Heterogeneous Fenton degradation of persistent organic pollutants using natural chalcopyrite: effect of water matrix and catalytic mechanism

Environmental Science and Pollution Research - Natural chalcopyrite was evaluated as heterogeneous Fenton catalyst. Catalytic performance was evaluated considering different systems, catalyst...     

Photocatalytic degradation of contaminants of concern with composite NF-TiO2 films under visible and solar light

This study reports the synthesis and characterization of composite nitrogen and fluorine co-doped titanium dioxide (NF-TiO₂) for the removal of contaminants of concern in wastewater under visible and solar light. Monodisperse anatase TiO₂ nanoparticles of different sizes and Evonik P25 were assembled to immobilized NF-TiO₂ by direct incorporation into the sol–gel or by the layer-by-layer technique. The composite films were characterized with X-ray diffraction, high-resolution transmission electron microscopy, environmental scanning electron microscopy, and porosimetry analysis. The photocatalytic degradation of atrazine, carbamazepine, and caffeine was evaluated in a synthetic water solution and in an effluent from a hybrid biological concentrator reactor (BCR). Minor aggregation and improved distribution of monodisperse titania particles was obtained with NF-TiO₂-monodisperse (10 and 50 nm) from the layer-by-layer technique than with NF-TiO₂?+?monodisperse TiO₂ (300 nm) directly incorporated into the sol. The photocatalysts synthesized with the layer-by-layer method achieved significantly higher degradation rates in contrast with NF-TiO₂-monodisperse titania (300 nm) and slightly faster values when compared with NF-TiO₂-P25. Using NF-TiO₂ layer-by-layer with monodisperse TiO₂ (50 nm) under solar light irradiation, the respective degradation rates in synthetic water and BCR effluent were 14.6 and 9.5?×?10^?3?min^?1 for caffeine, 12.5 and 9.0?×?10^?3?min^?1 for carbamazepine, and 10.9 and 5.8?×?10^?3?min^?1 for atrazine. These results suggest that the layer-by-layer technique is a promising method for the synthesis of composite TiO₂-based films compared to the direct addition of nanoparticles into the sol.     

喷射环流三相光催化反应器可见光下降解酸性湖兰A的研究

设计了一种喷射环流三相光催化反应器。用该反应器在可见光下,对染料酸性湖兰A在不同初始浓度、催化剂浓度、pH、光照时间下光催化降解脱色率的影响进行了研究。实验结果表明,反应最佳pH为6,反应最佳时间为20min,催化剂最佳投加量为8g／L。在最优条件下,染料脱色率达90％以上。     

物理场协同作用降解有机污染物研究进展

有机污染物是环境污染物的主要类型,通过物理场外加能量的作用可实现各种有机污染物的高效降解.对微波、超声波、紫外光、电场、磁场、等离子体这几类主要物理场相互协同降解有机污染物的研究现状进行综述,重点介绍了物理场协同作用降解有机污染物的机制、效果、影响因素及污染物类型,并展望了该类研究今后的应用前景和发展趋势.     

氮掺杂TiO_2可见光光催化剂的制备及性能

以尿素和钛酸丁酯为原料,通过溶胶-凝胶法低温下制备了高可见光催化活性的氮掺杂TiO2（NDT）光催化剂,采用XRD、TEM、BET和UV-Vis DRS等测试手段对其进行了表征,并在自制光催化反应器中降解甲基橙评价了样品的光催化活性。结果表明,当氮与钛的摩尔比为0.5∶1时,350℃焙烧的样品（NDT350）具有最佳的可见光光谱吸收和光催化活性,该催化剂为锐钛矿晶相,平均粒径为21 nm,比表面积为89.13 m2/g。可见光辐照下,NDT350降解甲基橙的表观反应速率常数为1.381×10-2min-1,是商业P25催化剂的16.85倍。NDT350优良的可见光催化活性与其大的比表面积和强烈的可见光光谱吸收有关。     

Altered toxicity of organic pollutants in water originated from simultaneous exposure to UV photolysis and CdSe/ZnS quantum dots

The paper reports unforeseen results of increased toxicity of water, subsequent to interactions between CdSe/ZnS quantum dots (QDs), phenol and toluene under UV irradiation. The consistent pattern of changes in measured toxicity (TU) was observed and correlated with degradation of phenol and/or toluene. Spearman rank coefficients (SRCs) for data pairs sum-parameters vs. TU were calculated. The highest correlation between toxicity and degradation by-products was observed for hydroquinone (0.86) and catechol (0.89). The presence of QDs in tested concentration range in the absence of UV has shown low toxicity and no interactions with phenol and/or toluene. The leak of constituent core and shell metal ions was observed. The minor differences in physical characteristics of tested QDs of the same chemical composition led to rather different degradation patterns of phenol and toluene, and the amount of leak of the metal ions as well.     

