Petr Lukes

GENERATION OF CHEMICALLY ACTIVE SPECIES BY ELECTRICAL DISCHARGES IN WATER

Pulse positive streamer corona discharges in water solution with a different conductivity have been investigated in reactors with the needle-plate and coaxial electrode geometry. A special composite anode was used in the coaxial geometry. With such an anode hundreds of streamers were generated at each voltage pulse. Production of H, O and OH radicals by the discharge was proved by emission spectroscopy and formation of H2O2 and degradation of phenol was demonstrated by chemical methods. Assuming that the broadening of the line profile was caused by the dynamic Stark effect, plasma with an electron density over 1018 cm-3 was generated during the initial phase of voltage pulse in the both reactors in spite of the very different electrode geometry and wave-forms of voltage pulses. Production of OH radicals was most effective at solution conductivity below .

Aqueous-phase chemistry and bactericidal effects from an air discharge plasma in contact with water: evidence for the formation of peroxynitrite through a pseudo-second-order post-discharge reaction of H2O2 and HNO2

The formation of transient species (OH?, NO2?, NO radicals) and long-lived chemical products (O3, H2O2, , ) produced by a gas discharge plasma at the gas?liquid interface and directly in the liquid was measured in dependence on the gas atmosphere (20% oxygen mixtures with nitrogen or with argon) and pH of plasma-treated water (controlled by buffers at pH 3.3, 6.9 or 10.1). The aqueous-phase chemistry and specific contributions of these species to the chemical and biocidal effects of air discharge plasma in water were evaluated using phenol as a chemical probe and bacteria Escherichia coli. The nitrated and nitrosylated products of phenol (4-nitrophenol, 2-nitrophenol, 4-nitrocatechol, 4-nitrosophenol) in addition to the hydroxylated products (catechol, hydroquinone, 1,4-benzoquinone, hydroxy-1,4-benzoquinone) evidenced formation of NO2?, NO? and OH? radicals and NO+ ions directly by the air plasma at the gas?liquid interface and through post-discharge processes in plasma-activated water (PAW) mediated by peroxynitrite (ONOOH). Kinetic study of post-discharge evolution of H2O2 and in PAW has demonstrated excellent fit with the pseudo-second-order reaction between H2O2 and . The third-order rate constant k?=?1.1???103?M?2?s?1 for the reaction was determined in PAW at pH 3.3 with the rate of ONOOH formation in the range 10?8?10?9?M?s?1. Peroxynitrite chemistry was shown to significantly participate in the antibacterial properties of PAW. Ozone presence in PAW was proved indirectly by pH-dependent degradation of phenol and detection of cis,cis-muconic acid, but contribution of ozone to the inactivation of bacteria by the air plasma was negligible.

Hydrogen peroxide and ozone formation in hybrid gas-liquid electrical discharge Reactors

Ozone in the gas phase and hydrogen peroxide in the liquid phase were simultaneously formed in hybrid electrical discharge reactors, known as the hybrid-series and hybrid-parallel reactors, which utilize both gas phase nonthermal plasma formed above the water surface and direct liquid phase corona-like discharge in the water. In the series configuration the high voltage needle-point electrode is submerged and the ground electrode is placed in the gas phase above the water surface. The parallel configuration employs a high voltage electrode in the gas phase and a high voltage needle-point electrode in the liquid phase with the ground electrode placed at the gas-liquid interface. In both hybrid reactors the gas phase concentration of ozone reached a power-dependent steady state, whereas the hybrid-parallel reactor produced a substantially larger amount of ozone than the hybrid series. Hydrogen peroxide was produced in both hybrid reactors at a similar rate to that of a single-phase liquid electrical discharge reactor. The resulting concentration of H/sub 2/O/sub 2/ in the hybrid reactors, however, depended on the pH of the solution and the gas phase ozone concentration since H/sub 2/O/sub 2/ was decomposed by dissolved ozone at high pH.

Plasma–liquid interactions: a review and roadmap

Plasma–liquid interactions represent a growing interdisciplinary area of research involving plasma science, fluid dynamics, heat and mass transfer, photolysis, multiphase chemistry and aerosol science. This review provides an assessment of the state-of-the-art of this multidisciplinary area and identifies the key research challenges. The developments in diagnostics, modeling and further extensions of cross section and reaction rate databases that are necessary to address these challenges are discussed. The review focusses on non-equilibrium plasmas.

Plasmachemical oxidation processes in a hybrid gas-liquid electrical discharge reactor

Oxidation processes induced in water by pulsed electrical discharges generated simultaneously in the gas phase in close proximity to the water surface and directly in the liquid were investigated in a hybrid series gas?liquid electrical discharge reactor. The mechanism of phenol degradation was studied through its dependence on the gas phase and liquid phase compositions using pure argon and oxygen atmospheres above the liquid and different initial pH values in the aqueous solution. Phenol degradation was significantly enhanced in the hybrid-series reactor compared with the phenol removal by the single-liquid phase discharge reactor. Under an argon atmosphere the mechanism of phenol degradation was mainly caused by the electrophilic attack of OH? radicals produced by the liquid phase discharge directly in water and OH? radicals produced by the gas phase discharge at the gas?liquid interface. Under an oxygen atmosphere the formation of gaseous ozone dominated over the formation of OH? radicals, and the contribution of the gas phase discharge in this case was determined mainly by the dissolution of gaseous ozone into the water and its subsequent interaction with phenol. At high pH phenol was degraded, in addition to the direct attack by ozone, also through indirect reactions of OH? radicals formed via a peroxone process by the decomposition of dissolved ozone by hydrogen peroxide produced by the liquid phase discharge. Such a mechanism was proved by the detection of cis,cis-muconic acid and pH-dependent degradation of phenol, which resulted in significantly higher removal of phenol from alkaline solution observed under oxygen atmosphere than in argon.

