Effect of NOM characteristics on brominated organics formation by ozonation

In this study, organic fractions, namely, humic acid, fulvic acid, hydrophobic base and neutral, and hydrophilic acid, base, and -neutral, were extracted from source water. First, the characteristics of the organic fractions, such as carboxylic acidity, phenolic acidity, ultraviolet absorbance, and aromatic content, were analyzed. Further, a systematic study was carried out to the by-products obtained when organic fractions, to which various amounts of bromide had been added, were oxidized with ozone. Samples after ozonation were analyzed for several brominated organics. The results indicate that the characteristics of the aquatic organic matter, including carboxylic/phenolic acidity, aromatic/aliphatic content, and ultraviolet absorbance, appear to affect the formation of halogenated organics. In general, hydrophobic organics having higher phenolic acidity, aromatic content, and ultraviolet absorbance have higher ozone consumption and produce higher concentrations of brominated organics than hydrophilic organics. It was also found that humic acid demonstrated the highest bromoform (CHBr(3)), dibromoacetic acid (DBAA), and 2,4-dibromophenol (2,4-DBP) formation, whereas hydrophilic neutral produced less CHBr(3) and 2,4-DBP than the rest of the organic fractions but produced the highest amount of dibromoacetone (DBAC) and dibromoacetonitrile (DBAN).     

改性活性炭催化臭氧深度处理化工废水的研究

采用非均相催化臭氧氧化工艺深度处理化工废水二级生化出水,探索负载不同活性组分的活性炭催化剂及该工艺处理化工废水的影响因素。结果表明:当进水COD为85~110 mg/L,臭氧投加量为60 mg/L,催化剂投加量为200 mg/L Cr时,臭氧氧化、ACCA-1、ACCA-2和ACCA-3催化臭氧氧化对出水COD的平均去除率分别为22.46%、32.7%、40.5%和35.7%,3种催化剂均可强化臭氧氧化效果。活性炭催化剂能提高臭氧利用率,叔丁醇对ACCA-2抑制效果最明显。     

Changes in biomass activity and characteristics of activated sludge exposed to low ozone dose

In this paper, the response mechanism of activated sludge exposed to low-dose ozone at less than 20 mg O₃ g⁻¹ total suspended solids (TSS) was studied by analyzing the changes in sludge activity and the evolution of C, N, P and metals from sludge following ozonation. The intracellular ATP concentration was not affected at less than 5 mg O₃ g⁻¹ TSS and thereafter decreased rapidly to around 60% when the ozone dose increased to 20 mg O₃ g⁻¹ TSS. Similarly, the efficiency of sludge solubilization initially changed a little and then increased rapidly to around 30% at an ozone dose of 20 mg O₃ g⁻¹ TSS. However, the activities of superoxide dismutase and protease decreased immediately upon exposure to ozone. These findings indicate that ozone firstly destroys the floc, leading to the disruption of the compact aggregates, which does not affect cells viability but induces a decrease in enzyme activities. Ozone then attacks the bacterial cells of the sludge, causing a decrease in cells viability. During ozonation, the content of carbon, nitrogen and phosphorus in the sludge matrix decreased, while the content of these elements in the micro-solids and supernatant gradually increased. Most of the released metals from the sludge matrix were found in the micro-solids.     

Activated carbon enhanced ozonation of oxalate attributed to HO. oxidation in bulk solution and surface oxidation： Effect of activated carbon dosage and pH

Ozonation of oxalate in aqueous phase was performed with a commercial activated carbon（AC）in this work. The effect of AC dosage and solution pH on the contribution of hydroxyl radicals（HOU） in bulk solution and oxidation on the AC surface to the removal of oxalate was studied. We found that the removal of oxalate was reduced by tert-butyl alcohol（tBA） with low dosages of AC,while it was hardly affected by tBA when the AC dosage was greater than 0.3 g/L. tBA also inhibited ozone decomposition when the AC dosage was no more than 0.05 g/L, but it did not work when the AC dosage was no less than 0.1 g/L. These observations indicate that HOUin bulk solution and oxidation on the AC surface both contribute to the removal of oxalate. HOU oxidation in bulk solution is significant when the dosage of AC is low, whereas surface oxidation is dominant when the dosage of AC is high. The oxalate removal decreased with increasing pH of the solution with an AC dosage of 0.5 g/L. The degradation of oxalate occurs mainly through surface oxidation in acid and neutral solution, but through HOUoxidation in basic bulk solution. A mechanism involving both HOUoxidation in bulk solution and surface oxidation was proposed for AC enhanced ozonation of oxalate.     

