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.     

Quantification of the interactions between Ca,Hg and extracellular polymeric substances (EPS) of sludge

The interactions between metals (Ca²⁺ and Hg²⁺) and extracellular polymeric substances (EPS) extracted from the aerobic and anaerobic sludge in wastewater treatment reactors were investigated using a combination of zeta potential measurement and 3-dimensional excitation–emission matrix (EEM) fluorescence spectroscopy with parallel factor (PARAFAC) analysis. Results show that Ca²⁺ had no substantial effects on the EEM fluorescence spectra of the EPS, but their zeta potentials increased with the increasing Ca²⁺ dosage. However, Hg²⁺ had a significant effect on the EEM fluorescence spectra of the EPS, while their zeta potentials seemed not to be affected by the dose of Hg²⁺. The interactions between Hg²⁺ and EPS were elucidated using the fluorescence quenching with PARAFAC analysis, while the interactions between Ca²⁺ and EPS were evaluated by the zeta potential technique. The binding constants for Hg²⁺ and EPS were two orders of magnitude higher than those for Ca²⁺ and EPS, suggesting that the binding mechanisms between Ca²⁺ and EPS were different from those between Hg²⁺ and EPS. The results might be useful for understanding the roles of EPS in bacterial self-protection against heavy metals and the aggregate formation mechanisms through ionic bridging interactions.     

二级出水微滤过程中对醋酸纤维素酯膜的有机污染特征

低压膜过滤技术(包括微滤和超滤)在再生水生产领域正引起越来越广泛的关注。然而如何解决低压膜过滤过程中的膜有机污染问题始终是膜技术所面临的技术挑战。本研究采用醋酸纤维素酯微孔滤膜对二级出水溶解性有机物(EfOM)及其不同亲疏水性组分、蛋白模拟溶液、腐殖酸(HA)等进行恒流过滤实验。对不同有机物污染后的膜表面使用全反射傅立叶红外光谱(ATR-FTIR)和X射线电子能谱(XPS)进行表征。结果表明,相对于蛋白质和EfOM等,HA所造成的膜污染最少。ATR-FTIR的结果同时显示,以官能团而言,更多的氨化物(1535cm-1)、脂肪族物质(2860～2970cm-1)和氢氧根(3400cm-1)存在于膜表面。TMP/V数据比较结果表明,在EfOM各亲疏水性组分、蛋白质和HA的对比中,EfOM中的疏水碱性物质(HPO-B)对膜污染的贡献最大,而HA的膜污染贡献最小。UVA和荧光激发-发射光谱(FEEM)结果表明,HPO-B和蛋白质对醋酸纤维素酯膜的污染贡献较大。综合不同分析手段可以对不同有机物造成膜污染的潜能大小得出如下排序:HPO-B>蛋白质>HPO-A、HPI>HA。     

Ozonation as an advanced oxidant in treatment of bamboo industry wastewater

The present study employed ozonation process to treat the bamboo industry wastewater (BIWW). The impact of ozone dosage and initial organic concentration on color, COD and TOC removal rates were studied along with characterization of the major organics in raw and treated wastewater. The results suggested the ozone dosage of 3.15 g h⁻¹ (concentration 52.5 mg L⁻¹) was suitable for the treatment. After 25 min ozonation of 1 L raw wastewater, the color, COD and TOC removal efficiencies were 95%, 56% and 40%, respectively, with an influent COD concentration of 835 mg L⁻¹. The ratio of kg O₃ kg⁻¹ COD at 3.15 g h⁻¹ was 2.8 (<3), revealing that ozonation was a cost effective process for tertiary treatment of BIWW. Longer oxidization time was required to achieve similar results for raw wastewater with higher COD concentration. The chromatogram from gel permeation chromatography revealed that ozonation resulted in the breakdown of high molecular weight compounds into lower molecular weight components but could not completely mineralize the organic matter. The majority of these compounds were identified in both raw and ozonated samples via GC-MS analysis. In addition to ester derivatives as the main intermediates of ozonation, 1-chloroctadecane, methyl stearate, benzophenone and α-cyperone were identified as the by-products of ozonation.     