Generation of ozone by pulsed corona discharge over water surface in hybrid gas–liquid electrical discharge reactor

Ozone formation by a pulse positive corona discharge generated in the gas phase between a planar high voltage electrode made from reticulated vitreous carbon and a water surface with an immersed ground stainless steel plate electrode was investigated under various operating conditions. The effects of gas flow rate (0.5–3 litre min−1), discharge gap spacing (2.5–10 mm), applied input power (2–45 W) and gas composition (oxygen containing argon or nitrogen) on ozone production were determined. Ozone concentration increased with increasing power input and with increasing discharge gap. The production of ozone was significantly affected by the presence of water vapour formed through vaporization of water at the gas–liquid interface by the action of the gas phase discharge. The highest energy efficiency for ozone production was obtained using high voltage pulses of approximately 150 ns duration in Ar/O2 mixtures with the maximum efficiency (energy yield) of 23 g kW h−1 for 40% argon content.

Ultraviolet radiation from the pulsed corona discharge in water

Quantitative analysis of ultraviolet radiation from the pulsed corona discharge in water with needle-plate electrode geometry (~1?3?J?pulse?1) was performed using the potassium ferrioxalate actinometry. Photon flux J190?280 and radiant energy Q190?280 of the UV light emitted from the discharge at spectral region 190?280?nm was determined in dependence on the applied voltage (17?29?kV, positive polarity) and the solution conductivity (100?500??S?cm?1). The intensity of the UV radiation strongly increased with increasing water conductivity and applied voltage. Depending on the applied voltage the determined photon flux varied by more than two orders of magnitude within the range of solution conductivities 100?500??S?cm?1. It was found that photon flux from the discharge may be directly related to the discharge pulse mean power Pp as J190?280 = 44.33 (quanta?pulse?1). A significant role of UV radiation in the production of hydrogen peroxide and bacterial inactivation by the corona discharge in water has been identified. As the solution conductivity increased the yield of H2O2 produced by the discharge decreased due to increasing photolysis of H2O2 accounting for up to 14% of the total decomposition rate of H2O2. As regards bactericidal effects, it was estimated that the UV radiation contributes about 30% to the overall inactivation of Escherichia coli.

Degradation of phenol by underwater pulsed corona discharge in combination with TiO2 photocatalysis

Non-thermal plasma-induced degradation of phenol by pulsed high-voltage discharge generated in water using point to plane geometry of electrodes was investigated in the presence of photocatalytically active TiO2. The phenol removal attributed directly to the effects of plasma chemical activity of the discharge was enhanced in the presence of TiO2. At the same time, higher formation of 1,4-benzoquinone as the main primary aromatic by-product and increased accumulation of hydrogen peroxide in the solution were found. The main effect of TiO2 addition was in the utilizing of ultraviolet radiation from the plasma resulting in the photocatalytical formation of OH radicals on the surface of TiO2 particles and, thus, in the increase of the yield of OH radicals available for phenol degradation.

Pulsed Electrical Discharge in Water Generated Using Porous-Ceramic-Coated Electrodes

A special metallic electrode covered by a thin layer of porous ceramic prepared by the technology of thermal plasma spraying has been developed and used for the generation of large-volume nonthermal plasma in water. Images of multichannel pulsed electrical discharge generated in water at the composite electrode as a function of solution conductivity are presented.

Membrane damage and active but nonculturable state in liquid cultures of Escherichia coli treated with an atmospheric pressure plasma jet

Electrical discharge plasmas can efficiently inactivate various microorganisms. Inactivation mechanisms caused by plasma, however, are not fully understood because of the complexity of both the plasma and biological systems. We investigated plasma-induced inactivation of Escherichia coli in water and mechanisms by which plasma affects bacterial cell membrane integrity. Atmospheric pressure argon plasma jet generated at ambient air in direct contact with bacterial suspension was used as a plasma source. We determined significantly lower counts of E. coli after treatment by plasma when they were assayed using a conventional cultivation technique than using a fluorescence-based LIVE/DEAD staining method, which indicated that bacteria may have entered the viable-but-nonculturable state (VBNC). We did not achieve resuscitation of these non-culturable cells, however, we detected their metabolic activity through the analysis of cellular mRNA, which suggests that cells may have been rather in the active-but-nonculturable state (ABNC). We hypothesize that peroxidation of cell membrane lipids by the reactive species produced by plasma was an important pathway of bacterial inactivation. Amount of malondialdehyde and membrane permeability of E. coli to propidium iodide increased with increasing bacterial inactivation by plasma. Membrane damage was also demonstrated by detection of free DNA in plasma-treated water.