木糖生产废水的脱色研究

实验表明用臭氧化法进行木糖生产废水的脱色处理效果颇佳。在30分钟内就能达到90％的去除率，反应速度受pH、温度等因素影响较小。实验同时表明，臭氧氧化法对COD的去除效果不理想，需要和其它方法结合处理。     

Kinetics of simazine advanced oxidation in water

Abstract

Comparison of the effects and kinetics of UV photolysis and four advanced oxidation systems (ozone, ozone/hydrogen peroxide, ozone/UV radiation and UV radiation/hydrogen peroxide) for the removal of simazine from water has been investigated. At the conditions applied, the order of reactivity was ozone < ozone/hydrogen peroxide < UV radiation < ozone/UV radiation and UV radiation/hydrogen peroxide. Rate constants of the reactions between ozone and simazine and hydroxyl radical and simazine were found to be 8.7 M^‐1s^‐1 and 2.1x10⁹ M^‐1s^‐1, respectively. Also, a quantum yield of 0.06 mol.photon^‐1 was found for simazine at 254 nm UV radiation. The high value of the quantum yield corroborated the importance of the direct photolysis process. Percentage contributions of direct reaction with ozone, reaction with hydroxyl radicals and direct photolysis were also quantified.     

Spectroscopic study of the degradation of antibiotics and the generation of representative EfOM oxidation products in ozonated wastewater

This study examined effects of ozonation on thirteen fluoroquinolone, macrolide and lincosamide antibiotics present in municipal wastewater. Transformations of effluent organic matter (EfOM) caused by ozonation were characterized using absorbance/fluorescence spectroscopy and high performance size exclusion chromatography (HPSEC). Concentrations of aldehydes and carboxylic acids generated via the oxidation of EfOM were also determined. The absorbance and fluorescence of ozonated wastewater decreased with increasing ozone dose or treatment time. HPSEC data showed that these phenomena corresponded to the oxidation of all EfOM fractions, with some preference towards the degradation of the EfOM molecules with high apparent molecular weight. The removal of antibiotics and production of aldehydes and carboxylic acids were strongly correlated with the changes in both EfOM absorbance and fluorescence. Applications of a model describing the concurrent degradation of trace level contaminants and relative changes of EfOM emission allowed achieving a good fitting between the experimental and modeled ΔC/C₀ vs. ΔA/A₀ and ΔC/C₀ vs. ΔF/F₀ data.     

Detailed characterization of polar compounds of residual oil in contaminated soil revealed by Fourier transform ion cyclotron resonance mass spectrometry

Effects of remediation technologies on polar compounds of crude oil in contaminated soils have not been well understood when compared to hydrocarbons. In this study, ultrahigh resolution Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) was used to characterize the changes in NSO polar compounds of crude oil and residual oil after long-term natural attenuation, biostimulation and subsequent ozonation following biostimulation of contaminated soils. N₁ and O₁ species, which were abundant in the crude oil, were selectively biodegraded, and species with higher double bond equivalent values and smaller carbon numbers appeared to be more resistant to microbial alteration. O₂-O₆ species were enriched by biodegradation and contained a large number of compounds with a high degree of unsaturation. Ozone could react with a variety of polar compounds in residual oil after biodegradation and showed high reactivity with polar species containing aromatic or multi-aliphatic rings, including the residual N₁ and O₁ species, naphthenic acids and unsaturated O₃-O₆ compounds. Fatty acids and O₃-O₈ species dominated by saturated alkyl compounds were resistant to ozonation or the primarily incomplete ozonation products. Principal component analysis of identified peaks in the FT-ICR MS spectra provided a comprehensive overview of the complex samples at the molecular level and the results were consistent with the detailed analysis. Taken together, these results showed the high complexity of polar compounds in residual oils after biodegradation or ozonation in contaminated soil and would contribute to a better understanding of bioremediation and ozonation processes.     

Micropollutant removal during biological wastewater treatment and a subsequent ozonation step

The design criteria for wastewater treatment plants (WWTP) and the sludge retention time, respectively, have a significant impact on micropollutant removal. The upgrade of an Austrian municipal WWTP to nitrogen removal (best available technology, BAT) resulted in increased elimination of most of the analyzed micropollutants. Substances, such as bisphenol-A, 17α-ethinylestradiol and the antibiotics erythromycin and roxithromycin were only removed after the upgrade of the WWTP. Nevertheless, the BAT was not sufficient to completely eliminate these compounds. Thus, a pilot scale ozonation plant was installed for additional treatment of the effluent. The application of 0.6 g O₃ g DOC⁻¹ increased the removal of most of the micropollutants, especially for compounds that were not degraded in the previous biological process, as for example carbamazepine and diclofenac. These results indicated that the ozonation of WWTP effluent is a promising technology to further decrease emissions of micropollutants from the treatment process.