Selective removal of diclofenac from contaminated water using molecularly imprinted polymer microspheres

A molecularly imprinted polymer (MIP) was synthesized by precipitation polymerization using diclofenac (DFC) as a template. Binding characteristics of the MIP were evaluated using equilibrium binding experiments. Compared to the non-imprinted polymer (NIP), the MIP showed an outstanding affinity towards DFC in an aqueous solution with a binding site capacity (Q_max) of 324.8 mg/g and a dissociation constant (K_d) of 3.99 mg/L. The feasibility of removing DFC from natural water by the MIP was demonstrated by using river water spiked with DFC. Effects of pH and humic acid on the selectivity and adsorption capacity of MIP were evaluated in detail. MIP had better selectivity and higher adsorption efficiency for DFC as compared to that of powdered activated carbon (PAC). In addition, MIP reusability was demonstrated for at least 12 repeated cycles without significant loss in performance, which is a definite advantage over single-use activated carbon.     

沉淀--吸附处理双氯灭痛高浓度有机废水的工艺研究

介绍了用沉淀－吸附法处理双氯灭痛高浓度有机废水的工艺。先用废盐酸将废水的ｐＨ调节到４,沉淀、过滤,然后将滤液依次经过炉渣、生炭串级吸附,处理后的废水ＣＯＤＣｒ、ｐＨ、ＳＳ均达到ＧＢ８９７８－８８污水综合排放制药行业二级标准。     

Effects of the pharmaceuticals gemfibrozil and diclofenac on biomarker expression in the zebra mussel (Dreissena polymorpha) and their comparison with standardised toxicity tests

Pharmaceuticals, including the lipid regulator gemfibrozil and the non-steroidal anti-inflammatory drug diclofenac have been identified in waste water treatment plant effluents and receiving waters throughout the western world. The acute and chronic toxicity of these compounds was assessed for three freshwater species (Daphnia magna,Pseudokirchneriella subcapitata, Lemna minor) using standardised toxicity tests with toxicity found in the non-environmentally relevant mid mg L⁻¹ concentration range. For the acute endpoints (IC₅₀ and EC₅₀) gemfibrozil showed higher toxicity ranging from 29 to 59 mg L⁻¹ (diclofenac 47-67 mg L⁻¹), while diclofenac was more toxic for the chronic D. magna 21 d endpoints ranging from 10 to 56 mg L⁻¹ (gemfibrozil 32-100 mg L⁻¹). These results were compared with the expression of several biomarkers in the zebra mussel (Dreissena polymorpha) 24 and 96 h after exposure by injection to concentrations of 21 and 21,000 μg L⁻¹ corresponding to nominal concentrations of 1 and 1000 μg L⁻¹. Exposure to gemfibrozil and diclofenac at both concentrations significantly increased the level of lipid peroxidation, a biomarker of damage. At the elevated nominal concentration of 1000 μg L⁻¹ the biomarkers of defence glutathione transferase and metallothionein were significantly elevated for gemfibrozil and diclofenac respectively, as was DNA damage after 96 h exposure to gemfibrozil. No evidence of endocrine disruption was observed using the alkali-labile phosphate technique. Results from this suite of biomarkers indicate these compounds can cause significant stress at environmentally relevant concentrations acting primarily through oxidation pathways with significant destabilization of the lysosomal membrane and that biomarker expression is a more sensitive endpoint than standardised toxicity tests.     

Water technology for specific water usage

BACKGROUND: Water is the basis for life and culture. In addition to the availability of water its quality has become a major issue in industrialized areas and in developing countries as well. Water usage has to be seen as part of the hydrological cycle. As a consequence water management has to be sustainable. The aim of the contribution is to give water usage oriented quality criteria and to focus on the technical means to achieve them. MAIN FEATURES: Water is used for many purposes, ranging from drinking and irrigation to a broad variety of technical processes. Most applications need specific hygienic, chemical and/or physical properties. RESULTS: To meet these demands separation and reaction principles are applied. The reuse of water and the application of water treatment with little or no waste and by-product formation is the way to go. Membrane separation and advanced oxidation including catalytic reactions are promising methods that apply natural processes in sustainable technical performance. Thus elimination of specific water constituents (e.g. salts and metals, microorganisms) and waste water cleaning (e.g. pollutants, nutrients and organic water) can be done efficiently. OUTLOOK: Learning from nature and helping nature with appropriate technology is a convincing strategy for sustainable water management.     

