Removal of formaldehyde over MnxCe1-xO2 catalysts: Thermal catalytic oxidation versus ozone catalytic oxidation

MnxCe1- xO2（x： 0.3–0.9） prepared by Pechini method was used as a catalyst for the thermal catalytic oxidation of formaldehyde（HCHO）. At x = 0.3 and 0.5, most of the manganese was incorporated in the fluorite structure of Ce O2 to form a solid solution. The catalytic activity was best at x = 0.5, at which the temperature of 100% removal rate is the lowest（270°C）. The temperature for 100% removal of HCHO oxidation is reduced by approximately 40°C by loading 5 wt.% Cu Oxinto Mn0.5Ce0.5O2. With ozone catalytic oxidation, HCHO（61 ppm） in gas stream was completely oxidized by adding 506 ppm O3 over Mn0.5Ce0.5O2 catalyst with a GHSV（gas hourly space velocity） of 10,000 hr-1at 25°C. The effect of the molar ratio of O3 to HCHO was also investigated. As O3/HCHO ratio was increased from 3 to 8, the removal efficiency of HCHO was increased from 83.3% to 100%. With O3/HCHO ratio of 8, the mineralization efficiency of HCHO to CO2 was 86.1%. At 25°C, the p-type oxide semiconductor（Mn0.5Ce0.5O2） exhibited an excellent ozone decomposition efficiency of 99.2%,which significantly exceeded that of n-type oxide semiconductors such as Ti O2, which had a low ozone decomposition efficiency（9.81%）. At a GHSV of 10,000 hr-1, [O3]/[HCHO] = 3 and temperature of 25°C, a high HCHO removal efficiency（≥ 81.2%） was maintained throughout the durability test of 80 hr, indicating the long-term stability of the catalyst for HCHO removal.     

On the effect of Fe(III) on proliferation of Microcystis aeruginosa at high nitrate and low chlorophyll condition

The impact of Fe concentrations on the growth of Microcystisaeruginosa in aquatic systems under high nitrate and low chlorophyll conditions was studied. The responses of cell density, total and cell chlorophyll-a intracellular Fe content and organic elemental composition of M. aeruginosa to different concentration gradients of Fe(III) in the solutions were analysed. The results showed that the proliferation speeds of M. aeruginosa were: (1) decelerated when the Fe(III) concentration was lower than 50 μg/L in the solutions, (2) promoted and positively related to the increase of Fe(III) concentration from 100 to 500 μg/L in the solutions over the experimental period, and (3) promoted in the early stage but decelerated in later stages by excess adsorption of Fe by cells when the Fe(III) concentration was higher than 500 μg/L in the solutions. The maximum cell density, total and cell chlorophyll-a were all observed at 500 μg Fe(III)/L concentration. The organic elemental composition of M. aeruginosa was also affected by the concentration of Fe(III) in the solutions, and the molecular formula of M. aeruginosa should be expressed as C_7–7.5H₁₄O_0.8–1.3N_3.5–5 according to the functions for different Fe(III) concentrations. Cell carbon and oxygen content appeared to increase slightly, while cell nitrogen content appeared to decrease as Fe(III) concentrations increased from 100 to 500 μg/L in the solutions. This was attributed to the competition of photosynthesis and nitrogen adsorption under varying cell Fe content.     

Synergistic effects of non-thermal plasma-assisted catalyst and ultrasound on toluene removal

A wire-mesh catalyst coated by La_0.8Sr_0.2MnO₃ was combined with a dielectric barrier discharge (DBD) reactor for toluene removal at atmospheric pressure. It was found that toluene removal efficiency and carbon dioxide selectivity were enhanced in the catalytic packed-bed reactor. In addition, ozone and nitrogen monoxide from the gas effluent byproducts decreased. This is the first time that ultrasound combined with plasma has been used for toluene removal. A synergistic effect on toluene removal was observed in the plasma-assisted ultrasound system. At the same time, the system increased toluene conversion and reduced ozone emission.     

