Activation of peroxydisulfate by gas-liquid pulsed discharge plasma to enhance the degradation of p-nitrophenol

Pulsed discharge in water and over water surfaces generates ultraviolet radiation,local high temperature,shock waves,and chemical reactive species,including hydroxyl radicals,hydrogen peroxide,and ozone.Pulsed discharge plasma (PDP) can oxidize and mineralize pollutants very efficiently,but high energy consumption restricts its application for industrial wastewater treatment.A novel method for improving the energy efficiency of wastewater treatment by PDP was proposed,in which peroxydisulfate (PDS) was added to wastewater and PDS was activated by PDP to produce more strong oxidizing radicals,including sulfate radicals and hydroxyl radicals,leading to a higher oxidation capacity for the PDP system.The experimental results show that the increase in solution conductivity slightly decreased the discharge power of the pulse discharge over the water surface.An increase in the discharge intensity improved the activation of PDS and therefore the degradation efficiency and energy efficiency of p-nitrophenol (PNP).An increase in the addition dosage of PDS greatly facilitated the degradation of PNP at a molar ratio of PDS to PNP of lower than 80∶1,but the performance enhancement was no longer obvious at a dosage of more than 80∶1.Under an applied voltage of 20 kV and a gas discharge gap of 2 rmm,the degradation efficiency and energy efficiency of the PNP reached 90.7％ and 45.0 mg kWh-1 for the plasma/PDS system,respectively,which was 34％ and 18.0 mg kWh-1 higher than for the discharge plasma treatment alone.Analysis of the physical and chemical effects indicated that ozone and hydrogen peroxide were important for PNP degradation and UV irradiation and heat from the discharge plasma might be the main physical effects for the activation of PDS.     

Oxidation of ciprofloxacin by the synergistic effect of DBD plasma and persulfate: reactive species and influencing factors analysis

A synergistic system of water falling film dielectric barrier discharge(DBD) plasma and persulfate(PS) was set up and used for oxidizing ciprofloxacin(CIP) in water. Results of reactive species formation in the DBD-only system as well as the DBD–PS system verified the PS activation in the DBD system. Influencing factors on CIP degradation and the degradation process were also been studied. The obtained results showed that the presence of PS could greatly improve the degradation and mineralizatio...     

Degradation of sulfamethoxazole in water by dielectric barrier discharge plasma jet: influencing parameters,degradation pathway,toxicity evaluation

Sulfamethoxazole (SMX) is an antibiotic and widely present in aquatic environments, so it presents a serious threat to human health and sustainable development. A dielectric barrier discharge (DBD) plasma jet was utilized to degrade aqueous SMX, and the effects of various operating parameters (working gas, discharge power, etc) on SMX degradation performance were studied. The experimental results showed that the DBD plasma jet can obtain a relatively high degradation efficiency for SMX when the discharge power is high with an oxygen atmosphere, the initial concentration of SMX is low, and the aqueous solution is under acidic conditions. The reactive species produced in the liquid phase were detected, and OH radicals and O3 were found to play a significant role in the degradation of SMX. Moreover, the process of SMX degradation could be better fitted by the quasi-first-order reaction kinetic equation. The analysis of the SMX degradation process indicated that SMX was gradually decomposed and 4-amino benzene sulfonic acid, benzene sulfonamide, 4-nitro SMX, and phenylsulfinyl acid were detected, and thus three possible degradation pathways were finally proposed. The mineralization degree of SMX reached 90.04% after plasma treatment for 20 min, and the toxicity of the solution fluctuated with the discharge time but eventually decreased.     

Strengthening decomposition of oxytetracycline in DBD plasma coupling with Fe-Mn oxide-loaded granular activated carbon

A catalytic approach using a synthesized iron and manganese oxide-supported granular activated carbon (Fe-Mn GAC) under a dielectric barrier discharge (DBD) plasma was investigated to enhance the degradation of oxytetracycline (OTC) in water. The prepared Fe-Mn GAC was characterized by x-ray diffraction and scanning electron microscopy, and the results showed that the bimetallic oxides had been successfully spread on the GAC surface. The experimental results showed that the DBD + Fe-Mn GAC exhibited better OTC removal efficiency than the sole DBD and DBD + virgin GAC systems. Increasing the fabricated catalyst and discharge voltage was favorable to the antibiotic elimination and energy yield in the hybrid process. The coupling process could be elucidated by the ozone decomposition after Fe-Mn GAC addition, and highly hydroxyl and superoxide radicals both play significant roles in the decontamination. The main intermediate products were identified by HPLC-MS to study the mechanism in the collaborative system.     

