Ozone produced by corona discharge in the presence of water

Significant levels of ozone have been detected in a reaction flask that was designed for studies using negative air ions generated from corona discharge. While diluting the gas in the vessel at the rate of 1.5 liters/min., more than 1.0 ppm O₃ was measured in the vessel when grounded water was present. Ozone levels were much less (15 ppb) in ambient air near the ion generator. Even in the absence of water, O₃ levels were only 7 ppb in the reaction flask. Without the corona discharge apparatus, levels of ozone in the gas phase (with water present) averaged 6 ppb. These results demonstrate that when negative air ions are generated from corona discharge in the presence of water, significant levels of ozone are produced. Therefore, O₃ could be directly responsible for many of the oxidizing effects that have been reportedly due to negative air ions.     

Disinfection of model indicator organisms in a drinking water pilot plant by using PEROXONE

PEROXONE is an advanced oxidation process generated by combining ozone and hydrogen peroxide. This process stimulates the production of hydroxyl radicals, which have been shown to be superior to ozone for the destruction of some organic contaminants. In this study, pilot-scale experiments were conducted to evaluate the microbicidal effectiveness of PEROXONE and ozone against three model indicator groups. Escherichia coli and MS2 coliphage were seeded into the influent to the preozonation contactors of a pilot plant simulating conventional water treatment and were exposed to four ozone dosages (0.5, 1.0, 2.0, and 4.0 mg/liter), four hydrogen peroxide/ozone (H2O2/O3) weight ratios (0, 0.3, 0.5, and 0.8), and four contact times (4, 5, 12, and 16 min) in two source waters--Colorado River water and state project water--of different quality. The removal of heterotrophic plate count bacteria was also monitored. Results of the study indicated that the microbicidal activity of PEROXONE was greatly affected by the applied ozone dose, H2O2/O3 ratio, contact time, source water quality, and type of microorganism tested. At contact times of 5 min or less, ozone alone was a more potent bactericide than PEROXONE at all H2O2/O3 ratios tested. However, this decrease in the bactericidal potency of PEROXONE was dramatic only as the H2O2/O3 ratio was increased from 0.5 to 0.8. The fact that the bactericidal activity of PEROXONE generally decreased with increasing H2O2/O3 ratios was thought to be related to the lower ozone residuals produced. The viricidal activity of PEROXONE and ozone was comparable at all of the H2O2/O3 ratios. Heterotrophic plate count bacteria were the most resistant group of organisms. Greater inactivation of E. coli and MS2 was observed in Colorado River water than in state project water and appeared to result from differences in the turbidity and alkalinity of the two waters. Regardless of source water, greater than 4.5 log10 of E. coli and MS2 was inactivated at an applied ozone dosage of 2.0 mg/liter (and a 4-min contact time) when the H2O2/O3 ratio was less than or equal to 0.5. Comparative disinfection experiments indicated that free chlorine was the most potent bactericidal agent, followed (in descending order of effectiveness) by ozone, PEROXONE, and chloramines. These results indicate that the PEROXONE process must be optimized for each source water to achieve microbicidal effectiveness.     

Disinfection of model indicator organisms in a drinking water pilot plant by using PEROXONE.