Ecotoxicologial evaluation of wastewater ozonation based on detritus-detritivore interactions

Advanced oxidation technologies such as ozonation have been proposed to improve removal efficiency of micropollutants during wastewater treatment. In a meta-analysis of peer-reviewed literature, we found no ecotoxicological effects of wastewater ozonation on invertebrates (n = 82), but significant adverse effects on bacteria (n = 24) and fish (n = 5). As information on functional endpoints or trophic interactions is lacking, we applied a bioassay relating to leaf litter decomposition to fill this gap. Leaf discs exposed to ozone-treated wastewater with a high (1.04 mg O₃ (mg DOC)⁻¹, n = 49) ozone concentration were significantly preferred by an aquatic detritivore, Gammarus fossarum, over discs conditioned in wastewater not treated with ozone. This effect might have been mediated by reduced bacterial and elevated fungal biomass, and appears to be the first demonstration of wastewater ozonation impacts on invertebrates and an associated ecosystem process. In accordance with the food-choice trials, chemical analyses revealed significantly decreased concentrations of organic micropollutants in wastewater treated with ozone at high concentrations. Thus, food-choice trials as applied here hold promise to assess environmental effects of advanced oxidation technologies in wastewater treatment and appear to be a valuable complement to the ecotoxicological toolbox in general.     

V2O5-TiO2-AlF3/Al2O3催化臭氧化2,4-滴丙酸的氧化效能

为了提高有机物的臭氧化降解效率,工作中利用浸渍法制备了一种新型的三组分催化剂(记为V2O5-TiO2-AlF3/Al2O3)。催化臭氧化降解2,4-滴丙酸的实验结果表明,该催化剂能有效提高臭氧化的效率,体系可能遵循羟基自由基的作用机理。利用相对法计算结果表明,与单独臭氧化相比,V2O5-TiO2-AlF3/Al2O3催化臭氧化体系具有更大的Rct值。重复实验结果表明,该催化剂具有相对较好的稳定性。以上研究结果对推广催化臭氧化技术在实际废水处理中的应用具有重要的实际意义。     

活性炭-微波辐照处理丁腈胶乳生产废水的研究

以活性炭-微波辐照工艺处理丁腈胶乳生产废水,考察了催化剂的种类及用量、废水初始浓度、废水初始pH值、微波辐照时间和微波功率等对废水COD去除率的影响.结果表明,采用3 g粉末活性炭处理100 mL COD浓度为3500 mg/L左右的丁腈胶乳废水,在微波辐照功率为200 W,辐照时间4 min的条件下,废水COD去除率最高可达96.6%.动力学研究表明,在最佳操作条件下的反应表观过程近似符合一级反应规律,动力学方程为In(C0/C)=0.6034t 0.9247(R=0.9926),反应速率常数k=0.6034 min-1,半衰期t1/2=1.15 min.     

Characterizing the interactions between polycyclic aromatic hydrocarbons and fulvic acids in water

Polycyclic aromatic hydrocarbons (PAHs) are persistent, bioaccumulative, and toxic chemicals and are listed as priority pollutants by the US EPA. Although they are sparsely soluble in water, their solubility can be increased by binding to dissolved organic matter in natural waters, which will further increase their environmental risk as toxic pollutants. In this study, the interaction between PAHs, exemplified by fluorene and anthracene, and fulvic acid (FA) was studied using fluorescence quenching titration method with fluorescence emission spectra, respectively. The association of FA with the mixture of fluorene and anthracene was also evaluated by excitation–emission matrix (EEM) fluorescence spectrometry combined with parallel factor (PARAFAC) analysis. Results demonstrate that EEM fluorescence spectrometry with PARAFAC analysis was sensitive and reliable to determine the binding properties of PAHs with FA in a mixed aqueous solution. The conditional stability constants and binding capacities show that both PAHs bind to FA tightly.     