Discoloration of Congo Red by Rod-Plate Dielectric Barrier Discharge Processes at Atmospheric Pressure

A dielectric barrier discharge (DBD) reactor with a rod-plate electrode configuration was used for the oxidative decomposition of Congo red dye in an aqueous solution.Plasma was generated in the gas space above the water interface under atmospheric pressure.Discharge characteristics were analyzed by voltage-current waveforms.Effects of applied voltage,initial conductivity,and initial concentration were also analyzed.Congo red discoloration increased with increased applied voltage and decreased conductivity.The initial conductivity significantly influenced the Congo red discoloration.Under the same conditions,the highest discoloration rate was obtained at 25 mg/L.The presence of ferrous ions in the solutions had a substantial positive effect on Fenton dye degradation and flocculation.At an applied voltage of 20 kV,about 100％of dye was degraded after 4 min of Fe2+/DBD treatment.Results showed that adding a certain dosage of hydrogen peroxide to the wastewater could enhance the discoloration rate.Possible pathways of Congo red discoloration by DBD plasma were proposed based on GC/MS,FTIR,and UV-vis spectroscopy analyses.     

Regulation characteristics of oxide generation and formaldehyde removal by using volume DBD reactor

Discharge plasmas in air can be accompanied by ultraviolet(UV) radiation and electron impact,which can produce large numbers of reactive species such as hydroxyl radical(OH·),oxygen radical(O·),ozone(O3),and nitrogen oxides(NOx),etc.The composition and dosage of reactive species usually play an important role in the case of volatile organic compounds(VOCs) treatment with the discharge plasmas.In this paper,we propose a volume discharge setup used to purify formaldehyde in air,which is configured by a plate-to-plate dielectric barrier discharge(DBD) channel and excited by an AC high voltage source.The results show that the relative spectral-intensity from DBD cell without formaldehyde is stronger than the case with formaldehyde.The energy efficiency ratios(EERs) of both oxides yield and formaldehyde removal can be regulated by the gas flow velocity in DBD channel,and the most desirable processing effect is the gas flow velocity within the range from2.50 to 3.33 m s-1.Moreover,the EERs of both the generated dosages of oxides(O3 and NO2) and the amount of removed formaldehyde can also be regulated by both of the applied voltage and power density loaded on the DBD cell.Additionally,the EERs of both oxides generation and formaldehyde removal present as a function of normal distribution with increasing the applied power density,and the peak of the function is appeared in the range from 273.5 to 400.0 W l-1.This work clearly demonstrates the regulation characteristic of both the formaldehyde removal and oxides yield by using volume DBD,and it is helpful in the applications of VOCs removal by using discharge plasma.     

Degradation of Aniline Wastewater Using Dielectric Barrier Discharges at Atmospheric Pressure

Aniline is a toxic water pollutant detected in drinking water and surface water,and this chemical is harmful to both human and aquatic life.A dielectric barrier discharge(DBD)reactor was designed in this study to investigate the treatment of aniline in aqueous solution.Discharge characteristics were assessed by measuring voltage and current waveforms,capturing light emission images,and obtaining optical emission spectra.The effects of several parameters were analyzed,including treatment distance,discharge power,DBD treatment time,initial pH of aniline solutions,and addition of sodium carbonate and hydrogen peroxide to the treatment.Aniline degradation increased with increasing discharge power.Under the same conditions,higher degradation was obtained at a treatment distance of 0 mm than at other treatment distances.At a discharge power of 21.5 W,84.32%of aniline was removed after 10 min of DBD treatment.Initial pH significantly influenced aniline degradation.Adding a certain dosage of sodium carbonate and hydrogen peroxide to the wastewater can accelerate the degradation rate of aniline.Possible degradation pathways of aniline by DBD plasmas were proposed based on the analytical data of GC/MS and TOC.     

