Sensitivity of Ozone Production to the Nmhc Composition, Aerosol Back-Scattering and High Chimney Emission

In this paper, three sensitivity studies are designed to analyze the effect of the NMHC (Non-Methane HydroCarbon) composition, the aerosol back-scattering and the high chimney NO_x emission to the photochemical prodution of ozone by using a one-dimensional photochemistry-diffusion model under a favourable meteorological condition. Measurements of the NMHC composition in Taipei indicated that the percentage of iso-butene, cis-2-butene, trans-2-butene and benzene in a unit volume was much higher than of those observed in other major cities. the high ratio of benzene was directly linked to its high percentage in gasoline. As to the unusually high amount of iso-butene, cis-2-butene and trans-2-butene, more researches are needed to identify their source. Concerns are raised as to how productive is NMHC composition is to the photochemical production of the surface ozone. A rough estimate shows that the total reactivity of the Taipei NMHC composition is about 1.21 × 10^-9 cm³ s^-1 which is 1.6 times that of the Los Angeles (LA) NMHC composition, while the simulated noon peak will be different by 28 ppbv, i.e. 18% more than that simulated with a LA composition.

Meanwhile, high aerosol loading is a serious problem in Taipei. the attenuation of the UV radiation by aerosols cannot be ignored. A numerical simulation shows that the noon ozone level will decrease from 178 to 141ppbv, i. e. about 21% reduction, with deterioration of the visual range from 85 to 5 km.

In the southern Taiwan, industry parks are mixed with the populated Kaohsiung city, hence the large emission of NO_x from high chimneys cannot be ignored. in this study, NO_x is assumed to be emitted in the layer between 235-460 m high with an emission rate of 0.05 or 0.145 ppbv/sec. the results show that the NO_x emitted from the elevated stack lead to a considerable reduction of surface ozone. Such conclusion is obtained due to the fact that a one-dimensional model is used in this paper. Whereas, if a three-dimensional regional model was used, then a higher productivity of ozone downstream would be simulated.     

Enhanced triallyl isocyanurate (TAIC) degradation through application of an O3/UV process: Performance optimization and degradation pathways

• UV/O₃ process had higher TAIC mineralization rate than O₃ process. • Four possible degradation pathways were proposed during TAIC degradation. • pH impacted oxidation processes with pH of 9 achieving maximum efficiency. • CO₃^2– negatively impacted TAIC degradation while HCO₃^– not. • Cl^– can be radicals scavenger only at high concentration (over 500 mg/L Cl^–). Triallyl isocyanurate (TAIC, C₁₂H₁₅N₃O₃) has featured in wastewater treatment as a refractory organic compound due to the significant production capability and negative environmental impact. TAIC degradation was enhanced when an ozone(O₃)/ultraviolet(UV) process was applied compared with the application of an independent O₃ process. Although 99% of TAIC could be degraded in 5 min during both processes, the O₃/UV process had a 70%mineralization rate that was much higher than that of the independent O₃ process (9%) in 30 min. Four possible degradation pathways were proposed based on the organic compounds of intermediate products identified during TAIC degradation through the application of independent O₃ and O₃/UV processes. pH impacted both the direct and indirect oxidation processes. Acidic and alkaline conditions preferred direct and indirect reactions respectively, with a pH of 9 achieving maximum Total Organic Carbon (TOC) removal. Both CO₃^2– and HCO₃^– decreased TOC removal, however only CO₃^2– negatively impacted TAIC degradation. Effects of Cl^– as a radical scavenger became more marked only at high concentrations (over 500 mg/L Cl^–). Particulate and suspended matter could hinder the transmission of ultraviolet light and reduce the production of HO· accordingly.     