COP-compost: a software to study the degradation of organic pollutants in composts

Composting has been demonstrated to be effective in degrading organic pollutants (OP) whose behaviour depends on the composting conditions, the microbial populations activated and interactions with organic matters. The fate of OP during composting involves complex mechanisms and models can be helpful tools for educational and scientific purposes, as well as for industrialists who want to optimise the composting process for OP elimination. A COP-Compost model, which couples an organic carbon (OC) module and an organic pollutant (OP) module and which simulates the changes of organic matter, organic pollutants and the microbial activities during the composting process, has been proposed and calibrated for a first set of OP in a previous study. The objectives of the present work were (1) to introduce the COP-Compost model from its convenient interface to a potential panel of users, (2) to show the variety of OP that could be simulated, including the possibility of choosing between degradation through co-metabolism or specific metabolism and (3) to show the effect of the initial characteristics of organic matter quality and its microbial biomass on the simulated results of the OP dynamic. In the model, we assumed that the pollutants can be adsorbed on organic matter according to the biochemical quality of the OC and that the microorganisms can degrade the pollutants at the same time as they degrade OC (by co-metabolism). A composting experiment describing two different ¹⁴C-labelled organic pollutants, simazine and pyrene, were chosen from the literature because the four OP fractions simulated in the model were measured during the study (the mineralised, soluble, sorbed and non-extractable fractions). Except for the mineralised fraction of simazine, a good agreement was achieved between the simulated and experimental results describing the evolution of the different organic fractions. For simazine, a specific biomass had to be added. To assess the relative importance of organic matter dynamics on the organic pollutants’ behaviour, a sensitivity analysis was conducted. The sensitivity analysis demonstrated that the parameters associated with organic matter dynamics and its initial microbial biomass greatly influenced the evolution of all the OP fractions, although the initial biochemical quality of the OC did not have a significant impact on the OP evolution.     

光化学氧化技术去除水中有机污染物的试验研究

以自来水为试验对象,对紫外－臭氧和紫外－二氧化钛两种光化学氧化技术对水中微量有机污染物的去除进行了试验研究,结果表明两种工艺的UVA（紫外吸光度）去除率均达到80％以上,对氯仿的去除也均能达到国家饮用水标准。在此基础上,自制了一种催化剂膜,并取得了预期的处理效果,有望在新型净水技术及设备的研制和开发上得到应用。     

Photocatalytic inactivation of Escherichia coli by natural sphalerite suspension: effect of spectrum, wavelength and intensity of visible light

The photocatalytic disinfection of Escherichia coli K-12 is investigated by the natural sphalerite (NS) under different spectra, wavelengths and intensities of visible light (VL) emitted by light-emitting-diode lamp (LED). The spectrum effect of VL on disinfection efficiency is studied by using white LED, fluorescent tube (FT) and xenon lamp (XE), which indicates that the “discreted peak spectrum” of FT is more effective to inactivate bacteria than “continuous spectrum” of LED and XE. Besides, the photocatalytic disinfection of bacteria is compared under different single spectrum (blue, green, yellow and red color) LEDs. The results show that the most effective wavelength ranges of VL for photocatalytic disinfection with the NS are 440-490 and 570-620 nm. Furthermore, a positive relationship is obtained between the disinfection efficiency and the VL intensity. The experiment shows that NS can completely inactivate 10⁷ cfu mL⁻¹E. coli K-12 within 8 h irradiation by white LED with the intensity of 200 mW cm⁻² at pH 8. Moreover, the destruction process of the cell wall and the cell membrane are directly observed by TEM. Finally, no bacterial colony can be detected within a 96 h regrowth test of inactivated bacteria, which reveals that the VL-photocatalytic disinfection leads to an irreversible damage to the bacterial cells.     