Development of low power non-thermal plasma jet and optimization of operational parameters for treating dyes and emerging contaminants

Non-thermal plasma has emerged as an effective treatment system against the latest class of highly recalcitrant and toxic environmental pollutants termed emerging contaminants (ECs). In the present work, a detailed experimental study is carried out to evaluate the efficacy of a non-thermal plasma jet with two dyes, Rd. B and Met. Blue, as model contaminants. The plasma jet provided a complete dye decoloration in 30 min with an applied voltage of 6.5 kV_p−p. ·OH, having the highest oxidation potential, acts as the main reactive species, which with direct action on contaminants also acts indirectly by getting converted into H2O2 and O3. Further, the effect of critical operational parameters viz, sample pH, applied voltage (4.5‒6.5 kV_p−p), conductivity (5‒20 mS cm⁻¹), and sample distance on plasma treatment efficacy was also examined. Out of all the assessed parameters, the applied voltage and sample conductivity was found to be the most significant operating parameters. A high voltage and low conductivity favored the dye decoloration, while the pH effect was not that significant. To understand the influence of plasma discharge gas on treatment efficacy, all the experiments are conducted with argon and helium gases under the fixed geometrical configuration. Both the gases provided a similar dye decoloration efficiency. The DBD plasma system with complete dye removal also rendered maximum mineralization of 73% for Rd. B, and 60% for Met. Blue. Finally, the system's efficiency against the actual ECs (four pharmaceutical compounds, viz, metformin, atenolol, acetaminophen, and ranitidine) and microbial contaminant (E. coli) was also tested. The system showed effectivity in the complete removal of targeted pharmaceuticals and a log2.5 E. coli reduction. The present systematic characterization of dye degradation could be of interest to large communities working towards commercializing plasma treatment systems.     

Ozone generation enhanced by silica catalyst in packed-bed DBD reactor

In this paper, three dielectric barrier discharge(DBD) configurations, which were plain DBD with no packing, DBD with packed pure quartz fibers and DBD with packed loaded quartz fibers, were employed to investigate the effect and catalytic mechanism of catalyst materials in a packed-bed ozone generator. From the experimental results, it was clear that the DBD configuration with packed pure fibers and packed loaded fibers promotes ozone generation. For the packed-bed reactor, ozone concentration and ozone yield were enhanced by an increase of electric field in the discharge gap with the packed-bed effect. Meanwhile, the enhancement of ozone concentration and yield for the DBD reactor packed by loaded fibers with silica nanoparticles was due to the catalysis of silica nanoparticles on the fiber surface. The adsorption of silica nanoparticles on the fiber surface can prolong the retention time of active species and enhance surface reactions.     

Generation of reactive species in atmospheric pressure dielectric barrier discharge with liquid water

Atmospheric pressure helium/water dielectric barrier discharge(DBD) plasma is used to investigate the generation of reactive species in a gas–liquid interface and in a liquid. The emission intensity of the reactive species is measured by optical emission spectroscopy(OES)with different discharge powers at the gas–liquid interface. Spectrophotometry is used to analyze the reactive species induced by the plasma in the liquid. The concentration of OH radicals reaches 2.2 μm after 3 min of discharge treatment. In addition, the concentration of primary longlived reactive species such as H_2O_2, NO_3~- and O_3 are measured based on plasma treatment time.After 5 min of discharge treatment, the concentration of H_2O_2, NO_3~-, and O_3 increased from 0 mg?·?L~(-1) to 96 mg?·?L~(-1), 19.5 mg?·?L~(-1), and 3.5 mg?·?L~(-1), respectively. The water treated by plasma still contained a considerable concentration of reactive species after 6 h of storage. The results will contribute to optimizing the DBD plasma system for biological decontamination.     