Photolysis and photooxidation of typical gaseous VOCs by UV Irradiation: Removal performance and mechanisms

UV photodegradation of 27 typical VOCs was systematically investigated. Contribution of photolysis and photooxidation to VOCs removal was identified. Gaseous VOC could be partially converted to particles by 185/254 nm UV irradiation. The mineralization and conversion of 27 VOCs by UV irradiation were reported. Photodegradation by ultraviolet irradiation (UV) is increasingly applied in volatile organic compound (VOC) and odor gas treatments. In this study, 27 typical VOCs, including 11 hydrocarbons and 16 hydrocarbon derivatives, at 150–200 ppm in air and nitrogen gas were treated by a laboratory-scale UV reactor with 185/254 nm irradiation to systematically investigate their removal and conversion by UV irradiation. For the tested 27 VOCs, the VOC removal efficiencies in air were within the range of 13%–97% (with an average of 80%) at a retention time of 53 s, which showed a moderate positive correlation with the molecular weight of the VOCs (R = 0.53). The respective contributions of photolysis and photooxidation to VOC removal were identified for each VOC. According to the CO₂ results, the mineralization rate of the tested VOCs was within the range of 9%–90%, with an average of 41% and were negatively correlated to the molecular weight (R = -0.63). Many of the tested VOCs exhibited high concentration particulate matters in the off-gases with a 3–283 mg/m³ PM₁₀ range and a 2–40 mg/m³ PM_2.5 range. The carbon balance of each VOC during UV irradiation was analyzed based on the VOC, CO₂ and PM₁₀ concentrations. Certain organic intermediates and 23–218 ppm ozone were also identified in the off-gases. Although the UV technique exhibited a high VOC removal efficiency, its drawbacks, specifically low mineralization, particulate matters production, and ozone emission, must be considered prior to its application in VOC gas treatments.     

Catalytic ozonation of reactive red X-3B in aqueous solution under low pressure: decolorization and OH· generation

Catalytic ozonation of Reactive Red X-3B in aqueous solution had been carried out in an ozone oxidation reactor where Mn-Fe-ceramic honeycomb was used as the catalysts. The presence of Mn-Fe-ceramic honeycomb catalyst could obviously improve the decoloration efficiency of Reactive Red X-3B and the utilization efficiency of ozone compared to the results from non-catalytic ozonation. Adsorption of Reactive Red X-3B had no obviously influence on the degradation efficiency. Addition of tert-butanol significantly decreased the degradation efficiency, indicating that the degradation of Reactive Red X-3B followed the mechanism of hydroxyl radical (OH·) oxidation. The operating variables such as reaction pressure and ozone supply had a positive influence on the degradation efficiency, mainly attributing to facilitate the ozone decomposition and OH· formation.     

Toward better understanding vacuum ultraviolet–iodide induced photolysis via hydrogen peroxide formation,iodine species change,and difluoroacetic acid degradation

• UV/VUV/I^– induces substantial H₂O₂ and IO₃^– formation, but UV/I^– does not. • Increasing DO level in water enhances H₂O₂ and iodate productions. • Increasing pH decreases H₂O₂ and iodate formation and also photo-oxidation. • The redox potentials of UV/VUV/I^– and UV/VUV changes with pH changes. • The treatability of the UV/VUV/I^– process was stronger than UV/VUV at pH 11.0. Recently, a photochemical process induced by ultraviolet (UV), vacuum UV (VUV), and iodide (I^–) has gained attention for its robust potential for contaminant degradation. However, the mechanisms behind this process remain unclear because both oxidizing and reducing reactants are likely generated. To better understand this process, this study examined the evolutions of hydrogen peroxide (H₂O₂) and iodine species (i.e., iodide, iodate, and triiodide) during the UV/VUV/I^– process under varying pH and dissolved oxygen (DO) conditions. Results show that increasing DO in water enhanced H₂O₂ and iodate production, suggesting that high DO favors the formation of oxidizing species. In contrast, increasing pH (from 6.0 to 11.0) resulted in lower H₂O₂ and iodate formation, indicating that there was a decrease of oxidative capacity for the UV/VUV/I^– process. In addition, difluoroacetic acid (DFAA) was used as an exemplar contaminant to verify above observations. Although its degradation kinetics did not follow a constant trend as pH increases, the relative importance of mineralization appeared declining, suggesting that there was a redox transition from an oxidizing environment to a reducing environment as pH rises. The treatability of the UV/VUV/I^– process was stronger than UV/VUV under pH of 11.0, while UV/VUV process presented a better performance at pH lower than 11.0.     