PEROXONE is an advanced oxidation process generated by combining ozone and hydrogen peroxide. This process stimulates the production of hydroxyl radicals, which have been shown to be superior to ozone for the destruction of some organic contaminants. In this study, pilot-scale experiments were conducted to evaluate the microbicidal effectiveness of PEROXONE and ozone against three model indicator groups. Escherichia coli and MS2 coliphage were seeded into the influent to the preozonation contactors of a pilot plant simulating conventional water treatment and were exposed to four ozone dosages (0.5, 1.0, 2.0, and 4.0 mg/liter), four hydrogen peroxide/ozone (H2O2/O3) weight ratios (0, 0.3, 0.5, and 0.8), and four contact times (4, 5, 12, and 16 min) in two source waters--Colorado River water and state project water--of different quality. The removal of heterotrophic plate count bacteria was also monitored. Results of the study indicated that the microbicidal activity of PEROXONE was greatly affected by the applied ozone dose, H2O2/O3 ratio, contact time, source water quality, and type of microorganism tested. At contact times of 5 min or less, ozone alone was a more potent bactericide than PEROXONE at all H2O2/O3 ratios tested. However, this decrease in the bactericidal potency of PEROXONE was dramatic only as the H2O2/O3 ratio was increased from 0.5 to 0.8. The fact that the bactericidal activity of PEROXONE generally decreased with increasing H2O2/O3 ratios was thought to be related to the lower ozone residuals produced. The viricidal activity of PEROXONE and ozone was comparable at all of the H2O2/O3 ratios. Heterotrophic plate count bacteria were the most resistant group of organisms. Greater inactivation of E. coli and MS2 was observed in Colorado River water than in state project water and appeared to result from differences in the turbidity and alkalinity of the two waters. Regardless of source water, greater than 4.5 log10 of E. coli and MS2 was inactivated at an applied ozone dosage of 2.0 mg/liter (and a 4-min contact time) when the H2O2/O3 ratio was less than or equal to 0.5. Comparative disinfection experiments indicated that free chlorine was the most potent bactericidal agent, followed (in descending order of effectiveness) by ozone, PEROXONE, and chloramines. These results indicate that the PEROXONE process must be optimized for each source water to achieve microbicidal effectiveness.     

Simulation of ethylene conversion initiated by a streamer corona in an air flow

The conversion of ethylene (C₂H₄) at concentrations of 400 and 930 ppm in an air flow at a temperature of 295 K is simulated. Ethylene is added to air either upstream of the discharge chamber or in the reaction tube, downstream of a pulsed corona discharge. It is taken into account that the distribution of the gas components in the discharge zone is nonuniform due to the streamer nature of the discharge. In the reaction tube, all of the components are assumed to be uniform. Simulation results agree with the experiments carried out at voltage pulse amplitudes of 30 and 40 kV, a gas flow rate of 2–10 l/min, and a specific energy deposition of up to 0.15 J/cm³. It is shown that the ozone produced plays a governing role in the C₂H₄ conversion. It is found that it is possible to minimize the energy spent on conversion by choosing the optimum pulse repetition rate and the specific energy deposited per pulse. The presence of water vapor impedes the ethylene conversion and increases the concentration of formaldehyde and methane.     

Optimizing methods to estimate zooplankton concentration based on generalized patterns of patchiness inside ballast tanks and ballast water discharges

Zooplankton populations are spatially heterogeneous in nature and inside ship ballast tanks. Sampling methods should take heterogeneity into account, particularly when estimating quantitative variables such as abundance or concentration. It is particularly important to generate unbiased estimates of zooplankton concentration in ballast water when assessing compliance with new international ballast water discharge standards. We measured spatial heterogeneity of zooplankton within ballast water using three sampling methodologies. In‐tank pump samples were collected at fixed depths within the vertical part of the ballast tank (side tank). Vertical net‐haul samples were collected from the upper portion of the tank as a depth‐integrated and historically relevant method. In‐line, time‐integrated samples were collected during ballast discharge by an isokinetic sample probe, likely representing the double bottom part of the ballast tank. The bias and precision associated with each sampling method were evaluated in reference to the estimated average abundance of the entire ballast tank, which was modeled from the data collected by all methods. In‐tank pump samples provided robust evidence for vertical stratification of zooplankton concentration in the side tank. A consistent trend was also observed for in‐line discharge samples, with zooplankton concentration decreasing through time as the ballast tank is being discharged. Sample representativeness, as compared to the tank average, varied depending on the depth or tank volume discharged. In‐line discharge samples provided the least biased and most precise estimate of average tank abundance (having lowest mean squared error) when collected during the time frame of 20%–60% of the tank volume being discharged. Results were consistent across five trips despite differences in ballast water source, season, and age.     