Evaluation on a double-chamber gas-liquid phase discharge reactor for benzene degradation

A double-chamber gas-liquid phase DBD reactor (GLDR), consisting of a gas-phase discharge chamber and a gas-liquid discharge chamber in series, was designed to enhance the degradation of benzene and the emission of NOx. The performance of the GLDR on discharge characteristics, reactive species production and benzene degradation was compared to that of the single-chamber gas phase DBD reactor (GPDR). The effects of discharge gap, applied voltage, initial benzene concentration, gas flow rate and solution conductivity on the degradation and energy yield of benzene in the GLDR were investigated. The GLDR presents a higher discharge power, higher benzene degradation and higher energy yield than that of the GPDR. NO₂ emission was remarkably inhibited in the GLDR, possibly due to the dissolution of NO₂ in water. The benzene degradation efficiency increased with the applied voltage, but decreased with the initial concentration, gas flow rate, and gas discharge gap, while the solution conductivity presented less influence on benzene degradation. The benzene degradation efficiency and the energy yield reached 61.11% and 1.45 g kWh^–1 at 4 mm total gas discharge gap, 15 kV applied voltage, 200 ppm benzene concentration, 0.2 L min⁻¹ gas flow rate and 721 μS cm⁻¹ water conductivity. The intermediates and byproducts during benzene degradation were detected by FT-IR, GC-MS and LC-MS primarily, and phenols, CO_x, and other aromatic substitutes, O₃, NO_x, etc, were determined as the main intermediates. According to these detected byproducts, a possible benzene degradation mechanism was proposed.     

Research on quinoline degradation in drinking water by a large volume strong ionization dielectric barrier discharge reaction system

Quinoline is widely used in the production of drugs as a highly effective insecticide, and its derivatives can also be used to produce dyes. It has a teratogenic carcinogen to wildlife and humans once entering into the aquatic environment. In this study, the degradation mechanism of quinoline in drinking water by a strong ionization dielectric barrier discharge(DBD) lowtemperature plasma with large volume was explored. High concentration of hydroxyl radical(·OH)(0.74 mmol l-1) and ozone(O3)(58.2 mg l-1) produced by strongly ionized discharge DBD system were quantitatively analyzed based on the results of electron spin resonance and O3 measurements. The influencing reaction conditions of input voltages, initial p H value, ·OH inhibitors, initial concentration and inorganic ions on the removal efficiency of quinoline were systematically studied. The obtained results showed that the removal efficiency and TOC removal of quinoline achieved 94.8% and 32.2%, degradation kinetic constant was 0.050 min-1 at 3.8 k V and in a neutral p H(7.2). The proposed pathways of quinoline were suggested based on identified intermediates as hydroxy pyridine, fumaric acid, oxalic acid, and other small molecular acids by high-performance liquid chromatography/tandem mass spectrometry analysis. Moreover, the toxicity analysis on the intermediates demonstrated that its acute toxicity, bioaccumulation factor and mutagenicity were reduced. The overall findings provided theoretical and experimental basis for the application of a high capacity strong ionization DBD water treatment system in the removal of quinoline from drinking water.     

Enhancing toluene removal in a plasma photocatalytic system through a black TiO_2 photocatalyst

An efficient toluene removal in air using a plasma photocatalytic system(PPS) not only needs favorable surface reactions over photocatalysts under the action of plasma,but also requires the photocatalysts to efficiently absorb light emitted from the discharge for driving the photocatalytic reactions. We report here that the PPS constructed by integrating a black titania(B-TiO_2)photocatalyst with a dielectric barrier discharge(DBD) can effectively remove toluene with above 70% CO_2 selectivity and remarkably reduced the concentration of secondary pollutants of ozone and nitrogen oxides at a specific energy input of 1500 J·l~(-1),while exhibiting good stability. Photocatalyst characterizations suggest that the B-TiO_2 provides a high concentration of oxygen vacancies for the surface oxidation of toluene in DBD,and efficiently absorbs ultraviolet–visible light emitted from the discharge to induce plasma photocatalytic oxidation of toluene. The presence of B-TiO_2 in the plasma region also results in a high discharge efficiency,facilitating the generation of large numbers of reactive species and thus the oxidation of toluene towards CO_2. The greatly enhanced performance of the PPS integrated with B-TiO_2 in toluene removal offers a promising approach to efficiently remove refractory volatile organic compounds from air at low temperatures.     