Removal of lead from aqueous solution by hydroxyapatite/manganese dioxide composite

A novel composite adsorbent, hydroxyapatite/manganese dioxide (HAp/MnO₂), has been developed for the purpose of removing lead ions from aqueous solutions. The combination of HAp with MnO₂ is meant to increase its adsorption capacity. Various factors that may affect the adsorption efficiency, including solution pH, coexistent substances such as humic acid and competing cations (Ca²⁺, Mg²⁺), initial solute concentration, and the duration of the reaction, have been investigated. Using this composite adsorbent, solution pH and coexistent calcium or magnesium cations were found to have no significant influence on the removal of lead ions under the experimental conditions. The adsorption equilibrium was described well by the Langmuir isotherm model, and the calculated maximum adsorption capacity was 769 mg·g⁻¹. The sorption processes obeyed the pseudo-second-order kinetics model. The experimental results indicate that HAp/MnO₂ composite may be an effective adsorbent for the removal of lead ions from aqueous solutions.     

Photocatalytic degradation of polybrominated diphenyl ethers in pure water system

Due to the low water solubility of polybrominated diphenyl ethers, organic solvent is usually added into the oxidation system to enhance the removal efficiency. In this study the photocatalytic degradation of decabromodiphenyl ether (BDE209), a type of polybrominated diphenyl ether used throughout the world, in pure water without the addition of organic solvent was investigated. In the pure water system, BDE209 was not dissolved but dispersed as nano-scale particles with a mean diameter of 166 nm. Most of BDE209 (>98%) were removed within 4 h and the final debromination ratio was greater than 80%. Although the addition of organic solvent (tetrahydrofuran, THF) could lead to a relatively high BDE209 degradation rate, the final debromination ratio (<50%) was much lower than that in pure water system. Major oxidation intermediates of tetrahydrofuran, including tetrahydro-2-furanol and γ-butyrolactone, were detected indicating the engagement of THF in the BDE209 degradation process. The photocatalytic degradation of BDE209 in the pure water system followed first-order kinetics. The BDE209 degradation rate constant increased from 0.0011 to 0.0023 min⁻¹ as the pH increased from 3 to 9.     

Fe-Mn-sepiolite as an effective heterogeneous Fenton-like catalyst for the decolorization of reactive brilliant blue

A study of the decolorization of reactive brilliant blue in an aqueous solution using Fe-Mn-sepiolite as a heterogeneous Fenton-like catalyst has been performed. The Fourier transform infrared (FTIR) spectra of the catalyst showed bending vibrations of the Fe-O. The X-ray diffraction (XRD) patterns of the catalyst showed characteristic diffraction peaks of α-Fe₂O₃, γ-Fe₂O₃ and MnO. A four factor central composite design (CCD) coupled with response surface methodology (RSM) was applied to evaluate and optimize the important variables (catalyst addition, hydrogen peroxide dosage, initial pH value and initial dye concentration). When the reaction conditions were catalyst dosage= 0.4 g, [H₂O₂]= 0.3 mL, pH= 2.5, [reactive brilliant blue]_o = 50 mg·L⁻¹, and volume of solution= 500 mL at room temperature, the decolorization efficiency of reactive brilliant blue was 91.98% within 60 min. Moreover, the Fe-Mn-sepiolite catalyst had good stability for the degradation of reactive brilliant blue even after six cycles. Leaching of iron ions (<0.4 mg·L⁻¹) was observed. The decoloring process was reactive brilliant blue specific via a redox reaction. The benzene ring and naphthalene ring were first oxidized to open ring; these were then oxidized to the alcohol and carboxylic acid. The reactive brilliant blue was decomposed mainly by the attack of ·OH radicals including surface-bound ·OH radicals generated on the catalyst surface.     