Adsorption of chlorpyrifos,penconazole and metalaxyl from aqueous solution by modified clays

Sorption of three pesticides (chlorpyrifos, metalaxyl and penconazole) has been measured on a commercial clay montmorillonite and on the same mineral modified with either of two cationic-surfactant micelles. Both micelle–clay complexes, commercial names Cloisite 20A and Cloisite 30B, showed a good capacity to sorb all three pesticides from water, whereas their sorption on the natural montmorillonite was not described by an isotherm. Modelling sorption on both micelle–clay complexes showed that the Freundlich sorption constant (K _F) was higher for chlorpyrifos on Cloisite 20A (K _F = 7.76) than on Cloisite 30B (K _F = 5.91), whereas the sorption of metalaxyl was stronger on Cloisite 30B (K _F = 1.07) than on Cloisite 20A (K _F = 0.57). Moreover the micelle–clay complex Cloisite 20A also showed a good affinity for penconazole, the maximum quantity adsorbed (q _m) of 6.33 mg g^?1 being 45% more than that on Cloisite 30B. Single-batch adsorption of each pesticide onto both micelle–clay complexes was studied using the Freundlich isotherm for chlorpyrifos and metalaxyl and the Langmuir isotherm for penconazole. The Cloisite 20A micelle–clay complex was predicted to require 23% less adsorbent to treat certain volumes of wastewater containing 30 mg L^?1 chlorpyrifos, 43% more to treat metalaxyl similarly and 57% less to treat penconazole compared with Cloisite 30B.     

SMX degradation by ozonation and UV radiation: a kinetic study

The rate constants of sulfamethoxazole (SMX) degradation by ozonation and UV₂₅₄ radiation were investigated under various parameters including influent ozone gas concentration, initial SMX concentration, UV light intensity, ionic strength, water quality in terms of varying anions (bicarbonate, sulfate and nitrate), humic acid (HA) and pH. The results indicated that the removal of SMX by ozonation and UV₂₅₄ radiation fitted well to a pseudo first-order kinetic model and the rate constants were in the range of (0.9-9.8) × 10⁻³ and (1.7-18.9) × 10⁻³ s⁻¹, respectively. The second-order rate constants of SMX with ozone (k_O3), under varying operational parameters, were also determined and varied in the range of (0.60-3.38) ± 0.13 × 10⁵ M⁻¹ s⁻¹. In addition, SMX degradation through UV pretreatment followed by ozonation in the presence of HA was proved to be an effective method which can remove SMX with a low ozone dose. The results suggested that ozonation of SMX was more affected by concentration of influent ozone gas, alkalinity, and HA, while incident UV light intensity, pH, and HA were the dominant factors influencing UV degradation of SMX.     

Catalytic ozonation of 2,4-Dichlorophenoxyacetic acid using alumina in the presence of a radical scavenger

Using a laboratory-scale mixed reactor, the performance of alumina in degrading 2,4-Dichlorophenoxyacetic acid with ozone in the presence of tert-butyl alcohol radical scavenger was studied. The operating variables investigated were the dose of alumina catalyst and solution pH. Results showed that using ozone and alumina leads to a significant increase in 2,4-D removal in comparison to non-catalytic ozonation and adsorption processes. The observed reaction rate constants (k_obs ) for 2,4-D during ozonation were found to increase linearly with increasing catalyst dose. At pH 5, the k_obs value increased from 19.3 to 26 M^?1 s^?1 and 67 M^?1 s^?1 when varying the alumina dose from 1 to 2 and 4 g L^?1, respectively. As pH was increased, higher reaction rates were observed for both non-catalytic ozonation and catalytic ozonation processes. Thus, at pH 3 and using a catalyst dose of 8 g L^?1, the k_obs values for non-catalytic ozonation and catalytic ozonation processes were 3.4 and 58.9 M^?1 s^?1, respectively, whereas at pH 5 reaction rate constants of 6.5 and 128.5 M^?1 s^?1 were observed, respectively. Analysis of total organic carbon suggested that catalytic ozonation with alumina achieved a considerable level of mineralization of 2,4-D. Adsorption of 2,4-D on alumina was found to play an important role in the catalytic ozonation process.     