Spin Trapping Study in the Lungs and Liver of F344 Rats after Exposure to Ozone

Fischer 344 rats were injected with the spin traps C-phenyl N-tert-butyl nitrone (PBN, 150 mg/kg bw, ip) or 4-pyridine-N-oxide N-tert -butyl nitrone (POBN, 775 mg/kg bw, ip), and exposed to clean air or 2 ppm ozone for two hours. The presence of spin adducts was determined by electron paramagnetic resonance (EPR) spectroscopy of chloroform extracts of lung and liver homogenates. No significant levels of adducts were detected in the lungs of air control animals. Benzoyl N-tert-butyl aminoxyl, attributed to direct reaction of ozone with PBN, and tert-butyl hydroaminoxyl, the scission product of the hydroxyl adduct of PBN, were detected in the lungs of ozone exposed rats. EPR signals for carbon-centred alkoxyl and alkyl adducts were also detected with PBN in the lungs and liver of animals exposed to ozone. With POBN, only carbon-centred alkyl radicals were detected. Senescent, 24 months old rats were found to retain about twice more ¹⁴C-PBN in blood, heart and lungs by comparison to juvenile, 2 months old animals. Accordingly, the EPR signals were generally stronger in the lungs of the senescent rats by comparison to juvenile rats. Together, the observations were consistent with the previously proposed notion that a significant flux of hydrogen peroxide produced from the reaction of ozone with lipids of the extracellular lining, or from activated macrophages in the lungs could be a source of biologically relevant amounts of hydroxyl radical.     

Variations of photosynthetic activity and growth of freshwater algae according to ozone contact time in ozone treatment

The activity of freshwater algae in drinking water supply at various ozone contact times was investigated to evaluate ozonation processes used for sterilization of algae. O production rates of algae just after ozonation were severely retarded even by short ozone contact. The algal growth rate was also declined with increase of ozone contact time and completely inhibited by ozonation for 60 min. These results implied that the usual treatment time applied in conventional ozonation processes is not sufficient but at least 60 min of ozonation is required for a complete sterilization of freshwater algae in drinking water source.     

Destruction of human hemoglobin in the presence of water and negative air ions generated by corona discharge

A buffered solution containing hemoglobin was exposed to negative air ions that were generated by corona discharge. In two hours, the optical absorbance at 405 nm decreased to ca., 40% of the value observed prior to the exposure to air ions. After 18 1/2 hours, the absorbance was further decreased to ca. 5% of the original values. The hemoglobin solution exposed to air for this duration did not show any appreciable change in absorbance at 405 nm. Concomitant with the decrease of absorbance at 405 nm, that at 205 nm increased several fold. The molecular weight of the specie(s) which absorbed strongly at 205 nm was ca. 400 daltons. Similar results were obtained when hemoglobin was exposed to ozone (O₃) instead of air ions. From these results and our earlier conclusion that O₃ is generated from negative air ions in the presence of water, it can be concluded that the destruction of hemoglobin was by O₃.     

Potential infection of grazing cattle via contaminated water: a theoretical modelling approach

Wastewater discharge and agricultural activities may pose microbial risks to natural water sources. The impact of different sources can be assessed by water quality modelling. The aim of this study was to use hydrological and hydrodynamic models to illustrate the risk of exposing grazing animals to faecal pollutants in natural water sources, using three zoonotic faecal pathogens as model microbes and fictitious pastures in Sweden as examples. Microbial contamination by manure from fertilisation and grazing was modelled by use of a hydrological model (HYPE) and a hydrodynamic model (MIKE 3 FM), and microbial contamination from human wastewater was modelled by application of both models in a backwards process. The faecal pathogens Salmonella spp., verotoxin-producing Escherichia coli O157:H7 (VTEC) and Cryptosporidium parvum were chosen as model organisms. The pathogen loads on arable land and pastures were estimated based on pathogen concentration in cattle faeces, herd prevalence and within-herd prevalence. Contamination from human wastewater discharge was simulated by estimating the number of pathogens required from a fictitious wastewater discharge to reach a concentration high enough to cause infection in cattle using the points on the fictitious pastures as their primary source of drinking water. In the scenarios for pathogens from animal sources, none of the simulated concentrations of salmonella exceeded the concentrations needed to infect adult cattle. For VTEC, most of the simulated concentrations exceeded the concentration needed to infect calves. For C. parvum, all the simulated concentrations exceeded the concentration needed to infect calves. The pathogen loads needed at the release points for human wastewater to achieve infectious doses for cattle were mostly above the potential loads of salmonella and VTEC estimated to be present in a 24-h overflow from a medium-size Swedish wastewater treatment plant, while the required pathogen loads of C. parvum at the release points were below the potential loads of C. parvum in a 24-h wastewater overflow. Most estimates in this study assume a worst-case scenario. Controlling zoonotic infections at herd level prevents environmental contamination and subsequent human exposure. The potential for infection of grazing animals with faecal pathogens has implications for keeping animals on pastures with access to natural water sources. As the infectious dose for most pathogens is more easily reached for calves than for adult animals, and young calves are also the main shedders of C. parvum, keeping young calves on pastures adjacent to natural water sources is best avoided.     