Combined process of biofiltration and ozone oxidation as an advanced treatment process for wastewater reuse

The effluent of a wastewater treatment plant was treated in a pilot plant for reclaimed water production through the denitrification biofilter (DNBF) process, ozonation (O₃), and biologic aerated filtration (BAF). The combined process demonstrated good removal performance of conventional pollutants, including concentrations of chemical oxygen demand (27.8 mg·L⁻¹) and total nitrogen (9.9 mg·L⁻¹) in the final effluent, which met the local discharge standards and water reuse purposes. Micropollutants (e.g., antibiotics and endocrine-disrupting chemicals) were also significantly removed during the proposed process. Ozonation exhibited high antibiotic removal efficiencies, especially for tetracycline (94%). However, micropollutant removal efficiency was negatively affected by the nitrite produced by DNBF. Acute toxicity variations of the combined process were estimated by utilizing luminescent bacteria. Inhibition rate increased from 9% to 15% during ozonation. Carbonyl compound concentrations (e.g., aldehydes and ketones) also increased by 58% as by-products, which consequently increased toxicity. However, toxicity eventually became as low as that of the influent because the by-products were effectively removed by BAF. The combined DNBF/O₃/BAF process is suitable for the advanced treatment of reclaimed water because it can thoroughly remove pollutants and toxicity.     

腐殖质的光化学降解及其对环境污染物环境行为的影响

腐殖质是地表环境中最重要的有机组分,也是生态环境中最主要的吸光物质之一,对环境污染物的形态、迁移、毒性和生物可利用性有着重要的影响。文章综述了腐殖质的结构特征和光化学降解反应过程和机理,指出腐殖质的光敏化和光化学降解过程对环境污染物的环境行为和归宿有重要的影响。通常,腐殖质的光敏化作用在低质量浓度下,尤其在一定铁离子的协同作用下可促进有机污染物的降解,但高质量浓度的腐殖质由于其本身的吸光作用以及参与自由基的竞争则抑制有机污染物的降解。腐殖质的光化学降解过程降低了环境体系的pH和腐殖质的分子量、破坏了腐殖质的芳环结构、改变了紫外和可见光区域的吸收等,导致其与重金属离子和有机污染物结合能力的下降,造成水体或颗粒态中游离的污染物质量浓度增加,对生态系统将造成更大的危害。目前对腐殖质和环境污染物本身的光化学降解机理已较为清晰,今后应加强对自然水体或土壤系统中腐殖质光化学降解的影响因素,腐殖质光化学降解过程中结构特性的变化机理,以及腐殖质的结构特性与环境污染物结合性质之间的构效关系等方面的研究。特别是随着平流层臭氧空洞的增加,增强了到达地球表面的紫外线强度,研究紫外线增强对腐殖质和有机污染物的降解以及对生态系统的影响可进一步深刻理解太阳光辐射对污染物环境行为和归宿的影响。     

Photoelectrocatalytic degradation of camphor on TiO2/RuO2 electrodes

The degradation of camphor using titanium/ruthenium dioxide (TiO₂/RuO₂; 70:30) electrodes was investigated in a photoelectrochemical thin-film reactor under near UV light irradiation. Two different electrolytes (Na₂SO₄ and NaCl) were used in this work. Camphor degradation was monitored by solvent extraction methods and gas chromatography (GC) analysis. Comparative studies between photoelectrochemical, electrochemical, photolytic, and heterogeneous photocatalytical process were carried out. When NaCl was used, the degradation efficiency of camphor was improved, probably on account of electrochemical generation of active chlorine species and their photochemical conversion to chlorine radicals. Under these conditions camphor was completely mineralized at reaction times of 30 min.     

Cadmium tolerance and accumulation in fifteen wetland plant species from cadmium-polluted water in constructed wetlands

Variations in cadmium (Cd) tolerances and accumulations among fifteen wetland plant species in moderately (0.5 mg·L⁻¹) and heavily (1.0 mg·L⁻¹) Cd-polluted wastewaters were investigated in constructed wetlands. Cd removal efficiencies from the wastewaters were more than 90%, and 23.5% and 16.8% of the Cd in the water accumulated in wetland plants for 0.5 and 1.0 mg·L⁻¹ Cd treatments, respectively. The variations among the plant species were 29.4-fold to 48.7-fold in plant biomasses, 5.4-fold to 21.9-fold in Cd concentrations, and 13.8-fold to 29.6-fold in Cd accumulations. The plant species were also largely diversified in terms of Cd tolerance. Some species were tolerant of heavy Cd stress, and some others were sensitive to moderate Cd level. Four wetland plant species were selected for the treatment of Cd-polluted wastewater for their high Cd accumulating abilities and relative Cd tolerances. Plant Cd quantity accumulations are correlated positively and significantly (P <0.05) with plant biomasses and correlated positively but insignificantly (P >0.05) with plant Cd concentrations. The results indicate that the Cd accumulation abilities of wetland plant species are determined mainly by their biomasses and Cd tolerances in growth, which should be the first criteria in selecting wetland plant species for the treating Cd-polluted wastewaters. Cd concentration in the plants may be the second consideration.     