Fate of bulk and trace organics during a simulated aquifer recharge and recovery (ARR)-ozone hybrid process

The attenuation of bulk organic matter and trace organic contaminants (TOrCs) was evaluated for various aquifer recharge and recovery (ARR)-ozone (O₃) hybrid treatment process combinations using soil-batch reactor and bench-scale ozonation experiments as a proof of concept prior to pilot and/or field studies. In water reclamation and especially potable reuse, refractory bulk organic matter and TOrCs are of potential health concern in recycled waters. In this study, the role of biotransformation of bulk organic matter and TOrCs was investigated considering different simulated treatment combinations, including soil passage (ARR) alone, ARR after ozonation (O₃-ARR), and ARR prior to ozonation (ARR-O₃). During oxic (aerobic) ARR simulations, soluble microbial-like substances (e.g., higher molecular weight polysaccharides and proteins) were easily removed while (lower molecular weight) humic substances and aromatic organic matter were not efficiently removed. During ARR-ozone treatment simulations, removals of bulk organic matter and TOrCs were rapid and effective compared to ARR alone. A higher reduction of effluent-derived organic matter, including aromatic organic matter and humic substances, was observed in the ARR-O₃ hybrid followed by the O₃-ARR hybrid. An enhanced attenuation of recalcitrant TOrCs was observed while increasing the ozone dose slightly (O₃: DOC = 1). TOrC removal efficiency also increased during the post-ozone treatment combination (i.e., ARR-O₃). In addition, the carcinogenic wastewater disinfection byproduct N-nitrosodimethylamine (NDMA) was eliminated below the method reporting limit (<5 ng L⁻¹) both during ARR treatment alone and the ARR-ozone hybrid.     

Degradation of atrazine by catalytic ozonation in the presence of iron scraps: performance,transformation pathway,and acute toxicity

Degradation of atrazine by catalytic ozonation in the presence of iron scraps (ZVI/O₃) was carried out. The key operational parameters (i.e., initial pH, ZVI dosage, and ozone dosage) were optimized by the batch experiments, respectively. This ZVI/O₃ system exhibited much higher degradation efficiency of atrazine than the single ozonation, ZVI, and traditional ZVI/O₂ systems. The result shows that the pseudo-first-order constant (0.0927?min^?1) and TOC removal rate (86.6%) obtained by the ZVI/O₃ process were much higher than those of the three control experiments. In addition, X-ray diffraction (XRD) analysis indicates that slight of γ-FeOOH and Fe₂O₃ were formed on the surface of iron scrap after ZVI/O₃ treatment. These corrosion products exhibit high catalytic ability for ozone decomposition, which could generate more hydroxyl radical (HO^?) to degrade atrazine. Six transformation intermediates were identified by liquid chromatography-mass spectrometry (LC-MS) analysis in ZVI/O₃ system, and the degradation pathway of atrazine was proposed. Toxicity tests based on the inhibition of the luminescence emitted by Photobacterium phosphoreum and Vibrio fischeri indicate the detoxification of atrazine by ZVI/O₃ system. Finally, reused experiments indicate the approving recyclability of iron scraps. Consequently, the ZVI/O₃ system could be as an effective and promising technology for pesticide wastewater treatment.     

Formation and emissions of carbonyls during and following gas-phase ozonation of indoor materials