The impact of preozonation on the coagulation of cellular organic matter produced by Microcystis aeruginosa and its toxin degradation

Ozonation pretreatment is typically implemented to improve algal cell coagulation. However, knowledge on the effect of ozonation on the characteristics and coagulation of associated algal organic matter, particularly cellular organic matter (COM), which is extensively released during algal bloom decay, is limited. Hence, this study aimed to elucidate the impact of ozonation applied before the coagulation of dissolved COM from the cyanobacteria Microcystis aeruginosa. Additionally, the degradation of microcystins (MCs) naturally present in the COM matrix was investigated. A range of ozone doses (0.1–1.0 mg O₃/mg of dissolved organic carbon – DOC) and ozonation pH values (pH 5, 7 and 9) were tested, while aluminium and ferric sulphate coagulants were used for subsequent coagulation. Despite negligible COM removal, ozonation itself eliminated MCs, and a lower ozone dose was required when performing ozonation at acidic or neutral pH (0.4 mg O₃/mg DOC at pH 5 and 7 compared to 0.8 mg O₃/mg DOC at pH 9). Enhanced MC degradation and a similar pattern of pH dependence were observed after preozonation-coagulation, whereas coagulation alone did not sufficiently remove MCs. In contrast to the benefits of MC depletion, preozonation using ≥ 0.4 mg O₃/mg DOC decreased the coagulation efficiency (from 42%/48% to 28%–38%/41%–44% using Al/Fe-based coagulants), which was more severe with increasing ozone dosage. Coagulation was also influenced by the preozonation pH, where pH 9 caused the lowest reduction in COM removal. The results indicate that ozonation efficiently removes MCs, but its employment before COM coagulation is disputable due to the deterioration of coagulation.     

Catalytic liquid-phase oxidation of acetaldehyde to acetic acid over a Pt/CeO2–ZrO2–SnO2/γ-alumina catalyst

Pt/CeO₂–ZrO₂–SnO₂/γ-Al₂O₃ catalysts were prepared by co-precipitation and wet impregnation methods for catalytic oxidation of acetaldehyde to acetic acid in water. In the present catalysts, Pt and CeO₂–ZrO₂–SnO₂ were successfully dispersed on the γ-Al₂O₃ support. Dependences of platinum content and reaction time on the selective oxidation of acetaldehyde to acetic acid were investigated to optimize the reaction conditions for obtaining both high acetaldehyde conversion and highest selectivity to acetic acid. Among the catalysts, a Pt(6.4 wt.%)/Ce_0.68Zr_0.17Sn_0.15O_2.0(16 wt.%)/γ-Al₂O₃ catalyst showed the highest acetaldehyde oxidation activity. On this catalyst, acetaldehyde was completely oxidized after the reaction at 0°C for 8 hr, and the selectivity to acetic acid reached to 95% and higher after the reaction for 4 hr and longer.     

Vertical distribution of aerosol optical properties based on aircraft measurements over the Loess Plateau in China

Vertical distributions of aerosol optical properties based on aircraft measurements over the Loess Plateau were measured for the first time during a summertime aircraft campaign, 2013 in Shanxi, China. Data from four flights were analyzed. The vertical distributions of aerosol optical properties including aerosol scattering coefficients (σ_sc), absorption coefficients (σ_ab), Angström exponent (α), single scattering albedo (ω), backscattering ratio (β_sc), aerosol mass scattering proficiency (Q_sc) and aerosol surface scattering proficiency (Q_sc^′) were obtained. The mean statistical values of σ_sc were 77.45 Mm^− 1 (at 450 nm), 50.72 Mm^− 1 (at 550 nm), and 32.02 Mm^− 1 (at 700 nm). The mean value of σ_ab was 7.62 Mm^− 1 (at 550 nm). The mean values of α, β_sc and ω were 1.93, 0.15, and 0.91, respectively. Aerosol concentration decreased with altitude. Most effective diameters (ED) of aerosols were less than 0.8 μm. The vertical profiles of σ_sc,, α, β_sc, Q_sc and Q_sc^′ showed that the aerosol scattering properties at lower levels contributed the most to the total aerosol radiative forcing. Both α and β_sc had relatively large values, suggesting that most aerosols in the observational region were small particles. The mean values of σ_sc, α, β_sc, Q_sc, Q_sc^′, σ_ab and ω at different height ranges showed that most of the parameters decreased with altitude. The forty-eight hour backward trajectories of air masses during the observation days indicated that the majority of aerosols in the lower level contributed the most to the total aerosol loading, and most of these particles originated from local or regional pollution emissions.     