Ozonation of the 5-fluorouracil anticancer drug and its prodrug capecitabine: Reaction kinetics,oxidation mechanisms,and residual toxicity

Specific second-order rate constants were determined for 5-FU and CAP with ozone. Reaction sites were confirmed by kinetics, Fukui analysis, and products. The olefin moiety was the main ozone reaction site for 5-FU and CAP. Carboxylic acids comprised most of the residual TOC for 5-FU. Ozonation removed the toxicity associated with 5-FU and products but not CAP. Anticancer drugs (ADs) have been detected in the environment and represent a risk to aquatic organisms, necessitating AD removal in drinking water and wastewater treatment. In this study, ozonation of the most commonly used antimetabolite ADs, namely 5-fluorouracil (5-FU) and its prodrug capecitabine (CAP), was investigated to determine reaction kinetics, oxidation mechanisms, and residual toxicity. The specific second-order rate constants between aqueous ozone and 5-FU, 5-FU⁻, 5-FU²⁻, CAP, and CAP⁻ were determined to be 7.07(±0.11)×10⁴ M⁻¹·s⁻¹, 1.36(±0.06)×10⁶ M⁻¹·s⁻¹, 2.62(±0.17)×10⁷ M⁻¹·s⁻¹, 9.69(±0.08)×10³ M⁻¹·s⁻¹, and 4.28(±0.07)×10⁵ M⁻¹·s⁻¹, respectively; furthermore, the second-order rate constants for ^•OH reaction with 5-FU and CAP at pH 7 were determined to be 1.85(±0.20)×10⁹ M⁻¹·s⁻¹ and 9.95(±0.26)×10⁹ M⁻¹·s⁻¹, respectively. Density functional theory was used to predict the main ozone reaction sites of 5-FU (olefin) and CAP (olefin and deprotonated secondary amine), and these mechanisms were supported by the identified transformation products. Carboxylic acids constituted a majority of the residual organic matter for 5-FU ozonation; however, carboxylic acids and aldehydes were important components of the residual organic matter generated by CAP. Ozone removed the toxicity of 5-FU to Vibrio fischeri, but the residual toxicity of ozonated CAP solutions exhibited an initial increase before subsequent removal. Ultimately, these results suggest that ozone is a suitable technology for treatment of 5-FU and CAP, although the residual toxicity of transformation products must be carefully considered.     

Treatment of swine wastewater in aerobic granular reactors: comparison of different seed granules as factors

The granulation process, physic-chemical properties, pollution removal ability and bacterial communities of aerobic granules with different feed-wastewater (synthetic wastewater, R1; swine wastewater, R2), and the change trend of some parameters of two types of granules in long-term operated reactors treating swine wastewater were investigated in this experiment. The result indicated that aerobic granulation with the synthetic wastewater had a faster rate compared with swine wastewater and that full granulation in R1 and R2 was reached on the 30th day and 39th day, respectively. However, although the feed wastewater also had an obvious effect on the biomass fraction and extracellular polymeric substances of the aerobic granules during the granulation process, these properties remained at a similar level after long-term operation. Moreover, a similar increasing trend could also be observed in terms of the nitrogen removal efficiencies of the aerobic granules in both reactors, and the average specific removal rates of the organics and ammonia nitrogen at the steady-state stage were 35.33 mg·g⁻¹ VSS and 51.46 mg·g⁻¹ VSS for R1, and 35.47 mg·g⁻¹ VSS and 51.72 mg·g⁻¹ VSS for R2, respectively. In addition, a shift in the bacterial diversity occurred in the granulation process, whereas bacterial communities in the aerobic granular reactor were not affected by the seed granules after long-term operation.     