Ozone concentrations that are several orders of magnitude greater than typical urban ambient concentrations are necessary for gas-phase ozonation of buildings, either for deodorization or for disinfection of biological agents. However, there is currently no published literature on the interaction of building materials and ozone under such extreme conditions. It would be useful to understand, for example in the case of building re-occupation planning, what types and amounts of reaction products may form and persist in a building after ozonation. In this study, 24 materials were exposed to ozone at concentrations of 1000 ppm in the inlet stream of experimental chambers. Fifteen target carbonyls were selected and measured as building ozonation by-products (BOBPs). During the 36 h that include the 16 h ozonation and 20 h persistence phase, the total BOBP mass released from flooring and wall coverings ranged from 1 to 20 mg m⁻², with most of the carbonyls being of lower molecular weight (C₁–C₄). In contrast, total BOBP mass released from wood-based products ranged from 20 to 100 mg m⁻², with a greater fraction of the BOBPs being heavier carbonyls (C₅–C₉). The total BOBP mass released during an ozonation event is a function of both the total surface area of the material and the BOBP emission rate per unit area of material. Ceiling tile, carpet, office partition, and gypsum wallboard with flat latex paint often have large surface areas in commercial buildings and these same materials exhibited relatively high BOBP releases. The greatest overall BOBP mass releases were observed for three materials that building occupants might have significant contact with: paper, office partition, and medium density fiberboard, e.g., often used in office furniture. These materials also exhibited extended BOBP persistence following ozonation; some BOBPs (e.g., nonanal) persist for months or more at emission rates large enough to result in indoor concentrations that exceed their odor threshold.     

Stability of 6:2 fluorotelomer sulfonate in advanced oxidation processes: degradation kinetics and pathway

Perfluorooctane sulfonate (PFOS), a widely used mist suppressant in hard chrome electroplating industry, has been listed in the Stockholm Convention for global ban. 6:2 Fluorotelomer sulfonate (6:2 FTS) acid and salts have been adopted as alternative products in the market, but no data about their abiotic degradation has been reported. In the present study, the degradability of 6:2 FTS potassium salt (6:2 FTS-K) was evaluated under various advanced oxidation processes, including ultraviolet (UV) irradiation, UV with hydrogen peroxide (H₂O₂), alkaline ozonation (O₃, pH = 11), peroxone (O₃/H₂O₂), and Fenton reagent oxidation (Fe²⁺/H₂O₂). UV/H₂O₂ was found to be the most effective approach, where the degradation of 6:2 FTS-K followed the pseudo-first-order kinetics. The intermediates were mainly shorter chain perfluoroalkyl carboxylic acid (C₇ to C₂), while sulfate (SO₄ ^2?) and fluoride (F^?) were found to be the final products. The high yields of SO₄ ^2? and F^? indicate that 6:2 FTS-K can be nearly completely desulfonated and defluorinated under UV/H₂O₂ condition. The degradation should firstly begin with the substitution of hydrogen atom by hydroxyl radicals, followed by desulfonation, carboxylation, and sequential “flake off” of CF₂ unit. Compared with PFOS which is inert in most advanced oxidation processes, 6:2 FTS-K is more degradable as the alternative.     

Comparison of antibiotic tolerance,lipids and respiration in the tomato pathogens Fusarium oxysporum lycopersici and F. oxysporum radicis lycopersici

Abstract

The respiration and lipid contents and the tolerance to mycostatin, chloramphenicol and cycloheximide were compared in the two morphologically similar forms of the tomato pathogens: Fusarium oxysporum lycopersici (FOL) and the virulent form F. oxysporum radicis lycopersici (FORL). The differential tolerances to mycostatin were the most significant feature of the comparisons. The MIC for FORL was 24 μg/mL for the mycelium and 38 μg/mL for the spores. For FOL, the MIC was 8 ug/mL for both. This pattern of higher mycostatin tolerance by FORL obtained at 19°C and 27°C. There were differences between FOL and FORL in their fatty acid composition. FORL contained about three times as much C_18:0 and over twice as much C_18:1 as FOL. Conversely FOL contains over two times as much C_16:1 as FORL. There appeared to be no significant differences between the respiration rates of the two pathogens. The data is discussed relative to their significance as the biochemical basis for examining pathogenicity and virulence between the two organisms.     