Decomposition of aqueous diphenyloxide by ozonolysis and by combined gamma-ray-ozone processing

Diphenyloxide (DPO) is one of many, rather toxic pollutants produced by combustion of fossil fuels, which are emitted to the atmosphere with flue gases and brought to ground water by rain and snow. Its decomposition is investigated by ozonolysis at room temperature and the major products like phenol, resorcinol, hydroquinone, dihydroxy-benzoic acid as well as the total yield of aldehydes and carboxylic acids were determined as a function of applied ozone concentration. In addition, the DPO-degradation was studied by a combined action of gamma-ray under continuous bubbling of a known ozone concentration. In this case the formation of the same products is observed, but their yields differ from the above ones. Based on the synergistic action of ozone and gamma-ray the DPO-radiolysis is rather efficient, leading to an initial-G-value of 11.3. Some probable reaction mechanisms are presented for explanation of the degradation process.     

Microwave Electromagnetic Field Affects the Corona Discharge Pattern of Water

We investigated the influence of microwave irradiation (cw; 10 GHz) on water by means of corona discharge electrography. Water drops from previously irradiated and control water were exposed to a high-voltage, high-frequency electric field on a photographic plate. Electrographs of the corona discharge around control and irradiated drops were taken simultaneously, and the images obtained were analyzed by computer. Several parameters relating to the luminosity, shape, and streamers of the image were calculated and tested nonparametrically. The results show a distinct, nonlinear behavior of corona discharge patterns (both radially and angularly) in water drops exposed to different microwave power densities (5 × 10^?1-5 × 10^?8 mWcm^?2).     

Alternating nonsteady gas-discharge modes in an atmospheric-pressure air flow blown through a point-plane gap

The electric and spectral characteristics of a nonsteady discharge in an atmospheric air flow blown through a point-plane interelectrode gap were investigated experimentally. The discharge was produced by applying a constant positive voltage to the point electrode, the amplitude of the applied voltage being much higher than the corona ignition voltage. The nonsteady character of the discharge is due to the spontaneously repeating streamer-spark breakdown, followed by the formation of either a diffuse ultracorona or a filamentary glow discharge. In the latter case, the length of the plasma column increases progressively, being blown off by the gas flow from the discharge gap. The extinction of a filamentary discharge is unrelated to the break of the current channel: the discharge decays abruptly when the filament length reaches its critical value. The distribution of active particles (O, OH, and N*₂) carried out from the discharge gap is determined from the data of spectral measurements.     

Variability in the response of the rabbit uterus to progesterone as influenced by prolactin

Ovariectomized rabbits from different breeders were treated at different times of the year with prolactin alone or with progesterone and the production of uteroglobin by the uterus was studied. There were seasonal, strain and dose variables in the uterine response to prolactin and progesterone. Treatment with prolactin (at 1 mg/day) plus progesterone generally induced higher levels of uteroglobin production than did treatment with progesterone alone. The differences were greatest in the winter for Tennessee animals and in the spring for animals from the New Mexico and North Carolina colonies. Ovariectomy produced a decrease (P less than 0.01) in the concentration of cytosolic oestrogen and progesterone receptors, and prolactin treatment restored the concentration to oestrous control values. However, there were no seasonally dependent changes in the concentration of the receptors for any of the treatment groups. Increased doses of prolactin (2 mg/day) induced high levels of uteroglobin production and new proteins to appear in uterine secretions of long-term ovariectomized rabbits but much lower levels (10-11%) when given to pregnant does. Additional ovulations were also noted plus adverse effects on the embryos.     