Sensitivity of Ozone Production to the Nmhc Composition,Aerosol Back-Scattering and High Chimney Emission

Abstract

In this paper, three sensitivity studies are designed to analyze the effect of the NMHC (Non-Methane HydroCarbon) composition, the aerosol back-scattering and the high chimney NO _x emission to the photochemical prodution of ozone by using a one-dimensional photochemistry-diffusion model under a favourable meteorological condition. Measurements of the NMHC composition in Taipei indicated that the percentage of iso-butene, cis-2-butene, trans-2-butene and benzene in a unit volume was much higher than of those observed in other major cities. the high ratio of benzene was directly linked to its high percentage in gasoline. As to the unusually high amount of iso-butene, cis-2-butene and trans-2-butene, more researches are needed to identify their source. Concerns are raised as to how productive is NMHC composition is to the photochemical production of the surface ozone. A rough estimate shows that the total reactivity of the Taipei NMHC composition is about 1.21 × 10^?9 cm³ s^?1 which is 1.6 times that of the Los Angeles (LA) NMHC composition, while the simulated noon peak will be different by 28 ppbv, i.e. 18% more than that simulated with a LA composition.

Meanwhile, high aerosol loading is a serious problem in Taipei. the attenuation of the UV radiation by aerosols cannot be ignored. A numerical simulation shows that the noon ozone level will decrease from 178 to 141ppbv, i. e. about 21% reduction, with deterioration of the visual range from 85 to 5 km.

In the southern Taiwan, industry parks are mixed with the populated Kaohsiung city, hence the large emission of NO _x from high chimneys cannot be ignored. in this study, NO _x is assumed to be emitted in the layer between 235–460 m high with an emission rate of 0.05 or 0.145 ppbv/sec. the results show that the NO _x emitted from the elevated stack lead to a considerable reduction of surface ozone. Such conclusion is obtained due to the fact that a one-dimensional model is used in this paper. Whereas, if a three-dimensional regional model was used, then a higher productivity of ozone downstream would be simulated.     

Selective photoreduction of acetonitrile to acetaldehyde in dilute aqueous solutions

Acetonitrile is a commonly used solvent in both industry and research. The treatment of acetonitrile wastes in dilute aqueous solutions with visible light offers advantages to chemical treatment and ultraviolet (UV) irradiation. This study presents the degradation of acetonitrile via a photoinduced electron transfer reaction in the presence of a photosensitizer (dye) and a sacrificial reductant under visible light. Acetonitrile photodegradation (photoreduction) was investigated utilizing a variety of sacrificial reductants and photosensitizers. Optimal results were observed in the presence of methylene green and tri-isopropanolamine with a decrease of acetonitrile in solution to 86% in 24 hours. The only photoreaction product observed was acetaldehyde and a plausible mechanism for the photochemical degradation of acetonitrile is proposed.     

Degradation of endocrine disruptor bisphenol A in drinking water by ozone oxidation

The ozone oxidation of endocrine disruptor bisphenol A in drinking water was investigated. A stainless completely mixed reactor was employed to carry out the degradation experiments by means of a batch model. With an initial concentration of 11.0 mg/L, the removal efficiencies of BPA (bisphenol A) could be measured up to 70%, 82%, and 90% when the dosages of ozone were 1, 1.5, and 2 mg/L, respectively. The impacts on BPA degradation under the conditions of different ozone dosages, water background values, BPA initial concentrations, and ozone adding time were analyzed. The results showed that ozone dosage plays a dominant role during the process of BPA degradation, while the impact of the contact time could be ignored. UV wavelength scanning was used to confirm that the by-products were produced, which could be absorbed at UV254. The value of UV254 was observed to have changed during the ozonation process. Based on the change of UV254, it could be concluded that BPA is not completely degraded at low ozone dosage, while shorter adding time of total ozone dosage, high ozone dosage, and improvement of dissolved ozone concentration greatly contribute to the extent of BPA degradation. The effects of applied H₂O₂ dose in ozone oxidation of BPA were also examined in this study. The O₃-H₂O₂ processes proved to have similar effects on the degradation of BPA by ozone oxidation.     