Analysis of the effects diclofenac has on Japanese medaka (Oryzias latipes) using real-time PCR

The expression levels of cytochrome P450 1A, p53 and vitellogenin were investigated in three different tissues of male medaka fish after exposure to diclofenac that is one of the main concerns among pharmaceuticals frequently found in sewage treatment plant (STP) effluents. The results showed that cytochrome P450 1A, p53 and vitellogenin were highly expressed in tissue-specific gene expression patterns after exposure to 8 mg/l and 1 μg/l of diclofenac. These elevated expression levels of three biomarkers suggested that diclofenac has potential to cause cellular toxicity, p53-related genotoxicity and estrogenic effects. It is also noteworthy that diclofenac has the potential to cause these effects even at an environmentally relevant concentration of diclofenac, 1 μg/l.     

Peroxymonosulfate-Co(II) oxidation system for the removal of the non-ionic surfactant Brij 35 from aqueous solution

The non-ionic surfactant Brij 35 was effectively removed from concentrated aqueous solution by the peroxymonosulfate/Co(II) system, using oxone (2KHSO₅·KHSO₄·K₂SO₄) as a source of peroxymonosulfate. At pH = 2.3 and initial Brij 35 concentration in the range 680-2410 mg L⁻¹, 86-94% removal was achieved after 24 h, using Co(II) = 15 μM and oxone = 5.9 mM. The effectiveness of removal did not change when initial pH was in the range 2.3-8.2. After five subsequent additions of Co(II) and oxone to the solution, COD and TOC removals increased up to 64% and 33%, respectively. Radical quenching tests confirmed that sulfate radical was the dominant radical species in the system. The main identified by-products from surfactant degradation were: (a) low molecular weight organic acids; (b) aldehydes and formates with shorter ethoxy chain than Brij 35; (c) alcohol ethoxylates carrying hydroxyl groups bonded to ethoxy chain. By-products identification allowed to hypothesize the pathways of Brij 35 degradation.     

The degradation of chlorpyrifos and diazinon in aqueous solution by ultrasonic irradiation: effect of parameters and degradation pathway

In this paper, elimination of two types of organophosphorus pesticides (OPPs), chlorpyrifos and diazinon spiked in aqueous solution by ultrasonic irradiation was investigated. Results showed that chlorpyrifos and diazinon could be effectively and rapidly degraded by ultrasonic irradiation, and the degradation of both pesticides was strongly influenced by ultrasonic power, temperature and pH value. Furthermore, two and seven products for the degradation of chlorpyrifos and diazinon formed during ultrasonic irradiation have been identified by gas chromatography-mass spectrometry, respectively. The hydrolysis, oxidation, hydroxylation, dehydration and decarboxylation were deduced to contribute to the degradation reaction and the degradation pathway for each pesticide under ultrasonic irradiation was proposed. Finally, the toxicity evaluation indicated that the toxicity decreased for diazinon solution after ultrasonic irradiation, but it increased for chlorpyrifos solution. The detoxification of OPPs by ultrasonic irradiation was discriminative.     

Recent progress on application of UV excilamps for degradation of organic pollutants and microbial inactivation

Excilamps as modern mercury-free sources of narrow-band UV radiation represent an attractive alternative in environmental applications. This review focuses on recent studies on the water and surface decontamination with excilamps by means of direct photolysis and advanced oxidation processes. To date, direct photolysis and advanced oxidation processes (AOPs) such as UV/H₂O₂, UV/Fenton and UV/O₃ have been applied for degradation of organic compounds (mainly, phenols, dyes and herbicides) in model aqueous solutions. Special emphasis is placed on studies combining UV irradiation (as a pre-treatment or post-treatment step) with biological treatment. In this review, the efficiencies of direct UV, UV/H₂O₂ and UV/TiO₂ processes for inactivation of a variety of pathogenic microorganisms in water and on surfaces are discussed. The analysis of the literature shows that more works need to be done on scaling up the processes, degradation/mineralization of target pollutant(s) in real effluents and evaluation of energy requirements.     

Advanced oxidation of alkylphenol ethoxylates in aqueous systems

Alkylphenols and alkylphenol ethoxylates are ubiquitous wastewater contaminants. In this study the oxidation of nonylphenol ethoxylates (NPEO) and octylphenol ethoxylates (OPEO) by oxidant systems generating hydroxide radicals was evaluated. The reaction of each oxidant with a technical mixture of NPEO (Tergitol™) and OPEO (Triton X-100™) in ultrapure laboratory water and four aqueous environmental matrices was carried out in order to develop an understanding of reaction kinetics. The oxidation of APEOs was evaluated by hydroxyl radical generated by (1) hydrogen peroxide in the presence of ultraviolet light, (2) Fenton’s reagent, and (3) a photo-Fenton’s process. The second order kinetic rate constant for both NPEO and OPEO with hydroxyl radical was calculated to be 1.1 × 10¹⁰ M⁻¹ s⁻¹. The efficacy of the AOPs within an aqueous environmental matrix was dependent on the rate of formation of hydroxyl radical and the scavenging capacity of the matrix. A model based on the hydroxyl radical formation, scavenging capacity and the kinetic rate constant of target APEO was developed from the existing literature and applied to predict the concentration of APEOs in solution during advanced oxidation in different aqueous environmental matrices.     