Interactions between multiple filaments and bacterial biofilms on the surface of an apple

In this paper, the interactions between two dielectric barrier discharge(DBD) filaments and three bacterial biofilms are simulated. The modeling of a DBD streamer is studied by means of 2D finite element calculation. The model is described by the proper governing equations of air DBD at atmospheric pressure and room temperature. The electric field in the computing domain and the self-consistent transportation of reactive species between a cathode and biofilms on the surface of an apple are realized by solving a Poisson equation and continuity equations. The electron temperature is solved by the electron energy conservation equation. The conductivity and permittivity of bacterial biofilms are considered, and the shapes of the bacterial biofilms are irregular in the uncertainty and randomness of colony growth. The distribution of the electrons suggests that two plasma channels divide into three plasma channels when the streamer are 1 mm from the biofilms. The toe-shapes of the biofilms and the simultaneous effect of two streamer heads result in a high electric field around the biofilms, therefore the stronger ionization facilitates the major part of two streamers combined into one streamer and three streamers arise.The distribution of the reactive oxygen species and the reactive nitrogen species captured by time fluences are non-uniform due to the toe-shaped bacterial biofilms. However, the plasma can intrude into the cavities in the adjacent biofilms due to the μm-scale mean free path. The two streamers case has a larger treatment area and realizes the simultaneous treatment of three biofilms compared with one streamer case.     

Degradation of tetracycline in water by gas-liquid plasma in conjunction with rGO-TiO2 nanocomposite

Tetracycline(TC)is an antibiotic mainly used in livestock production and respiratory infection.Traditional methods are not effective in removing TC from solution.In this study,TC was degraded by gas-liquid plasma in the presence of rGO-TiO2 in solution.The rGO-TiO2 was prepared by modified hummers and hydrothermal method.The electrical and optical properties of the gas-liquid discharge plasma were studied and the produced long-lived reactive species were analyzed by spectrophotometer.The degradation efficiency of TC was improved by 41.4％after plasma treatment for 12 min in presence of 30 mg l-1 rGO-TiO2 compared to that with plasma alone.The degradation efficiency increased with increasing discharge power,but as the initial concentration was increased from 20 to 80 mg l-1,the degradation efficiency of TC decreased.The initial pH had no significant effect on the degradation of TC.The intermediate products were determined by UV-vis spectrophotometry and ESI(+)-MS,and the degradation mechanism was analyzed.The reactive species,including O3,OH,and H2O2,etc.,produced in the plasma/catalyst system attracted electron-rich functional groups(amino group,aromatic ring,and double bond).Therefore,the gas-liquid plasma/catalyst system could be an effective and promising method for pharmaceutical wastewater treatment in future.     

Effects of O2 addition on the plasma uniformity and reactivity of Ar DBD excited by ns pulsed and AC power supplies

Dielectric barrier discharges (DBDs) have been widely used in ozone synthesis, materials surface treatment, and plasma medicine for their advantages of uniform discharge and high plasma-chemical reactivity. To improve the reactivity of DBDs, in this work, the O₂ is added into Ar nanosecond (ns) pulsed and AC DBDs. The uniformity and discharge characteristics of Ar ns pulsed and AC DBDs with different O₂ contents are investigated with optical and electrical diagnosis methods. The DBD uniformity is quantitatively analyzed by gray value standard deviation method. The electrical parameters are extracted from voltage and current waveforms separation to characterize the discharge processes and calculate electron density n_e. The optical emission spectroscopy is measured to show the plasma reactivity and calculate the trend of electron temperature T_e with the ratio of two emission lines. It is found that the ns pulsed DBD has a much better uniformity than AC DBD for the fast rising and falling time. With the addition of O₂, the uniformity of ns pulsed DBD gets worse for the space electric field distortion by O₂⁻, which promotes the filamentary formation. While, in AC DBD, the added O₂ can reduce the intensity of filaments, which enhances the discharge uniformity. The ns pulsed DBD has a much higher instantaneous power and energy efficiency than AC DBD. The ratio of Ar emission intensities indicates that the T_e drops quickly with the addition of O₂ both ns pulsed and AC DBDs and the ns pulsed DBD has an obvious higher T_e and n_e than AC DBD. The results are helpful for the realization of the reactive and uniform low temperature plasma sources.     

