强化高锰酸钾氧化去除水中有机污染物的技术综述

探讨投加催化剂或与其他技术联合提高高锰酸钾氧化效能的方法,综述了过渡金属、腐殖酸、络合剂、ABTS、二氧化锰和超声等强化高锰酸钾氧化效能的技术,分析每种技术的优势和缺陷,认为后续研究应注重铁基或者其他过渡金属非均相催化剂的开发,既降低催化剂的成本,也实现催化剂的回收利用。     

Removal of persistent polar pollutants through improved treatment of wastewater effluents (P-THREE).

The EU-project P-THREE started with the establishment of analytical methods for persistent polar pollutants (P3) and quality assurance, followed by screening of P3 in influents and effluents of known wastewater (WW) treatment plants (TP), receiving waters and tap water produced thereof in several European countries. A final selection of analytes for further studies has been performed. Model MBR reactors have been constructed and an optimisation on synthetic wastewater spiked with P3 (linear alkylbenzene sulfonates (LAS), naphthalene sulfonates) has been performed. An initial dynamic modelling of treatment processes has also started. Advanced oxidation process (AOP) treatment has been done in groundwater with isoproturon and nonylphenol ethoxylates (NPEO). The analysis of individual P3 and potential degradation products was also performed. An integrated systeme analysis of the WW treatment processes has also been initiated.     

Priority organic pollutants in the urban water cycle (Toulouse, France)

Application of the European Water Framework Directive requires Member States to have better understanding of the quality of surface waters in order to improve knowledge of priority pollutants. Xenobiotics in urban receiving waters are an emerging concern. This study proposes a screening campaign of nine molecular species of xenobiotics in a separated sewer system. Five sites were investigated over one year in Toulouse (France) using quantitative monitoring. For each sample, polycyclic aromatic hydrocarbons, polychlorinated biphenyls, nonylphenols, diethelhexylphthalate, linear alkylbenzene sulphonates, methyl tert-butylether, total hydrocarbons, estradiol and ethinylestradiol were analysed. Ground, rain and roof collected water concentrations are similar to treated wastewater levels. Run-off water was the most polluted of the five types investigated, discharged into the aquatic environment. The wastewater treatment plant reduced xenobiotic concentrations by 66% before discharge into the environment. Regarding environmental quality standards, observed concentrations in waters were in compliance with standards. The results show that xenobiotic concentrations are variable over time and space in all urban water compartments.     

Simultaneous removal of nitrate and phosphate using cross-flow micellar-enhanced ultrafiltration (MEUF).

The feasibility of cross-flow micellar-enhanced ultrafiltration (MEUF) was investigated to remove nitrate and phosphate simultaneously. At the above critical micelle concentration (CMC), a cationic surfactant added in wastewater forms micelles, which have positive charge on their surface. Anionic contaminants such as nitrate and phosphate can be bound on the micelles by electrostatic interaction, and the micelle-pollutants complex is removed effectively by ultrafiltration. In this study, a cross-flow MEUF system was designed and investigated the feasibility of MEUF for field application. A cationic surfactant, cetylpyridinium chloride (CPC), was used, and the synthetic wastewater was treated by the polyacrylonitrile membranes with molecular weight cut-off (MWCO) of 30,000 Da and 10,000 Da. With the molar ratio of CPC to total pollutants of > 3, > 86% of nitrate and > 91% of phosphate were removed, respectively, and > 97% of CPC was also rejected. The flux was maintained 20-30% of the flux of distilled water. Therefore, it is feasible to remove nitrate and phosphate simultaneously using the cross-flow MEUF system.     

Fenton高级氧化技术去除水中有机污染物2-MIB的影响因素研究

针对目前比较关注的致嗅物质污染问题,选用Fenton高级氧化技术研究了其对水中致嗅物质2-甲基异莰醇（2-MIB）的去除,探讨了Fenton反应对水中致嗅物质的去除效能及H2O2/Fenton摩尔比、Fe2＋浓度、反应时间和溶液pH值各因素对氧化反应的影响。提出了Fenton氧化反应去除2-MIB的最佳反应条件。实验结果表明：Fenton高级氧化能有效去除水中的2-MIB。在H2O2/Fenton摩尔比为3.0、Fe2＋浓度10 mg/L、反应时间10 min和溶液pH值为3.0时,去除效率达到97.9%。Fenton氧化反应的操作条件（浓度、pH值等）比较容易实现,因此Fenton氧化技术在实际污染处理中有很大的应用前景。     

