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.     

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.     

Tracking the reactivity of ozonation towards effluent organic matters from WWTP using two-dimensional correlation spectra

The characteristics of effluent organic matter (EfOM) from a wastewater treatment plant (WWTP) during ozonation were investigated using excitation and emission matrix (EEM) spectra, Fourier transform infrared spectroscopy (FT-IR) and high-performance size exclusion chromatography (HPSEC) at different ozone dosages. The selectivity of ozonation towards different constituents and functional groups was analysed using two-dimensional correlation spectra (2D-COS) probed by FT-IR, synchronous fluorescence spectra and HPSEC. The results indicated that ozonation can destroy aromatic structures of EfOM and change its molecular weight distribution (MWD). According to 2D-COS analysis, microbial humic-like substances were preferentially removed, and then the protein-like fractions. Terrestrial humic-like components exhibited inactivity towards ozonation compared with the above two fractions. Protein-like substances with small molecular weight were preferentially reacted during ozonation based on 2D-COS probed by HPSEC. In addition, the selectivity of ozone towards different functional groups of EfOM exhibited the following sequence: phenolic and alcoholic CO groups?>?aromatic structures containing CC double bonds?>?aliphatic CH. X-ray photoelectron spectroscopy (XPS) further elucidated the preferential reaction of aromatic structures in EfOM during ozonation.     

臭氧氧化去除吐氏酸溶液COD的动力学研究

研究了臭氧氧化条件下，吐氏酸水溶液在鼓光反应器内的COD去除动力学，考察了pH值、温度、自由基抑制剂及进气口臭氧浓度等因素对反应的影响。结果表明：在pH=8左右时，COD去除效果较好；在17－30℃范围内，温度对反应影响不大；自由基抑制剂明显影响氧化效果，说明氧化过程是分子臭氧和其分解产生的自由基共同参与的结果；氧化降解效果与进气中臭氧浓度与正相关；臭氧氧化明显改善吐氏酸的生物降解性能，BOD5／COD可达0．18。研究表明：吐氏酸臭氧化的COD去除过程符合一级反应动力学。     

Investigation and assessment of micropollutants and associated biological effects in wastewater treatment processes

Currently, the wastewater treatment plants (WWTPs) attempt to achieve the shifting from general pollution parameters control to reduction of organic micropollutants discharge. However, they have not been able to satisfy the increasing ecological safety needs. In this study, the removal of micropollutants was investigated, and the ecological safety was assessed for a local WWTP. Although the total concentration of 31 micropollutants detected was reduced by 83% using the traditional biological treatment processes, the results did not reflect chemicals that had poor removal efficiencies and low concentrations. Of the five categories of micropollutants, herbicides, insecticides, and bactericides were difficult to remove, pharmaceuticals and UV filters were effectively eliminated. The specific photosynthesis inhibition effect and non-specific bioluminescence inhibition effect from wastewater were detected and evaluated using hazardous concentration where 5% of aquatic organisms are affected. The photosynthesis inhibition effect from wastewater in the WWTP was negligible, even the untreated raw wastewater. However, the bioluminescence inhibition effect from wastewater which was defined as the priority biological effect, posed potential ecological risk. To decrease non-specific biological effects, especially of macromolecular dissolved organic matter, overall pollutant reduction strategy is necessary. Meanwhile, the ozonation process was used to further decrease the bioluminescence inhibition effects from the secondary effluent; ≥ 0.34 g O₃/g DOC of ozone dose was recommended for micropollutants elimination control and ecological safety.     

Evaluation of Fenton and ozone-based advanced oxidation processes as mature landfill leachate pre-treatments

Fenton treatment (Fe²⁺/H₂O₂) and different ozone-based Advanced Oxidation Processes (AOPs) (O₃, O₃/OH⁻ and O₃/H₂O₂) were evaluated as pre-treatment of a mature landfill leachate, in order to improve the biodegradability of its recalcitrant organic matter for subsequent biological treatment. With a two-fold diluted leachate, at optimised experimental conditions (initial pH 3, H₂O₂ to Fe²⁺ molar ratio of 3, Fe²⁺ dosage of 4 mmol L⁻¹, and reaction time of 40 min) Fenton treatment removed about 46% of chemical oxygen demand (COD) and increased the five-day biochemical oxygen demand (BOD₅) to COD ratio (BOD₅/COD) from 0.01 to 0.15. The highest removal efficiency and biodegradability was achieved by ozone at higher pH values, solely or combined with H₂O₂. These results confirm the enhanced production of hydroxyl radical under such conditions. After the application for 60 min of ozone at 5.6 g O₃ h⁻¹, initial pH 7, and 400 mg L⁻¹ of hydrogen peroxide, COD removal efficiency was 72% and BOD₅/COD increased from 0.01 to 0.24. An estimation of the operating costs of the AOPs processes investigated revealed that Fe²⁺/H₂O₂ was the most economical system (8.2 € m⁻³ g⁻¹ of COD removed) to treat the landfill leachate. This economic study, however, should be treated with caution since it does not consider the initial investment, prices at plant scale, maintenance and labour costs.     

稠油废水处理工艺研究

介绍了稠油废水的来源与性质,提出3种处理技术,即"水解酸化-接触氧化-臭氧催化氧化",出水CODCr为48.6 mg/L,去除率达到86.55%,处理成本为6.03元/m3;"活性焦预吸附-厌氧-固定化微生物BAF-活性焦后吸附",出水CODCr为40.2 mg/L,去除率达到88.97%,处理成本为5.45元/m3;"强化絮凝-活性污泥MBR",出水CODCr为36.8 mg/L,去除率达到82.64%,处理成本为5.76元/m3。第2种工艺处理效率与处理成本略优。     

Comparison of different combined treatment processes to address the source water with high concentration of natural organic matter during snowmelt period

The source water in one forest region of the Northeast China had very high natural organic matter (NOM) concentration and heavy color during snowmelt period. The efficiency of five combined treatment processes was compared to address the high concentration of NOM and the mechanisms were also analyzed. Conventional treatment can hardly remove dissolved organic carbon (DOC) in the source water. KMnO₄ pre-oxidization could improve the DOC removal to 22.0%. Post activated carbon adsorption improved the DOC removal of conventional treatment to 28.8%. The non-sufficient NOM removal could be attributed to the dominance of large molecular weight organic matters in raw water, which cannot be adsorbed by the micropore upon activated carbon. O₃ + activated carbon treatment are another available technology for eliminating the color and UV₂₅₄ in water. However, its performance of DOC removal was only 36.4%, which could not satisfy the requirement for organicmatter. The limited ozone dosage is not sufficient to mineralize the high concentration of NOM. Magnetic ion-exchange resin combined with conventional treatment could remove 96.2% of color, 96.0% of UV₂₅₄ and 87.1% of DOC, enabling effluents to meet the drinking water quality standard. The high removal efficiency could be explained by the negative charge on the surface of NOM which benefits the static adsorption of NOM on the anion exchange resin. The results indicated that magnetic ion-exchange resin combined with conventional treatment is the best available technology to remove high concentration of NOM.