Research on the degradation mechanism of dimethyl phthalate in drinking water by strong ionization discharge

The degradation mechanism of dimethyl phthalate(DMP) in the drinking water was investigated using strong ionization discharge technology in this study. Under the optimized condition, the degradation efficiency of DMP in drinking water was up to 93% in 60 min. A series of analytical techniques including high-performance liquid chromatography, liquid chromatography mass spectrometry, total organic carbon analyzer and ultraviolet–visible spectroscopy were used in the study. It was found that a high concentration of ozone(O_3) produced by dielectric barrier discharge reactor was up to 74.4 mg l~(-1) within 60 min. Tert-butanol, isopropyl alcohol,carbonate ions(CO_3~(2-)) and bicarbonate ions (HCO_3~-) was added to the sample solution to indirectly prove the presence and effect of hydroxyl radicals(·OH). These analytical findings indicate that mono-methyl phthalate, phthalic acid(PA) and methyl ester PA were detected as the major intermediates in the process of DMP degradation. Finally, DMP and all products were mineralized into carbon dioxide(CO_2) and water(H_2O) ultimately. Based on these analysis results, the degradation pathway of DMP by strong ionization discharge technology were proposed.     

Degradation of phenol using a combination of granular activated carbon adsorption and bipolar pulse dielectric barrier discharge plasma regeneration

A combined method of granular activated carbon (GAC) adsorption and bipolar pulse dielectric barrier discharge (DBD) plasma regeneration was employed to degrade phenol in water. After being saturated with phenol, the GAC was filled into the DBD reactor driven by bipolar pulse power for regeneration under various operating parameters. The results showed that different peak voltages, air flow rates, and GAC content can affect phenol decomposition and its major degradation intermediates, such as catechol, hydroquinone, and benzoquinone. The higher voltage and air support were conducive to the removal of phenol, and the proper water moisture of the GAC was 20％. The amount of H2O2 on the GAC was quantitatively determined, and its laws of production were similar to phenol elimination. Under the optimized conditions, the elimination of phenol on the GAC was confirmed by Fourier transform infrared spectroscopy,and the total removal of organic carbons achieved 50.4％. Also, a possible degradation mechanism was proposed based on the HPLC analysis. Meanwhile, the regeneration efficiency of the GAC was improved with the discharge treatment time, which attained 88.5％ after 100 min of DBD processing.     

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.     

A comparative study on the activity of TiO2 in pulsed plasma under different discharge conditions

In the present study,a combination of pulsed discharge plasma and TiO_2(plasma/TiO_2)has been developed in order to study the activity of TiO_2by varying the discharge conditions of pulsed voltage,discharge mode,air flow rate and solution conductivity.Phenol was used as the chemical probe to characterize the activity of TiO_2in a pulsed discharge system.The experimental results showed that the phenol removal efficiency could be improved by about 10%by increasing the applied voltage.The phenol removal efficiency for three discharge modes in the plasma-discharge-alone system was found to be highest in the spark mode,followed by the spark–streamer mode and finally the streamer mode.In the plasma/TiO_2system,the highest catalytic effect of TiO_2was observed in the spark–streamer discharge mode,which may be attributed to the favorable chemical and physical effects from the spark–streamer discharge mode,such as ultraviolet light,O_3,H_2O_2,pyrolysis,shockwaves and high-energy electrons.Meanwhile,the optimal flow rate and conductivity were 0.05 m~3l~(-1)and 10μS cm~(-1),respectively.The main phenolic intermediates were hydroquinone,catechol,and p-benzoquinone during the discharge treatment process.A different phenol degradation pathway was observed in the plasma/TiO_2system as compared to plasma alone.Analysis of the reaction intermediates demonstrated that p-benzoquinone reduction was selectively catalyzed on the TiO_2surface.The effective decomposition of phenol constant(D_e)increased from 74.11%to 79.16%when TiO_2was added,indicating that higher phenol mineralization was achieved in the plasma/TiO_2system.     

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.     

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.     

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...     

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.     

Degradation and mineralization of ciprofloxacin by gas–liquid discharge non-thermal plasma

A typical quinolones antibiotic ciprofloxacin(CIP) in aqueous solution was degraded by a gas–liquid discharge non-thermal plasma system. The discharge plasma power and the emission intensity of the excited reactive species(RS) generated in the gas phase were detected by the oscilloscope and the optical emission spectroscopy. The effects of various parameters on CIP degradation, i.e. input powers, initial concentrations addition of radical scavengers and p H values were investigated. With the increase of discharge power, the degradation efficiency increased but the energy efficiency significantly reduced. The degradation efficiency also reduced under high concentration of initial CIP conditions due to the competitive reactions between the plasma-induced RS with the degradation intermediates of CIP. Different radical scavengers(isopropanol and CCl_4) on ·OH and H· were added into the reaction system and the oxidation effects of ·OH radicals have been proved with high degradation capacity on CIP.Moreover, the long-term degradation effect on CIP in the plasma-treated aqueous solution proved that the long-lived RS(H_2O_2 and O_3, etc) might play key roles on the stay effect through multiple aqueous reactions leading to production of ·OH. The degradation intermediates were determined by the method of electrospray ionization(+)-mass spectroscopy, and the possible degradation mechanism were presented.     

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.     

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.     