A novel approach to treat combined domestic wastewater and excess sludge in MBR

Domestic wastewater was treated by combined anaerobic biofilm-aerobic membrane bioreactor(MBR) process, and part biomass in MBR was withdrawn, to treat with ozone, then the ozonated sludge was returned to anaerobic inlet. In aerobic MBR, MLSS and DO were controlled at 3000—3500 mg/L and 0.8 mg/L respectively. Comparing the experimental results of two stages, it was noticed that ozonation did not affect the removal efficiency for organics but had a significant influence on the removals of NHs-N and TN. During the ozonation period of two months, no excess sludge was wasted, and a zero sludge yield was obtained.     

Reaction mechanism and metal ion transformation in photocatalytic ozonation of phenol and oxalic acid with Ag+/TiO2

Photocatalytic ozonation of phenol and oxalic acid （OA） was conducted with a Ag^＋/TiO2 catalyst and different pathways were found for the degradation of different compounds. Ag^＋ greatly promoted the photocatalytic degradation of contaminants due to its role as an electron scavenger. It also accelerated the removal rate of OA in ozonation and the simultaneous process for its complex reaction with oxalate. Phenol could be degraded both in direct ozonation and photolysis, but the TOC removal rates were much higher in the simultaneous processes due to the oxidation of hydroxyl radicals resulting from synergetic effects. The sequence of photo-illumination and ozone exposure in the combined process showed quite different effects in phenol degradation and TOC removal. The synergetic effects in different combined processes were found to be highly related to the properties of the target pollutants. The color change of the solution and TEM result confirmed that Ag＋ was easily reduced and deposited on the surface of Tit2 under photo-illumination, and dissolved again into solution in the presence of ozone. This simple cycle of enrichment and distribution of Ag^＋ can greatly benefit the design of advanced oxidation processes, in which the sequences of ozone and photo-illumination can be varied according to the needs for catalyst recycling and the different properties of pollutants.     

Comparative study on the removal technologies of 2-methylisoborneol (MIB) in drinking water

Removal of 2-methylisoborneol （MIB） in drinking water by ozone, powdered activated carbon （PAC）, potassium permanganate and potassium ferrate was investigated. The adsorption kinetics of MIB by both wood-based and coat-based PACs show that main removal of MIB occurs within contact time of 1 h. Compared with the wood-based PAC, the coat-based PAC evidently improved the removal efficiency of MIB. The removal percentage of trace MIB at any given time for a particular carbon dosage was irrelative to the initial concentration of MIB. A series of experiments were performed to determine the effect of pH on the ozonation of MIB. The results show that pH has a significant effect on the ozonation of MIB. It is conclusive that potassium permanganate and potassium ferrate are ineffective in removing the MIB in drinking water.     

Degradation of benzophenone in aqueous solution by Mn-Fe-K modified ceramic honeycomb-catalyzed ozonation

Comparative studies of ozonation alone, ceramic honeycomb-catalyzed and Mn-Fe-K modified ceramic honeycomb catalyzed ozonation processes have been undertaken with benzophenone as the model organic pollutant. The experimental results showed that the presence of Mn-Fe-K modified ceramic honeycombs significantly increased the removal rate of benzophenone and TOC compared with that achieved by ozonation alone or ceramic honeycomb-catalyzed ozonation. The electron paramagnetic resonance （EPR） experiments verified that higher benzophenone removal rate was attribute to more hydroxyl radicals generated in the Mn-Fe-K modified ceramic honeycomb-catalyzed ozonation. Under the conditions of this experiment, the degradation rate of all the three ozonation processes are increasing with the amount of catalyst, temperature and value of pH increased in the solution. We also investigated the effects of different process of ozone addition, the optimum conditions for preparing catalyst and influence of the Mn-Fe-K modified ceramic honeycomb after multiple-repeated use.     