美国ICR数据库有机物去除分析及对我国的借鉴作用

我国《生活饮用水卫生标准》(GB 5749-2006)对有机物指标的要求,给我国给水处理的运行带来了新的挑战。依照美国第一阶段消毒剂与消毒副产物标准中对有机物指标(TOC)的去除率要求,用美国ICR(Information Collection Rule)数据库分析了常规工艺及增加生物活性炭(BAC)的深度处理工艺对水中有机物的去除。结果表明,常规工艺对有机物的去除效果随原水的TOC增大而变好,随碱度增大而变差;对于水中有机物的去除,常规工艺的去除率中位数为32%,BAC的深度处理工艺中位数为40%。混凝和BAC工艺弥补了各自的不足,尤其是当原水碱度较高TOC较低,在混凝工艺后增加BAC工艺可以更好地去除水中的有机物。     

厌氧氨氧化脱氮技术的研究进展

介绍厌氧氨氧化技术机理以及与此相关的微生物生理生态学特征,综述该脱氧技术研究现状及具体应用以及不同反应器应用厌氧氨氧化技术的脱氧情况,比较不同脱氧工艺,探讨了厌氧氨氧化技术未来的研究重点。     

Monitoring metal and persistent organic contaminant trends through time using quagga mussels (Dreissena bugensis) collected from the Niagara River

Historically, the Niagara River received the discharge of persistent bioaccumulative and toxic chemicals from municipal and industrial outfalls and hazardous waste landfills. American and Canadian governments have coordinated investigations of chemicals entering the river and initiated remedial measures and monitoring programs with a goal to reduce loadings of toxic chemicals to the river. This study, a component of the Ontario Ministry of Environment Mussel Biomonitoring Program, compares contaminant concentrations in quagga mussels (Dreissena bugensis) collected from nine locations in the Niagara River in 1995 and 2003 to assess anticipated changes in tissue concentrations of contaminants in response to ongoing remedial efforts by government agencies and local industries. The concentrations of persistent organic compounds (e.g., PCBs, hexachlorobenzene, hexachlorobutadiene, octachlorostyrene) in quagga mussels in 2003 were lower than concentrations measured in 1995, consistent with a decrease in reported mean annual concentrations of these compounds in water. Significant differences in total PCB concentrations in mussels between stations (F = 4.6; P < 0.001) suggested sources of PCBs on the American side of the upper Niagara River. In general, highest concentrations of persistent organic compounds were found downstream of the Occidental Chemical Corporation Buffalo Avenue facility suggesting local sources of these contaminants notwithstanding remedial efforts. In contrast, metal concentrations in quagga mussels in 2003 were similar to concentrations found in 1995 and to values reported in the literature for mussels collected from industrialized areas in the Great Lakes. Overall, our results suggest that remedial efforts to improve water quality in the Niagara River have been successful.     

Differentiation of wastewater effluent organic matter (EfOM) from natural organic matter (NOM) using multiple analytical techniques.

Using three analytical techniques of size exclusion chromatography (SEC), fluorescence excitation-emission matrix (EEM), and dissolved organic nitrogen (DON) measurement, differentiating characteristics of effluent organic matter (EfOM) from natural organic matter (NOM) have been investigated. SEC reveals a wide range of molecular weight (MW) for EfOM and high amount of high MW polysaccharides, and low MW organic acids compared to NOM. Clear protein-like peaks using fluorescence EEM were a major feature of EfOM distinguishing it from NOM. Fluorescence index (FI), an indicator to distinguish autochthonous origin from allochthonous origin, differentiated EfOM from NOM by exhibiting higher values, indicating a microbial origin. In EfOM samples, DON present in higher amounts than NOM.     