Photocatalytic degradation of aqueous methyl-tert-butyl-ether (MTBE) in a supported-catalyst reactor

Contamination of groundwater by methyl-tert-butyl ether (MTBE) poses increasing problems to water companies. Here we demonstrate the feasibility of using a cylindrical, supported-catalyst reactor for photocatalytic degradation of MTBE in water. It was shown that photocatalytic degradation of MTBE follows pseudo first-order kinetics. The maximum reaction rate constant observed was 0.47 hr^–1. The reaction rate increases linearly with increasing light intensity. It was also found that the reaction rate is linearly proportional to the ratio of catalyst surface area to volume of reactor. Complete degradation of MTBE was reached with an excess supply of oxygen.     

Optimization of the O3/H2O2 process with response surface methodology for pretreatment of mother liquor of gas field wastewater

• Real ML-GFW with high salinity and high organics was degraded by O₃/H₂O₂ process. • Successful optimization of operation conditions was attained using RSM based on CCD. • Single-factor experiments in advance ensured optimal experimental conditions. • The satisfactory removal efficiency of TOC was achieved in spite of high salinity. • The initial pH plays the most significant role in the degradation of ML-GFW. The present study reports the use of the O₃/H₂O₂ process in the pretreatment of the mother liquor of gas field wastewater (ML-GFW), obtained from the multi-effect distillation treatment of the gas field wastewater. The range of optimal operation conditions was obtained by single-factor experiments. Response surface methodology (RSM) based on the central composite design (CCD) was used for the optimization procedure. A regression model with Total organic carbon (TOC) removal efficiency as the response value was established (R² = 0.9865). The three key factors were arranged according to their significance as: pH>H₂O₂ dosage>ozone flow rate. The model predicted that the best operation conditions could be obtained at a pH of 10.9, an ozone flow rate of 0.8 L/min, and H₂O₂ dosage of 6.2 mL. The dosing ratio of ozone was calculated to be 9.84 mg O₃/mg TOC. The maximum removal efficiency predicted was 75.9%, while the measured value was 72.3%. The relative deviation was found to be in an acceptable range. The ozone utilization and free radical quenching experiments showed that the addition of H₂O₂ promoted the decomposition of ozone to produce hydroxyl radicals (·OH). This also improved the ozone utilization efficiency. Gas chromatography-mass spectrometry (GC-MS) analysis showed that most of the organic matters in ML-GFW were degraded, while some residuals needed further treatment. This study provided the data and the necessary technical supports for further research on the treatment of ML-GFW.     

Local production,downward and regional transport aggravated surface ozone pollution during the historical orange-alert large-scale ozone episode in eastern China

Increasing severe and persistent ozone pollution in China has resulted in serious harm to human health in recent years, yet the precise pollution sources are poorly known because there is few knowledge on large-scale extreme ozone episodes. Here, we studied the formation of the historical orange-alert regional ozone episode in eastern China on 6 June, 2021, by combining process analysis, integrated source apportionment modelling, and chemical and meteorological data. Results show that during the pollution episode, 94% of cities in eastern China suffered ozone pollution, and 39% had daily maximum 8-h average ozone concentrations higher than 100 ppb. This is explained by favorable local ozone formation and transports provided by the prevailing northwestern winds in the upper air, and by sinking atmospheric motions favoring the persistence of high surface ozone concentrations. During daytime, local photochemical production induced an ozone increase of 0.3–28.4 ppb h^?1 and vertical transport induced an ozone increase of 0.4–56.1 ppb h^?1. As a consequence, vertical downward transport of ozone generated in the upper air by photochemical reactions aggravated surface ozone pollution. Surface ozone concentrations include 25.8–53.9% of ozone from local provincial emissions, 0–42.6% of ozone from inter-regional transports from neighboring regions, 4.6–23.1% of ozone from outer-regional transport, and 13.6–52.9% of ozone from boundary conditions in the selected cities. Overall, our findings show that favorable meteorological conditions promoted the chemical productions of ozone on the surface and at high altitudes, thus resulting in this heavy ozone pollution. In addition, regional and vertical downward transports of aloft ozone further aggravated the surface ozone pollution, leading to the large-scale extreme ozone pollution episode.