Glucose production from hydrolysis of cellulose over a novel silica catalyst under hydrothermal conditions

A novel silica catalyst was synthesized by evaporation-induced self-assembly (EISA) method and tested for the catalytic selective hydrolysis of cellulose to glucose. This silica catalyst exhibited a higher catalytic activity than other oxides prepared by the same method, such as ZrO₂, TiO₂, and Al₂O₃. Using silica as a catalyst, cellulose was selectively hydrolyzed into glucose with a glucose yield as high as 50% under hydrothermal conditions without hydrogen gas. The silica catalyst was characterized by Brunauer-Emmett-Teller (BET), X-ray diffraction (XRD) and transmission electron microscopy (TEM). The results of temperature-programmed desorption of ammonia (NH₃-TPD) and textural properties indicated that the synergistic effect between strong acidity and a suitable pore diameter of the silica catalyst may be responsible for its high activity. In addition, the catalyst was recyclable and showed excellent stability during the recycle catalytic runs.     

Toluene removal characteristics by a superimposed wire-plate dielectric barrier discharge plasma reactor

A superimposed wire-plate dielectric barrier discharge reactor was used to remove toluene in this study. The effects of oxygen content, gas flow rate, gas initial concentration and with/without catalyst on toluene decomposition were investigated. It was found that an optimal toluene removal was achieved when the oxygen content was about 5%. Under this condition, the highest toluene removal efficiency of 80.8% was achieved when the gas concentration was 80 mg/m^3. The toluene removal efficiency decreased with the increase of the gas flow rate and the initial concentration of toluene. In addition, the ozone concentration decreased with the increase of the initial concentration of toluene. It suggested that combining DBD （dielectric barrier discharge） with Co3O4/Al2O3/foam nickel catalyst in-situ could improve the toluene removal efficiency and suppress ozone formation. Products analysis showed that the main products were CO and CO2 when oxygen was more than 5%.     

Biological removal of antiandrogenic activity in gray wastewater and coking wastewater by membrane reactor process

A recombinant human androgen receptor yeast assay was applied to investigate the occurrence of antiandrogens as well as the mechanism for their removal during gray wastewater and coking wastewater treatment. The membrane reactor (MBR) system for gray wastewater treatment could remove 88.0% of antiandrogenic activity exerted by weakly polar extracts and 97.3% of that by moderately strong polar extracts, but only 32.5% of that contributed by strong polar extracts. Biodegradation by microorganisms in the MBR contributed to 95.9% of the total removal. After the treatment, the concentration of antiandrogenic activity in the effluent was still 1.05 μg flutamide equivalence (FEQ)/L, 36.2% of which was due to strong polar extracts. In the anaerobic reactor, anoxic reactor, and membrane reactor system for coking wastewater treatment, the antiandrogenic activity of raw coking wastewater was 78.6 mg FEQ/L, and the effluent of the treatment system had only 0.34 mg FEQ/L. The antiandrogenic activity mainly existed in the medium strong polar and strong polar extracts. Biodegradation by microorganisms contributed to at least 89.2% of the total antiandrogenic activity removal in the system. Biodegradation was the main removal mechanism of antiandrogenic activity in both the wastewater treatment systems.     

Pulsed corona discharge for improving treatability of coking wastewater

Coking wastewater(CW) contains toxic and macromolecular substances that inhibit biological treatment. The refractory compounds remaining in biologically treated coking wastewater(BTCW) provide chemical oxygen demand(COD) and color levels that make it unacceptable for reuse or disposal. Gas-phase pulsed corona discharge(PCD) utilizing mostly hydroxyl radicals and ozone as oxidants was applied to both raw coking wastewater(RCW) and BTCW wastewater as a supplemental treatment. The energy efficiency of COD,phenol, thiocyanate and cyanide degradation by PCD was the subject of the research. The cost-effective removal of intermediate oxidation products with addition of lime was also studied. The energy efficiency of oxidation was inversely proportional to the pulse repetition frequency: lower frequency allows more effective utilization of ozone at longer treatment times. Oxidative treatment of RCW showed the removal of phenol and thiocyanate at 800 pulses per second from 611 to 227 mg/L and from 348 to 86 mg/L, respectively, at 42 k Wh/m~3 delivered energy, with substantial improvement in the BOD5/COD ratio(from 0.14 to 0.43).The COD and color of BTCW were removed by 30% and 93%, respectively, at 20 k Wh/m~3,showing energy efficiency for the PCD treatment exceeding that of conventional ozonation by a factor of 3–4. Application of lime appeared to be an effective supplement to the PCD treatment of RCW, degrading COD by about 28% at an energy input of 28 k Wh/m3 and the lime dose of 3.0 kg/m~3. The improvement of RCW treatability is attributed to the degradation of toxic substances and fragmentation of macromolecular compounds.     