Nitrogen Fixation By Corona Discharge On The Early Precambrian Earth

We report the first experimental study of nitrogen fixation by corona discharge on the anoxic primitive Earth. The energy yields of nitric oxide (NO) and nitrous oxide (N₂O) were experimentally determined over a wide range of CO₂-N₂ mixtures simulating the evolution of the Earth's atmosphere during the Hadean and Archean eras (from 4.5 ba to 2.5 ba). NO, the principal form of fixed nitrogen in lightning and coronal discharge in early Earth, is produced ten times less efficiently in the latter type of electrical discharge with an estimated maximum annual production rate of the order of 10¹⁰ g yr⁻¹. For N₂O the maximum production rate was estimated to be ∼10⁹ g yr⁻¹. These low rates of syntheses indicate that corona discharges as point discharges on the clouds and ground did not play a significant role in the overall pool of reactive nitrogen needed for the emergence and sustainability of life.     

Spin Trapping Study in the Lungs and Liver of F344 Rats after Exposure to Ozone

Fischer 344 rats were injected with the spin traps C-phenyl N-tert-butyl nitrone (PBN, 150 mg/kg bw, ip) or 4-pyridine-N-oxide N-tert -butyl nitrone (POBN, 775 mg/kg bw, ip), and exposed to clean air or 2 ppm ozone for two hours. The presence of spin adducts was determined by electron paramagnetic resonance (EPR) spectroscopy of chloroform extracts of lung and liver homogenates. No significant levels of adducts were detected in the lungs of air control animals. Benzoyl N-tert-butyl aminoxyl, attributed to direct reaction of ozone with PBN, and tert-butyl hydroaminoxyl, the scission product of the hydroxyl adduct of PBN, were detected in the lungs of ozone exposed rats. EPR signals for carbon-centred alkoxyl and alkyl adducts were also detected with PBN in the lungs and liver of animals exposed to ozone. With POBN, only carbon-centred alkyl radicals were detected. Senescent, 24 months old rats were found to retain about twice more ¹⁴C-PBN in blood, heart and lungs by comparison to juvenile, 2 months old animals. Accordingly, the EPR signals were generally stronger in the lungs of the senescent rats by comparison to juvenile rats. Together, the observations were consistent with the previously proposed notion that a significant flux of hydrogen peroxide produced from the reaction of ozone with lipids of the extracellular lining, or from activated macrophages in the lungs could be a source of biologically relevant amounts of hydroxyl radical.     

Ozone concentration in leaf intercellular air spaces is close to zero

Transpiration and ozone uptake rates were measured simultaneously in sunflower leaves at different stomatal openings and various ozone concentrations. Ozone uptake rates were proportional to the ozone concentration up to 1500 nanoliters per liter. The leaf gas phase diffusion resistance (stomatal plus boundary layer) to water vapor was calculated and converted to the resistance to ozone multiplying it by the theoretical ratio of diffusion coefficients for water vapor and ozone in air (1.67). The ozone concentration in intercellular air spaces calculated from the ozone uptake rate and diffusion resistance to ozone scattered around zero. The ozone concentration in intercellular air spaces was measured directly by supplying ozone to the leaf from one side and measuring the equilibrium concentration above the other side, and it was found to be zero. The total leaf resistance to ozone was proportional to the gas phase resistance to water vapor with a coefficient of 1.68. It is concluded that ozone enters the leaf by diffusion through the stomata, and is rapidly decomposed in cell walls and plasmalemma.     

Phenomenology of a high-current negative point-to-plane corona in nitrogen

Results are presented from experimental studies of a steady-state negative point-to-plane corona in atmospheric-pressure nitrogen at anomalously high (milliampere) currents. The evolution of the corona glow with increasing discharge current is traced up to the corona conversion into a spark. It was found that the structure and current-voltage characteristic of the corona change significantly when the working gas is slowly blown trough the discharge cell. It is shown that, starting from a current of I≥0.5 mA, a negative corona in a nitrogen flow acts as a streamer corona, whereas there are no streamers in the absence of gas blowing. In contrast to the quadratic dependence of the current versus voltage in a low-current corona, the current-voltage characteristic of a high-current corona is linear. The time evolution of the radial profile of the current density at the anode is studied under different experimental conditions.     