Identification of a phytotoxic photo-transformation product of diclofenac using effect-directed analysis

The pharmaceutical diclofenac (DCF) is released in considerably high amounts to the aquatic environment. Photo-transformation of DCF was reported as the main degradation pathway in surface waters and was found to produce metabolites with enhanced toxicity to the green algae Scenedesmus vacuolatus. We identified and subsequently confirmed 2-[2-(chlorophenyl)amino]benzaldehyde (CPAB) as a transformation product with enhanced toxicity using effect-directed analysis. The EC₅₀ of CPAB (4.8 mg/L) was a factor of 10 lower than that for DCF (48.1 mg/L), due to the higher hydrophobicity of CPAB (log K_ow = 3.62) compared with DCF (log D_ow = 2.04) at pH 7.0.     

UV/O3降解水样中COD的动力学建模

建立动力学模型可以对UV/O3降解有机物的过程进行有效的分析和预测,帮助改进水处理工艺以提高有机物的降解效率和降低能源消耗。然而,已有的方法无法满足实际水样中未知有机物降解过程的建模需求。在化学反应机理的基础上,结合对有机物降解生成CO2浓度演化规律的分析,建立了一种可预测未知有机物降解反应的数学模型。通过改变氧化消解的条件,从理论上检验了该模型的灵敏度;同时,实验采用了含有葡萄糖、尿素和邻苯二甲酸氢钾的混合溶液作为测试水样,考察了模型的准确性,实验值与预测值的趋势一致。     

Simultaneous E. coli inactivation and NOM degradation in river water via photo-Fenton process at natural pH in solar CPC reactor. A new way for enhancing solar disinfection of natural water

Bacteria inactivation and natural organic matter oxidation in river water was simultaneously conducted via photo-Fenton reaction at “natural” pH (6.5) containing 0.6 mg L⁻¹ of Fe³⁺ and 10 mg L⁻¹ of H₂O₂. The experiments were carried out by using a solar compound parabolic collector on river water previously filtered by a slow sand filtration system and voluntarily spiked with Escherichia coli. Fifty five percent of 5.3 mg L⁻¹ of dissolved organic carbon was mineralized whereas total disinfection was observed without re-growth after 24 h in the dark.     

微波-Fenton高级氧化工艺降解水中BPA

以提高目标物的降解效果和投加药剂利用率、缩短反应时间及节约处理成本为目的,探讨4种不同光助-Fenton氧化工艺对环境内分泌干扰物双酚A（BPA）的降解效果。以BPA的去除率和反应速率作为评价指标,采用紫外分光光度计、TOC测定仪及分子荧光光度计分别对BPA的去除率、反应体系的矿化度和·OH的生成量进行研究。确定了微波-Fenton氧化工艺降解水中BPA的效果最佳,并深入研究pH值、H2O2投加量、n（H2O2）/n（Fe2+）、微波反应功率及时间对微波-Fenton氧化工艺的影响。结果表明：pH=3,n（H2O2）/n（Fe2+）为20,H2O2浓度为2 mmol·L-1,反应时间为5 min,反应功率为300 W的条件下,BPA初始浓度为100 mg·L-1时其去除率最高达99.67%,矿化度达53%;pH值在2~6范围内对BPA均有降解效果,铁泥量也有一定的减少。为微波-Fenton氧化工艺的实际应用奠定了理论基础,并且提供了技术支持。     

Elimination of selected heterocyclic aromatic emerging contaminants from water using soybean peroxidase

Environmental Science and Pollution Research - Widespread occurrence of various heterocyclic aromatic compounds is reported in concentrations from 1 to 20 μg/L in surface and groundwater as...     

Sequential photochemical-biological degradation of chlorophenols

UV/TiO₂/H₂O₂, UV/TiO₂ and UV/H₂O₂ were compared as pre-treatment processes for the detoxification of mixtures of 4-chlorophenol (4CP), 2,4-dichlorophenol (DCP), 2,4,6-trichlorophenol (TCP) and pentachlorophenol (PCP) prior to their biological treatment. When each chlorophenol was initially supplied at 50 mg l⁻¹, UV/TiO₂/H₂O₂ treatment supported the highest pollutant removal, COD removal, and dechlorination efficiencies followed by UV/TiO₂ and UV/H₂O₂. The remaining toxicity to Lipedium sativum was similar after all pre-treatments. Chlorophenol photodegradation was always well described by a first order model kinetic (r² > 0.94) and the shortest 4CP, DCP, TCP and PCP half-lives of 8.7, 7.1, 4.5 and 3.3 h, respectively, were achieved during UV/TiO₂/H₂O₂ treatment. No pollutant removal was observed in the controls conducted with H₂O₂ or TiO₂ only. Inoculation of all the photochemically pre-treated mixtures with activated sludge microflora was followed by complete removal of the remaining pollutants. Combined UV/TiO₂/H₂O₂-biological supported the highest detoxification, dechlorination (99%) and COD removal (88%) efficiencies. Similar results were achieved when each chlorophenol was supplied at 100 mg l⁻¹. COD and Cl mass balances indicated UV, UV/H₂O₂, and UV/TiO₂ treatments lead to the formation of recalcitrant photoproducts, some of which were chlorinated.     