Persistent organic pollutants,metals, and the bacterial community composition associated with microplastics in Muskegon Lake (MI)

Three different types of microplastics (MPs): low density polyethylene; polypropylene; and polyester, were incubated for one and three months at two sites (Channel and Lake) in Muskegon Lake (MI). After retrieval, MPs were analyzed for polyaromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs), organochlorine pesticides (OCs), select metals, and genomic characterization of the attached microbial biofilm. Polyaromatic hydrocarbons accumulated at similar levels on all microplastic types, but were ~one order of magnitude lower than sediment concentrations and ~three orders of magnitude lower than the Probable Effect Concentration (PEC): the concentration in sediment above which adverse biological effects are likely to occur. In contrast, PCB levels were 4–6× greater on polyethylene than on polypropylene or polyester, although all plastic-associated PCB concentrations were at least one order of magnitude less than the PEC. Organochlorine pesticide concentrations were very low (<1 ppb) on all microplastics and at all sites. Metal concentrations also were well below their respective PEC levels. The most abundant bacterial groups as part of the plastisphere were Burkholderiales, Rhodocyclaceae, Comamonadaceae, and Pseudomonadaceae. Polyester microplastics contained a higher number of bacterial families and the relative abundance of those families were more evenly distributed compared to the other plastic types. Overall, our results indicate that persistent organic pollutants are capable of accumulating on MPs but the concentrations generally were low; feeding trials are needed to determine if these environmentally realistic concentrations of pollutants attached to microplastics result in impacts to aquatic biota.     

Biofilm control in water by advanced oxidation process (AOP) pre-treatment: effect of natural organic matter (NOM)

The main goal of this study was to examine the influence of natural organic matter (NOM) on the efficiency of H?O?/UV advanced oxidation process (AOP) as a preventive treatment for biofilm control. Pseudomonas aeruginosa PAO1 biofilm-forming bacteria were suspended in water and exposed to various AOP conditions with different NOM concentrations, and compared to natural waters. H?O?/UV prevented biofilm formation: (a) up to 24 h post treatment - when residual H?O? was neutralized; (b) completely (days) - when residual H?O? was maintained. At high NOM concentrations (i.e. 25 mg/L NOM or 12.5 mg/L DOC) an additive biofilm control effect was observed for the combined H?O?/UV system compared to UV irradiation alone, after short biofilm incubation times (<24 h). This effect was H?O? concentration dependent and can be explained by the high organic content of these water samples, whereby an increase in NOM could enhance (?)OH production and promote the formation of additional reactive oxygen species. In addition, maintaining an appropriate ratio of bacterial surviving conc.: residual H?O? conc. post-treatment could prevent bacterial regrowth and biofilm formation.     

Degradation of bisphenol A using electrochemical assistant Fe(II)-activated peroxydisulfate process

Degradation of bisphenol A(BPA) in aqueous solution using sulfate radicals was investigated using the Fe(II)-activated peroxydisulfate(PDS) process, electrochemical process, electrochemical process with 2.5 mmol/L Na2S2O8 without Fe(II), and electrochemical assistant Fe(II)-activated PDS process. It was found that the electrochemical assistant Fe(II)-activated PDS process performed best in the degradation of BPA.The variables considered to influence the degradation efficiency of BPA were the initial concentration of Fe2 t, the initial concentration of Na2S2O8, and the current density. More than 97% of the BPA removals were achieved within 120 min under the optimum operational condition.The degradation of BPA was accompanied by the formation of phenol, hydroquinone, and small-molecule compounds such as succinic acid. The electron transfer was the principal step in the oxidation of BPA.     

SUVA as control parameter for the effective ozonation of organic pollutants in secondary effluent.

Recent research projects have shown a good suitability of the ozonation process to transform trace concentrations of most pharmaceuticals in wastewater treatment plant (WWTP) effluents. The concentrations of carbamazepine and 17 alpha-ethinylestradiol, for instance, were reduced below their detection limits by use of ozone dosages resulting in a specific ozone consumption of 0.5 mg O3/mg DOC0. At the same time a good disinfection performance was achieved. The given hygienic requirements of the EU bathing water directive (e.g. 2,000 N/100 mL faecal coliforms) are fulfilled without the formation of bromate (<10 microg/L). As technical control parameter of the ozonation process usually the residual ozone in the liquid phase or in the off-gas are used. However, at very low specific ozone consumptions, ozone reacts instantaneously with dissolved compounds and cannot be detected. Hence, alternative parameters should be used for effective operation control. The present paper evaluates the relation between UVA decrease and the removal of different compounds (endocrine disrupting compounds, pharmaceuticals, iodinated X-ray contrast media), microbial parameters and bromate formation. The results can be used as a guideline for the control of the oxidation performance at large scale ozonation units.     