Fluorescence spectroscopic characterization of DOM fractions isolated from a filtered river water after ozonation and catalytic ozonation

Fluorescence spectra were applied to investigate the structural changes of four dominant dissolved natural organic matter (DOM) fractions of a filtered river water before and after ozonation and catalytic ozonation. The ozonation and catalytic ozonation with synthetic goethite (FeOOH) and cerium dioxide (CeO(2)) were carried out under normal conditions, i.e. pH 7, reaction time of 10 min, and ozone/DOC ratio of about 1. The fluorescence spectra were recorded at both excitation-emission matrix (EEM) and synchronous scanning modes. EEM results reveal that ozonation of these DOM fractions causes a significant decrease of the aromaticity of humic-like structures and an increase of electron withdrawing groups, e.g., carboxylic groups. The catalysts can further improve the destruction of the humic-like structures in catalytic ozonation. Synchronous spectra reveal that ozonation of hydrophobic acid and hydrophilic acid (HIA) yields a significant amount of by-products with low aromaticity and low molecular weight. Catalytic ozonation enhances substantially the formation of these by-products from HIA and improves the destruction of highly polycyclic aromatic structures for all examined DOM fractions.     

Application of pier waste sludge for catalytic activation of proxy-monosulfate and phenol elimination from a petrochemical wastewater

This investigation aimed to remove phenol from real wastewater (taken from a petrochemical company) by activating peroxy-monosulfate (PMS) using catalysts extracted from pier waste sludge. The physical and chemical properties of the catalyst were evaluated by FE-SEM/EDS, XRD, FTIR, and TGA/DTG tests. The functional groups of O–H, C–H, CO₃^2?, C–H, C–O, N–H, and C–N were identified on the catalyst surface. Also, the crystallinity of the catalyst before and after reaction with petrochemical wastewater was 103.4 nm and 55.8 nm, respectively. Operational parameters of pH (3–9), catalyst dose (0–100 mg/L), phenol concentration (50–250 mg/L), and PMS concentration (0–250 mg/L) were tested to remove phenol. The highest phenol removal rate (94%) was obtained at pH=3, catalyst dose of 80 mg/L, phenol concentration of 50 mg/L, PMS concentration of 150 mg/L, and contact time of 150 min. Phenol decomposition in petrochemical wastewater followed the first-order kinetics (k> 0.008 min^?1, R²> 0.94). Changes in pH factor were very effective on phenol removal efficiency, and maximum efficiency (≈83%) was achieved in pH 3. The catalyst stability test was performed for up to five cycles, and phenol removal in the fifth cycle was reduced to 42%. Also, the energy consumption in this study was 77.69 kW h/m³. According to the results, the pier waste sludge catalyst/PMS system is a critical process for eliminating phenol from petrochemical wastewater.

     

臭氧氧化6-APA制药厂生化处理出水的特性及动力学简

通过现场实验研究了6-APA制药厂生化处理出水的臭氧氧化特性及其动力学规律。结果表明,当臭氧浓度为27.5 mg/L,气水接触时间为80 min时,COD、UV₂₅₄、NH₃-N和色度的去除率分别可达72.95%、73.28%、72%和96.25%,达到《发酵类制药废水工业水污染物排放标准》（GB 21903-2008）排放控制要求。拟合结果表明,在0~10、10~30和30~90 min时段内,臭氧氧化过程遵循拟一级反应,但反应速率逐渐降低。当气水接触时间为30 min时,废水可生化性可由0.1提高至0.35,采用臭氧/生物处理的联合工艺也有望使出水达到相同的排放控制要求。     

Uptake of Cd(II) and Pb(II) by microalgae in presence of colloidal organic matter from wastewater treatment plant effluents

The present study addresses the key issue of linking the chemical speciation to the uptake of priority pollutants Cd(II) and Pb(II) in the wastewater treatment plant effluents, with emphasis on the role of the colloidal organic matter (EfOM). Binding of Cd(II) and Pb(II) by EfOM was examined by an ion exchange technique and flow field-flow fractionation coupled to inductively coupled plasma mass spectrometry in parallel to bioassays with green microalga Chlorella kesslerii in ultrafiltrate (<1 kDa) and colloidal isolates (1 kDa to 0.45 μm). The uptake of Cd by C. kesslerii was consistent with the speciation analysis and measured free metal ion concentrations, while Pb uptake was much greater than that expected from the speciation measurement. Better understanding of the differences in the effects of the EfOM on Cd(II) and Pb(II) uptake required to take into account the size dependence of metal binding by EfOM.