Degradation of ethylenethiourea pesticide metabolite from water by photocatalytic processes

In this study, photocatalytic (photo-Fenton and H₂O₂/UV) and dark Fenton processes were used to remove ethylenethiourea (ETU) from water. The experiments were conducted in a photo-reactor with an 80 W mercury vapor lamp. The mineralization of ETU was determined by total organic carbon analysis, and ETU degradation was qualitatively monitored by the reduction of UV absorbance at 232 nm. A higher mineralization efficiency was obtained by using the photo-peroxidation process (UV/H₂O₂). Approximately 77% of ETU was mineralized within 120 min of the reaction using [H₂O₂]₀ = 400 mg L^?1. The photo-Fenton process mineralized 70% of the ETU with [H₂O₂]₀ = 800 mg L^?1 and [Fe²⁺] = 400 mg L^?1, and there is evidence that hydrogen peroxide was the limiting reagent in the reaction because it was rapidly consumed. Moreover, increasing the concentration of H₂O₂ from 800 mg L^?1 to 1200 mg L^?1 did not enhance the degradation of ETU. Kinetics studies revealed that the pseudo-second-order model best fit the experimental conditions. The k values for the UV/H₂O₂ and photo-Fenton processes were determined to be 6.2 × 10^?4 mg L^?1 min^?1 and 7.7 × 10^?4 mg L^?1 min^?1, respectively. The mineralization of ETU in the absence of hydrogen peroxide has led to the conclusion that ETU transformation products are susceptible to photolysis by UV light. These are promising results for further research. The processes that were investigated can be used to remove pesticide metabolites from drinking water sources and wastewater in developing countries.     

Principle and applications of microbubble and nanobubble technology for water treatment

In recent years, microbubble and nanobubble technologies have drawn great attention due to their wide applications in many fields of science and technology, such as water treatment, biomedical engineering, and nanomaterials. In this paper, we discuss the physics, methods of generation of microbubbles (MBs) and nanobubbles (NBs), while production of free radicals from MBs and NBs are reviewed with the focuses on degradation of toxic compounds, water disinfection, and cleaning/defouling of solid surfaces including membrane. Due to their ability to produce free radicals, it can be expected that the future prospects of MBs and NBs will be immense and yet more to be explored.     

炼油厂含油冷却水处理回用技术研究

开展了O3 氧化和强碱性阴离子交换组合工艺用于炼油厂含油冷却水回用处理的实验研究。结果表明 ,O3 氧化过程中的最佳pH值约为 10 .5 ,O3 氧化的除油效率为 86 .7% (紫外法测定 ) ,去除 1mg石油类约需消耗 5 .7mgO3 ,O3 氧化后产物以乙酸和丙酸等挥发性脂肪酸为主。离子交换处理后油的含量达到未检出的水平。研究结果表明 ,O3 氧化和离子交换组合处理技术能使炼油厂含油冷却水达到回用水水质标准。     

The OH-induced degradation mechanism of 4-chloro-2-methylphenoxyacetic acid (MCPA) with two forms in the water: a DFT comparison

The initial degradation mechanisms of OH and 4-chloro-2-methylphenoxyacetic acid (MCPA) including molecular form and anionic form are studied at the MPWB1K/6-311+G(3df, 2p)//MPWB1K/6-31+G(d, p) level. Possible reaction pathways of H-atom abstraction and OH addition are considered in detail. By result comparison analysis, it is found that the reaction mechanisms for OH and two forms of MCPA are different, and most reactions for anionic MCPA are easier than those for molecular MCPA. For H-atom abstraction reactions, the calculated energies show that OH abstracting H-atom from -CH₃ group of molecular MCPA is the most kinetically favorable process; the potential energy surface for anionic MCPA indicates that H-atom in -CH₂ group is slightly easier to be abstracted than that in -CH₃ group. For OH addition reactions, the addition of OH to the C1 site is the initial step for molecular MCPA and the predominant product is 4-chloro-2-methylphenol (denoted P3), while the C4 site is the most reactive site for anionic MCPA and the primary product results from the hydroxylation of the aromatic ring, which is in good agreement with the experimental observation. In additional, results from PCM calculations show that most reactions in water phase are more kinetically favorable than those in gas phase, though the mechanisms discussed above will not be changed.