DBD coupled with MnOx/γ-Al2O3 catalysts for the degradation of chlorobenzene

This paper investigates the degradation of chlorobenzene by dielectric barrier discharge(DBD)coupled with MnOx/γ-Al2O3 catalysts.MnOx/γ-Al2O3 catalysts were prepared using the impregnation method and were characterized in detail by N2 adsorption/desorption,x-ray diffraction and x-ray photoelectron spectroscopy.Compared with the single DBD reactor,the coupled reactor has a better performance on the removal rate of chlorobenzene,the selectivity of COx,and the inhibition of ozone production,especially at low discharge voltages.The degradation rate of chlorobenzene and selectivity of COx can reach 96.3%and 53.0%,respectively,at the specific energy density of 1350 J l-1.Moreover,the ozone concentration produced by the discharge is significantly reduced because the MnOx/Al2O3 catalysts contribute to the decomposition of ozone to form oxygen atoms for the oxidation of chlorobenzene.In addition,based on analysis of the byproducts,the decomposition mechanism of chlorobenzene in the coupled reactor is also discussed.     

Water Content Effect on Oxides Yield in Gas and Liquid Phase Using DBD Arrays in Mist Spray

Electric discharge in and in contact with water can accompany ultraviolet (UV) radiation and electron impact,which can generate a large number of active species such as hydroxyl radicals (OH),oxygen radical (O),ozone (O3) and hydrogen peroxide (H2O2).In this paper,a non thermal plasma processing system was established by means of dielectric barrier discharge (DBD) arrays in water mist spray.The relationship between droplet size and water content was examined,and the effects of the concentrations of oxides in both treated water and gas were investigated under different water content and discharge time.The relative intensity of UV spectra from DBD in water mist was a function of water content.The concentrations of both O3 and nitrogen dioxide (NO2) in DBD room decreased with increasing water content.Moreover,the concentrations of H2O2,O3 and nitrogen oxides (NOx) in treated water decreased with increasing water content,and all the ones enhanced after discharge.The experimental results were further analyzed by chemical reaction equations and commented by physical principles as much as possible.At last,the water containing phenol was tested in this system for the concentration from 100 mg/L to 9.8 mg/L in a period of 35 min.     

Surface treatment of titanium dioxide nanopowder using rotary electrode dielectric barrier discharge reactor

Titanium dioxide (TiO2) nanopowder (P-25;Degussa AG) was treated using dielectric barrier discharge (DBD) in a rotary electrode DBD (RE-DBD) reactor.Its electrical and optical characteristics were investigated during RE-DBD generation.The treated TiO2 nanopowder properties and structures were analyzed using x-ray diffraction (XRD) and Fourier-transform infrared spectroscopy (FTIR).After RE-DBD treatment,XRD measurements indicated that the anatase peak theta positions shifted from 25.3° to 25.1°,which can be attributed to the substitution of new functional groups in the TiO2 lattice.The FTIR results show that hydroxyl groups (OH) at 3400 cm-1 increased considerably.The mechanism used to modify the TiO2 nanopowder surface by air DBD treatment was confirmed from optical emission spectrum measurements.Reactive species,such as OH radical,ozone and atomic oxygen can play key roles in hydroxyl formation on the TiO2 nanopowder surface.     

Analysis of the critical active species for methylene blue decoloration in a dielectric barrier discharge plasma system

In the paper, a hybrid gas–liquid dielectric barrier discharge (DBD) plasma system was set up to treat a methylene blue (MB) solution. The effects of the change of the carrier gas, the gas bubbling rate and different kinds of scavenger addition, including sodium carbonate (Na₂CO₃), para benzoquinone (p-BQ), triethylenediamine and sodium dihydrogen phosphate (NaH₂PO₄), on the MB decoloration were reviewed to clarify the critical active species for the dye decoloration in the DBD plasma system. The obtained results show that higher decoloration of the MB solution could be achieved when O₂ was used as the carrier gas, which could be 100% after 20 min discharge treatment, and the result confirmed the crucial effect of O₃ in the MB decoloration. Based on the experiments of the scavenger addition, it could be concluded that O₂⁻ and ¹O₂ were two other important reactive oxygen species (ROS) for the MB decoloration. The results of the higher chemical oxygen demand removal and faster disappearance of the characteristic peak of the MB from the UV–vis analysis under O₂ bubbling conditions also proved the critical effect of the ROS formed by O₂ on the MB decoloration.