Cerium-modified amorphous manganese oxides for efficient catalytic removal of ozone

Manganese-based catalysts were widely developed for catalytic removal of ozone, and the low stability and water inactivation are major challenges. To improve removal performance of ozone, three methods were applied to modify amorphous manganese oxides, including acidification, calcination and Ce modification. The physiochemical properties of prepared samples were characterized, and the catalytic activity for ozone removal was evaluated. All modification methods can promote the removal of ozone b...     

Biological sulfate removal from acrylic fiber manufacturing wastewater using a two-stage UASB reactor

A two-stage UASB reactor was employed to remove sulfate from acrylic fiber manufacturing wastewater. Mesophilic operation (35±0.5℃) was performed with hydraulic retention time (HRT) varied between 28 and 40 hr. Mixed liquor suspended solids (MLSS) in the reactor was maintained about 8000 mg/L. The results indicated that sulfate removal was enhanced with increasing the ratio of COD/SO₄^2-. At low COD/SO₄^2-, the growth of the sulfate-reducing bacteria (SRB) was carbon-limited. The optimal sulfate removal efficiencies were 75% when the HRT was no less than 38 hr. Sulfidogenesis mainly happened in the sulfate-reducing stage, while methanogenesis in the methane-producing stage. Microbes in sulfate-reducing stage performed granulation better than that in methane-producing stage. Higher extracellular polymeric substances (EPS) content in sulfate-reducing stage helped to adhere and connect the flocculent sludge particles together. SRB accounted for about 31% both in sulfate-reducing stage and methane-producing stage at COD/SO₄^2- ratio of 0.5, while it dropped dramatically from 34% in sulfate-reducing stage to 10% in methane-producing stage corresponding to the COD/SO₄^2- ratio of 4.7. SRB and MPA were predominant in sulfate-reducing stage and methane-producing stage respectively.     

Degradation behavior of 17αup-ethinylestradiol by ozonation in the synthetic secondary effluent

Endocrine disrupting chemicals (EDCs) in the secondary effluent discharged from wastewater treatment plants (WWTPs) are of great concern in the process of water reuse. Ozonation has been reported as a powerful oxidation technology to eliminate micropollutants in water treatment. Due to the complexity of the wastewater matrix, orthogonal experiments and single factor experiments were conducted to study the influence of operational parameters on the degradation of 17αup-ethinylestradiol (EE2) in the synthetic secondary effluent. The results of the orthogonal experiments indicated that the initial ozone and natural organic matter (NOM) concentration significantly affected EE2 degradation efficiency, which was further validated by the single factor confirmation experiments. EE2 was shown to be effectively degraded by ozonation in the conditions of low pH (6), NOM (10 mg/L), carbonate (50 mg/L), but high suspended solid (20 mg/L) and initial ozone concentration (9 mg/L). The study firstly revealed that the lower pH resulted in higher degradation of EE2 in the synthetic secondary effluent, which differed from EDCs ozonation behavior in pure water. EE2 degradation by ozone molecule instead of hydroxyl radical was proposed to play a key role in the degradation of EDCs by ozonation in the secondary effluent. The ratio between O₃ and TOC was identified as an appropriate index to assess the degradation of EE2 by ozonation in the synthetic secondary effluent.     