Assessing the removal potential of soil-aquifer treatment systems for bulk organic matter.

The fate of effluent organic matter (EfOM) during groundwater recharge was investigated by studying the removal behavior of four bulk organic carbon fractions isolated from a secondary effluent: Hydrophilic organic matter (HPI), hydrophobic acids (HPO-A), colloidal organic matter (OM), and soluble microbial products (SMPs). Short-term removal of the bulk organic fractions during soil infiltration was simulated in biologically active soil columns. Results revealed that the four organic fractions showed a significantly different behavior with respect to biological removal. HPI and colloidal OM were prone to biological removal during initial soil infiltration (0-30 cm) and supported soil microbial biomass growth in the infiltrative surface. Additionally, colloidal OM was partly removed by physical adsorption or filtration. HPO-A and SMPs reacted recalcitrant towards biological degradation as indicated by low soil biomass activity responses. Adsorbability assessment of the biologically refractory portions of the fractions onto powered activated carbon (PAC) indicated that physical removal is not likely to play a significantly role in further diminishing recalcitrant HPO-A, HPI and SMPs during longer travel times in the subsurface.     

Removal of endocrine disrupting chemicals (EDCs) using low pressure reverse osmosis membrane (LPROM).

Endocrine disrupting chemicals (EDCs) are the focus of current environmental issues, as they can cause adverse health effects to animals and human, subsequent to endocrine function. The objective of this study was to remove a specific compound of EDCs (i.e. pentachlorophenol, C(6)OCL(5)Na, molecular weight of 288 g/mol) using low pressure reverse osmosis membrane (LPROM). A cross flow module of LPROM was used to observe the effects of operating parameters, i.e. pH, operating pressure and temperature. The design of the experiment was based on MINITAB(TM) software, and the analysis of results was conducted by factorial analysis. It was found that the rejection of pentachlorophenol was higher than 80% at a recovery rate of 60 to 70%. The rejection was subjected to increase with the increase of pH. The flux was observed to be increased with the increase of operating pressure and temperature. This study also investigated the interaction effects between operating parameters involved.     

基于响应面法的Fe~0/S_2O_8~(2-)体系氧化垃圾渗滤液去除UV_(254)研究

为提高Fe~0/S_2O_8~(2-)体系氧化垃圾渗滤液去除有机物的效果,试验采用响应面法优化反应条件,借助响应面法的中心组合试验设计了以紫外吸光度UV_(254)的去除率为响应值的二次回归模型,分析零价铁(Fe~0)投加量、初始pH值和S_2O_8~(2-)与12COD_0的质量比3个因素的交互作用,确定最优反应条件。结果表明在Fe~0投加量为31.3mmol/L、初始pH值为4.4,ω(S_2O_8~(2-)/12COD_0)为1.14条件下,UV_(254)的去除率达到最大值72%。     

Removal of pharmaceuticals using combination of UV/H(2)O(2)/O(3) advanced oxidation process

Water and wastewater effluents contain a vast range of pharmaceutical chemicals. The present study aims to determine the potential of the advanced oxidation technology UV/H(2)O(2)/O(3) and its sub-processes (i.e. UV, UV/H(2)O(2), UV/O(3), O(3) and H(2)O(2)/O(3)) for the degradation of the antibiotics ciprofloxacin (CIP) and trimethoprim (TMP), and the antineoplastic drug cyclophosphamide (CPD) from water. Creating AOP conditions improved in most cases the degradation rate of the target compounds (compared with O(3) and UV alone). H(2)O(2) concentration was found to be an important parameter in the UV/H(2)O(2) and H(2)O(2)/O(3) sub-processes, acting as (?)OH initiator as well as (?)OH scavenger. Out of the examined processes, O(3) had the highest degradation rate for TMP and H(2)O(2)/O(3) showed highest degradation rate for CIP and CPD. The electrical energy consumption for both CIP and CPD, as calculated using the E(EO) parameter, was in the following order: UV > UV/O(3) > UV/H(2)O(2)/O(3) > O(3) > H(2)O(2)/O(3). Whereas for TMP O(3) was shown to be the most electrical energy efficient. Twelve degradation byproducts were identified following direct UV photolysis of CIP.     