Characteristics of gas-liquid diaphragm discharge and its application on decolorization of brilliant red B in aqueous solution

A simple gas-liquid diaphragm discharge reactor was designed and characteristics of the discharge and its application on decolorization of brilliant red B in an aqueous solution were investigated. The results showed that strong oxidizing agents such as ·OH and ·O radicals were generated. Average electron temperature of the discharge was 0.72 eV, 1.15 eV and 0.83 eV with air, oxygen and argon as the discharge gas, respectively. Solution p H and conductivity changed little when oxygen or argon was used as the discharge gas; however, these two parameters changed significantly when the discharge was performed in air. During the discharge treatment,the characteristic absorption peaks of brilliant red B gradually decreased where the decolorization followed the first-order kinetics. With 10 min of discharge, the decolorization of brilliant red B(30 mg L~(-1)) can reach 96%, 81% and 62% in the cases of oxygen, argon and air,respectively. The analysis of by-products showed that the brilliant red B molecule can be effectively destroyed in this discharge mode.     

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.     

Oxidative Degradation of o-Chlorophenol with Contact Glow Discharges in Aqueous Solution

Contact glow discharge electrolysis (CGDE) of o-chlorophenol (2-CP) was investigated under different pH, voltages and initial concentrations. And the mechanism of the oxidation was explored. The results suggested that the degradation followed the first order kinetic law; Fe^2 had a remarkable catalytic effect on the removal rate of o-chloropenol. In the presence of Fe^2 , 2-CP underwent an exhaustive degradation, from which the major intermediates included o-dihydroxybenze, p-hydroxybenze, p-benzoquione and carboxlic acids.     

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.     

Study on the Removal of SO2 from Simulated Flue Gas Using Dry Calcium-Spray with DBD Plasma

In this study, lime-hydrate （Ca（OH）2） desulfurizer was treated by plasma with strong ionization discharge of a dielectric barrier. The removal of SO2 from simulated flue gas was investigated. The principles of SO2 removal are discussed. Several factors affecting the efficiency of SO2 removal were studied. They included the ratio of calcium to sulfur （Ca/S）, desulfurizer granularity, residence time of the flue gas, voltage applied to the discharge electrode in the plasma generator, and energy consumption. Experimental results indicate that the increase in Ca/S ratio, the applied voltage and discharge power, the residence time, and the reduction in the desulfurizer granularity all can raise the SO2 removal efficiency. The SO2 removal efficiency was up to 91.3% under the following conditions, namely a primary concentration of SO2 of 2262×10^-6 （v/v） in the emission gas, 21%（v/v） of oxygen, 1.8% （v/v） of water, a Ca/S ratio of 1.48, a residence time of 2.8 s, a 3.4 kV voltage and a 10kHz frequency power applied to the discharge electrodes in the plasma generator, and a flow rate of 100 m^3/h for emission gas.     

Degradation of antibiotic contaminants from water by gas–liquid underwater discharge plasma

Antibiotic contamination adversely affects human health and ecological balance.In this study,gasliquid underwater discharge plasma was employed to simultaneously degrade three antibiotics,sulfadiazine(SDZ),tetracycline(TC),and norfloxacin(NOR),to address the growing problem of antibiotic contaminants in water.The effects of various parameters on the antibiotic degradation efficiency were evaluated,including the discharge gas type and flow rate,the initial concentration and pH of the solution,and...     

Dielectric barrier discharge plasma pretreatment on hydrolysis of microcrystalline cellulose

Dielectric barrier discharge (DBD) plasma was used as a pretreatment method for downstream hydrolysis of microcrystalline cellulose (MCC).The degree of polymerization (DP) of MCC decreased after it was pretreated by DBD plasma under a carder gas of air/argon.The effectiveness of depolymerization was found to be influenced by the crystallinity of MCC when under the pretreatment of DBD plasma.With the addition of tert-butyl alcohol in the treated MCC water suspension solution,depolymerization effectiveness of MCC was inhibited.When MCC was pretreated by DBD plasma for 30 min,the total reducing sugar concentration (TRSC) and liquefaction yield (LY) of pretreated-MCC (PMCC) increased by 82.98％ and 34.18％ respectively compared with those for raw MCC.     

Influence of electrical parameters on H2O2 generation in DBD non-thermal reactor with water mist

A dielectric barrier discharge (DBD) reactor is introduced to generate H2O2 by non-thermal plasma with a mixture of oxygen and water mist produced by an ultrasonic atomizer.The results of our experiment show that the energy yield and concentration of the generated H2O2 in the pulsed discharge are much higher than that in AC discharge,due to its high energy efficiency and low heating effect.Micron-sized liquid droplets produced by an ultrasonic atomizer in water mist have large specific surface area,which greatly reduces mass transfer resistance between hydroxyl radicals and water liquids,leading to higher energy yield and H2O2 concentration than in our previous research.The influence of applied voltage,discharge frequency,and environmental temperature on the generated H2O2 is discussed in detail from the viewpoint of the DBD mechanism.The H2O2 concentration of 30 mg 1-1,with the energy yield of 2 g kW-1h 1 is obtained by pulsed discharge in our research.     

Study on purification technology of polyacrylamide wastewater by non-thermal plasma

In this work, non-thermal plasma has been applied to treat polyacrylamide (PAM) wastewater. We have investigated the influence of the rule of PAM wastewater initial pH, solution concentration and discharge time, discharge voltage on chemical oxygen demand (COD) degradation rate. At the same time, the effect of pH and discharge time on the viscosity removal rate of PAM solution was also studied. Then, the effect of pH on the viscosity removal rate of 1.0 gl ⁻¹ PAM solution was studied separately. Through orthogonal test, the factors affecting the COD degradation rate of PAM wastewater were determined as follows: discharge time>discharge voltage>solution concentration>wastewater initial pH. The COD highest removal rate of PAM wastewater reached 85.74%, when the optimal conditions are as follows: discharge voltage 40 kV, discharge time 5 h, solution concentration 1.0 gl ⁻¹, pH 1.5. This research provides some basic data and new theoretical basis for PAM wastewater purification.