Anthraquinone acted as a catalyst for the removal of triphenylmethane dye containing tertiary amino group: Characteristics and mechanism

Herein, we found that anthraquinone (AQ) acted as a catalyst for the rapid and effective removal of triphenylmethane dye containing tertiary amino group (TDAG). Results showed that AQ had an enhanced catalytic reactivity towards the removal of TDAG compared to hydro-quinone, which was further proved and explained using density functional theory (DFT) calculations. AQs could achieve a TDAG removal efficiency and rate of approximately 100% and 0.3583 min⁻¹, respectively, within 20 min. Quenching experiments and electron paramagnetic resonance (EPR) tests indicated that the superoxide radical (O₂^•−) generated through the catalytic reduction of an oxygen molecule (O₂) by AQ contributed to the effective removal of the TDAG. In addition, it was found that the electrophilic attack of the O₂^•− radical on the TDAG was the driving force for the dye degradation process. Decreasing the pH led to protonation of the substituted group of AG, which resulted in formation of an electron deficient center in the TDAG molecule (TDAG-EDC⁺) through delocalization of the π electron. Therefore, the possibility of the electrophilic attack for the dye by the negative O₂^•- radical was significantly enhanced. This study revealed that the H⁺ and the O₂^•− generated by the catalytic reduction of O₂ have synergistic effects that led to a significant increase in the dye removal rate and efficiency, which were higher than those obtained through persulfate oxidation.     

Cytogenetic studies of chromium (III) oxide nanoparticles on Allium cepa root tip cells

The current study evaluates the cytogenetic effects of chromium (III) oxide nanoparticles on the root cells of Allium cepa. The root tip cells of A. cepa were treated with the aqueous dispersions of Cr₂O₃ nanoparticles (NPs) at five different concentrations (0.01, 0.1, 1, 10, and 100 μg/mL) for 4 hr. The colloidal stability of the nanoparticle suspensions during the exposure period were ascertained by particle size analyses. After 4 hr exposure to Cr₂O₃ NPs, a significant decrease in mitotic index (MI) from 35.56% (Control) to 35.26% (0.01 μg/mL), 34.64% (0.1 μg/mL), 32.73% (1 μg/mL), 29.6% (10 μg/mL) and 20.92% (100 μg/mL) was noted. The optical, fluorescence and confocal laser scanning microscopic analyses demonstrated specific chromosomal aberrations such as—chromosome stickiness, chromosome breaks, laggard chromosome, clumped chromosome, multipolar phases, nuclear notch, and nuclear bud at different exposure concentrations. The concentration-dependent internalization/bio-uptake of Cr₂O₃ NPs may have contributed to the enhanced production of anti oxidant enzyme, superoxide dismutase to counteract the oxidative stress, which in turn resulted in observed chromosomal aberrations and cytogenetic effects. These results suggest that A. cepa root tip assay can be successfully applied for evaluating environmental risk of Cr₂O₃ NPs over a wide range of concentrations.     

Catalytic performance of Fe3O4-CoO/Al2O3 catalyst in ozonation of 2-(2,4-dichlorophenoxy)propionic acid, nitrobenzene and oxalic acid in water

Fe3O4-CoO/Al2O3 catalyst was prepared by incipient wetness impregnation using Fe(NO3) 3·9H2O and Co(NO3) 2·6H2O as the precursors,and its catalytic performance was investigated in ozonation of 2-(2,4-dichlorophenoxy) propionic acid(2,4-DP) ,nitrobenzene and oxalic acid.The experimental results indicated that Fe3O4-CoO/Al2O3 catalyst enabled an interesting improvement of ozonation eciency during the degradation of each organic pollutant,and the Fe3O4-CoO/Al2O3 catalytic ozonation system followed a radical-type mechanism.The kinetics of ozonation alone and Fe3O4-CoO/Al2O3 catalytic ozonation of three organic pollutants in aqueous solution were discussed under the mere consideration of direct ozone reaction and OH radical reaction to well investigate its performance.In the catalytic ozonation of 2,4-DP,the apparent reaction rate constants(k) were determined to be 1.456×10-2 min-1 for ozonation alone and 4.740×10-2 min-1 for O3/Fe3O4-CoO/Al2O3.And O3/Fe3O4-CoO/Al2O3 had a larger Rct(6.614×10-9) calculated by the relative method than O3 did(1.800×10-9) ,showing O3/Fe3O4-CoO/Al2O3 generated more hydroxyl radical.Similar results were also obtained in the catalytic ozonation of nitrobenzene and oxalic acid.The above results demonstrated that the catalytic performance of Fe3O4-CoO/Al2O3 in ozonation of studied organic substance was universal to a certain degree.