL, 105 cfu/mL and 107 cfu/mL were used to observe the variation in deactivation constant. The variation in deactivation rate using pulsed streamer is shown in Fig. 2. For the complete disinfection, 2 min to 6 min of treatment time was required and the rate constant for deactivation at different cell concentration is presented in Table 1. The rate of bacterial deactivation decreases with decrease in initial cell concentration of E. coli. Therefore initial cell concentration is also an important factor for deciding the rate of degradation. 2 Fig. 3. Effect of voltage on dye degradation for initial dye concentration of 50 mg/L 3.2.2. Effect of initial dye concentration and reactor volume Initial pollutant concentration and volume tends to affect the rate of degradation. Dye degradation efficiency of streamer discharge for different dye concentration is P-III-9-27 shown in Fig. 4. Similarly dye degradation efficiency of streamer plasma for different reactor volume is shown in Fig. 5. From the study it was found that, the MB follows first order kinetics for the degradation and it can be represented by Eq. 1. 𝐶 log � � = −𝑘𝑘 𝐶0 (1) where, C 0 = Initial dye concentration, C = Concentration of dye at time‘t’ and k = First order rate constant. The rate constant for dye degradation (Figs. 4 and 5) was calculated by Eq. 1 and is presented in Table 2. From the result it can be concluded that the concentration of dye and reactor volume also decides the rate of dye degradation. Table 2. Rate constant of dye degradation for different initial concentration of dye and reactor volume. Parameters Fig. 5. Dye degradation with respect to time for different reactor volume at 23 kV input voltage 4. Conclusion The current study demonstrated the applicability of pulsed streamer technique for the treatment of pollutants like bacteria and organic dye present in water. From the current study complete disinfection was achieved in 6 min of streamer discharge at 23 kV input voltage for a bacterial reduction of 7 orders of magnitude (107 cfu/mL). And complete dye decolourization was achieved in 8 min of treatment time for a dye concentration of 50 mg/L. It is shown that the operating parameter like voltage magnitude enhances the rate of treatment process P-III-9-27 R2 Initial dye concentration (mg/L) 10 20 30 40 50 0.57 0.56 0.52 0.45 0.44 0.99 0.99 0.98 0.99 0.96 Initial reactor volume (mL) 10 20 30 40 50 Fig. 4. Dye degradation with respect to time for different initial concentration of methylene blue at 23 kV input voltage Rate constant (min-1) 0.58 0.48 0.34 0.25 0.24 0.91 0.93 0.98 0.99 0.92 significantly and initial pollutant concentration has also got an effect on degradation rate. It is thus proved, that the treatment time and reactor size for water treatment can be significantly reduced by adapting pulsed streamer technique. Studies of this kind enable to develop pilot scale studies for the water treatment in industries. 5. Acknowledgement The authors acknowledge the financial support from department of science and technology (DST), India throughout the study. 6. References [1] World Health Organization, 2012. Water fact sheet, Retrieved on November 4, 2014, from http://www.who.int/mediacentre/factsheets/fs391/en /. [2] B.P. Dojčinović, G.M. Roglić, B.M. Obradović, M.M. Kuraica, M.M. Kostić, J. Nešić, et al., Decolorization of reactive textile dyes using water falling film dielectric barrier discharge., J. Hazard. Mater. 192, 763–71 (2011). [3] R. V. Khandare, A.N. Kabra, A. a. Kadam, S.P. Govindwar, Treatment of dye containing wastewaters by a developed lab scale phytoreactor and enhancement of its efficacy by bacterial augmentation, Int. Biodeterior. Biodegradation. 78, 89–97 (2013). [4] C. Tian, R. Liu, H. Liu, J. Qu, Disinfection byproducts formation and precursors transformation during chlorination and chloramination of highly-polluted source water: Significance of ammonia. Water Research, 47, 5901-5910 (2013). [5] R.G. Harvey, Historical overview of chemical carcinogenesis, Chemical Carcinogenesis, T. M. Penning (Ed.), Humana, New York, chapter -1, pp. 1-26 (2011). [6] E. Cabiscol, J. Tamarit, J. Ros, Oxidative stress in 3 bacteria and protein damage by reactive oxygen species, International Microbiology, 3, 3-8 (2000). [7] I. Oller, S. Malato, J.A. Sanchez-Perez, Combination of advanced oxidation processes and biological treatments for waste water decontamination: A review, Science of the Total Environment, 409, 4141-4166 (2015). [8] J. C. Crittenden, R. R. Trussell, D. W. Hand, K. J. Howe, G. Tchobanoglous, Water treatment principles and design, John willy& sons, Inc., 3rd edition, New Jersey, chap-18, pp. 1415-1484 (2012). [9] F. Rossi, O. Kylian, H. Rauscher, M. Hasiwa, Low pressure plasma discharges for the sterilization and decontamination of surfaces, New Journal of Physics, 11(11), 115017 (2009). [10] M. Sahni, B.R. Locke, Quantification of Hydroxyl Radicals Produced in Aqueous Phase Pulsed Electrical Discharge Reactors, (2006) 5819–5825. [11] H. Wang, J. Li, X. Quan, Decoloration of azo dye by a multi-needle-to-plate high-voltage pulsed corona discharge system in water, J. Electrostat. 64 (2006) 416– 421. 4 P-III-9-27
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