Development of adsorbent for the simultaneous removal of organic and inorganic contaminants from aqueous solution

In this study, a modified adsorbent, alginate complex beads, was prepared and applied to the removal of mixed contaminants from wastewater. The alginate complex beads were generated by the immobilization of powdered activated carbon and synthetic zeolites onto alginate gel beads, which were then dried at 110 °C for 20 h until the diameter had been reduced to 1 mm. This dry technique increased the hardness of the adsorbent to assure its durability and application. The adsorption onto the alginate complex beads of organic and inorganic compounds, as target contaminants, was investigated by performing both equilibrium and kinetic batch experiments. From the adsorption isotherms, according to the Langmuir equation, the alginate complex bead was capable of effectively removing benzene, toluene, zinc and cadmium. From kinetic batch experiments, the removal efficiencies of benzene, toluene, zinc and cadmium were found to be 66.5, 92.4, 74.1 and 76.7%, respectively, for initial solution concentrations of 100 mg L(-1). The results indicated that the adsorbent developed in this study has the potential to be a promising material for the removal of mixed pollutants from industrial wastewater or contaminated groundwater.     

Efficient removal of Cr(VI) by polydopamine-modified lignin from aqueous solution: Batch and XAFS studies

Lignocellulose has the potential to become a bio-based adsorbent due to its biodegradability and renewability. In this study, a novel polydopamine-functionalized-lignin (lignin@PDA), prepared via self-polymerization of dopamine (PDA) on lignin, was used as a bio-based adsorbent for rapid scavenging of hexavalent chromium (Cr(VI)). The morphology, functional groups, crystalline structure, and chemical composition of lignin@PDA were characterized with a scanning electron microscope–energy dispersive spectrometer, Fourier transform infrared spectroscopy, X-ray diffraction, and X-ray photoelectron spectroscopy. The Cr(VI) adsorption process of lignin@PDA was studied using batch experiments as a function of pH, ionic strength, adsorbent dose, and contact time at room temperature. The adsorption rate of lignin@PDA was five times greater than that of the unmodified lignin, with a maximum adsorption capacity of 102.6 mg/g in an acidic medium. The adsorption of Cr(VI) on lignin@PDA fit the pseudo-second-order equation and the Freundlich model, indicating that the adsorption process was mainly dominated by chemisorption and surface complexation. The thermodynamic parameters showed that adsorption of Cr(VI) on lignin@PDA was an endothermic and spontaneous process. The X-ray absorption fine structure results showed that sorption and reduction of Cr(VI) into Cr(III) occurred simultaneously on lignin. Moreover, PDA coating not only improved the reactivity of lignin but also promoted the complete reduction of Cr(VI) by lignin. According to these results, polydopamine-functionalized-lignin is a promising bio-based adsorbent for immobilization of Cr(VI) from wastewater.

     

Effect of support and second metal in catalytic in-situ generation of hydrogen peroxide by Pd-supported catalysts: application in the removal of organic pollutants by means of the Fenton process

A catalytic system for the generation of H2O2 from formic acid and oxygen at ambient conditions has been developed. Pd-supported catalysts (Pd/C, Pd/TiO2 and Pd/Al2O3) have been tested, showing that for bulk purposes Pd/Al2O3 is more favourable while for in-situ applications Pd/TiO2 seems to be preferable. However, when these catalysts were tested in the in-situ H2O2 generation for the oxidation of phenol by means of the Fenton process (in the presence of ferrous ion), Pd/TiO2 did not demonstrate the expected results, whereas Pd/Al2O3 showed to be an efficient catalyst. Therefore, Pd/Al2O3 is offered as a good catalyst for Fenton's reactions with in-situ generated H2O2. In order to optimize the operating cost of the process, different initial concentrations of formic acid have been tested with Pd/Al2O3, and it has been seen that lowering the initial amount of formic acid favours the efficiency of the process. The effect of the addition of a second metallic (Pt, Au, Fe, Cu) active phase was studied. Concerning H2O2 generation, best results were obtained with a Pd-Au catalyst for bulk production (long time) while for in-situ application Pd-Fe showed interesting results. The Pd-Fe catalyst also performed similarly to the semi-heterogeneous Fenton system involving Pd/Al2O3 and ferrous ion in the degradation of phenol. Therefore, Pd-Fe catalyst offered an interesting prospect for making a full heterogeneous catalyst for Fenton reaction involving in-situ generation of H2O2.