Differential Inactivation of Fungal Spores in Water and on Seeds by Ozone and Arc Discharge Plasma

Seed sterilization is essential for preventing seed borne fungal diseases. Sterilization tools based on physical technologies have recently received much attention. However, available information is very limited in terms of efficiency, safety, and mode of action. In this study, we have examined antifungal activity of ozone and arc discharge plasma, potential tools for seed sterilization. In our results, ozone and arc discharge plasma have shown differential antifungal effects, depending on the environment associated with fungal spores (freely submerged in water or infected seeds). Ozone inactivates Fusarium fujikuroi (fungus causing rice bakanae disease) spores submerged in water more efficiently than arc discharge plasma. However, fungal spores associated with or infecting rice seeds are more effectively deactivated by arc discharge plasma. ROS generated in water by ozone may function as a powerful fungicidal factor. On the other hand, shockwave generated from arc discharge plasma may have greatly contributed to antifungal effects on fungus associated with rice seeds. In support of this notion, addition of ultrasonic wave in ozone generating water has greatly increased the efficiency of seed disinfection.     

Superoxide anion is elevated in sympathetic neurons in DOCA-salt hypertension via activation of NADPH oxidase

Superoxide anion (O2-*) production is elevated in sympathetic ganglion neurons and in the vasculature of hypertensive animals; however, it is not known what enzymatic pathway(s) are responsible for O2-* production. To determine the pathway(s) of O2-* production in sympathetic neurons, we examined the presence of mRNA of NADPH oxidase subunits in sympathetic ganglionic neurons and differentiated PC-12 cells. The mRNAs for NADPH oxidase subunits p47phox, p22phox, gp91phox, and NOX1 were present in sympathetic neurons and PC-12 cells, whereas the NOX4 homologue was present in sympathetic neurons but not PC-12 cells. Freshly dissociated celiac ganglion neurons from normal rats and PC-12 cells produced O2-* when treated with the PKC activator PMA; O2-* production increased by 317% and 254%, respectively. The PMA-evoked increases were reduced by pretreatment with the NADPH oxidase inhibitor apocynin. These findings indicate that NADPH oxidase is the primary source of O2-* in sympathetic ganglion neurons. When celiac ganglia from hypertensive rats were incubated with apocynin, O2-* levels were reduced to the same levels as normotensive animals, indicating that NADPH oxidase activity accounted for the elevated O2-* levels in hypertensive animals. To test this latter finding, we compared NADPH oxidase activity in extracts of prevertebral sympathetic ganglia of DOCA-salt hypertensive rats and sham-operated rats. NADPH oxidase activities were 49.9% and 78.6% higher in sympathetic ganglia of DOCA rats compared with normotensive controls when using beta-NADH and beta-NADPH as substrates, respectively. Thus elevated O2-* levels in hypertension may be a result of the increased activity of NADPH oxidase in postganglionic sympathetic neurons.     

Investigation of the decolorization efficiency of two pin-to-plate corona discharge plasma system for industrial wastewater treatment

In this article, a dual pin-to-plate high-voltage corona discharge system is introduced to study experimentally the gap distance, the contact time, the effect of pin and plate materials, the thickness of ground plate and the conductivity on the amount of Acid Blue 25 dye color removal efficiency from polluted water. A study for the optimum air gap distance between dual pin and surface of Acid Blue 25 dye solution is carried out using 3D-EM simulator to find maximum electric field intensity at the tip of both pins. The outcomes display that the best gap for corona discharge is approximately 5 mm for 15-kV source. This separation is constant during the study of other factors. In addition, an investigation of the essential reactive species responsible for oxidation of the dye organic compounds (O₃ in air discharge, O₃ in water, and H₂O₂) during the experimental time is conducted. Three various materials such as: stainless steel, copper and aluminum are used for pins and plate. The maximum color removal efficiencies of Acid Blue 25 dyes are 99.03, 82.04, and 90.78% after treatment time 15 min for stainless steel, copper, and aluminum, respectively. Measurement results for the impact of thickness of an aluminum ground plate on color removal competence show color removal efficiencies of 86.3, 90.78, and 98.06% after treatment time 15 min for thicknesses of 2, 0.5, and 0.1 mm, respectively. The increasing of the solution conductivity leads to the reduction of decolorization efficiency. A kinetic model is used to define the performance of corona discharge system. The models of pseudo-zero-order, pseudo-first-order, and pseudo-second-order reaction kinetics are utilized to investigate the decolorization of Acid Blue 25 dye. The rate of degradation of Acid Blue 25 dye follows the pseudo-first-order kinetics in the dye concentration.