Photocatalytic degradation of phenol by visible light-responsive iron-doped TiO2 and spontaneous sedimentation of the TiO2 particles

Fe-doped TiO₂ was prepared by the calcination of Fe_xTiS₂ (x = 0, 0.002, 0.005, 0.008, 0.01) and characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and UV–visible diffuse reflectance spectra. All the Fe-doped TiO₂ were composed of an anatase crystal form and showed red shifts to a longer wavelength. The activity of the Fe-doped TiO₂ for the degradation of phenol was investigated by varying the iron content during UV (365 nm) and visible light (405 nm and 436 nm) irradiation. The degradation rate depended on the Fe content and the Fe-doped TiO₂ was responsive to the visible light as well as the elevated activity toward UV light. The molar ratio of 0.005 was the optimum for both the UV and visible light irradiations. The result was discussed on the basis of the balance of the excited electron–hole trap by the doped Fe³⁺ and their charge recombination on the doped Fe³⁺ level. The Fe-doped TiO₂ (x = 0.005) was more active than P25 TiO₂ under solar light irradiation. The suspended Fe-doped TiO₂ spontaneously precipitated once the stirring of the reaction mixture was terminated.     

Photocatalytic degradation kinetics and mechanism of phenobarbital in TiO2 aqueous solution

5-Ethyl-5-phenylpyrimidine-2,4,6(1H, 3H, 5H)-trione is an anti-convulsant used to treat disorders of movement, e.g. tremors. This work deals with the transformation of phenobarbital by UV/TiO₂ heterogeneous photocatalysis, to assess the decomposition of the pharmaceutical compound, to identify intermediates, as well as to elucidate some mechanistic details of the degradation. The photocatalytic removal efficiency of 100 μm phenobarbital is about 80% within 60 min, while the degradation efficiency of phenobarbital was better in alkaline solution. The study on contribution of reactive oxidative species (ROSs) has shown that OH is responsible for the major degradation of phenobarbital, while the photohole, photoelectrons and the other ROSs have the minor contribution to the degradation. Finally, based on the identification of degradation intermediates, two main photocatalytic degradation pathways have been tentatively proposed, including the hydroxylation and cleavage of pyrimidine ring in the phenobarbital molecule respectively. Certainly, the phenobarbital can be mineralized when the photocatalytic reaction time prolongs.     

Effective collection of hydrophobic organic pollutants in water with aluminum hydroxide and hydrophobically modified polyacrylic acid

Polyacrylic acid was hydrophobically modified with dodecylamine and used as a coagulant for coprecipitation of hydrophobic organic pollutants from water. The polymer coagulant induced effective aggregation of aluminum hydroxide having hydrophobic regions which are essential for the incorporation of hydrophobic organic pollutants. Recoveries of the organic pollutants increased with increasing the dodecylamine content, which indicated that the dodecylamine moiety played an important role in the formation of hydrophobic area on the precipitate. Different hydrophobic organic pollutants that had hardly been removed by the conventional coprecipitation were successfully collected by the proposed method.     

Attenuation of landfill leachate by UK Triassic sandstone aquifer materials: 2. Sorption and degradation of organic pollutants in laboratory columns

The sorption and degradation of dissolved organic matter (DOM) and 13 organic micropollutants (BTEX, aromatic hydrocarbons, chloro-aromatic and -aliphatic compounds, and pesticides) in acetogenic and methanogenic landfill leachate was studied in laboratory columns containing Triassic sandstone aquifer materials from the English Midlands. Solute sorption and degradation relationships were evaluated using a simple transport model. Relative to predictions, micropollutant sorption was decreased up to eightfold in acetogenic leachate, but increased up to sixfold in methanogenic leachate. This behaviour reflects a combination of interactions between the micropollutants, leachate DOM and aquifer mineral fraction. Sorption of DOM was not significant. Degradation of organic fractions occurred under Mn-reducing and SO₄-reducing conditions. Degradation of some micropollutants occurred exclusively under Mn-reducing conditions. DOM and benzene were not significantly degraded under the conditions and time span (up to 280 days) of the experiments. Most micropollutants were degraded immediately or after a lag phase (32–115 days). Micropollutant degradation rates varied considerably (half-lives of 8 to >2000 days) for the same compounds (e.g., TeCE) in different experiments, and for compounds (e.g., naphthalene, DCB and TeCA) within the same experiment. Degradation of many micropollutants was both simultaneous and sequential, and inhibited by the utilisation of different substrates. This mechanism, in combination with lag phases, controls micropollutant degradation potential in these systems more than the degradation rate. These aquifer materials have a potentially large capacity for in situ bioremediation of organic pollutants in landfill leachate and significant degradation may occur in the Mn-reducing zones of leachate plumes. However, degradation of organic pollutants in acetogenic leachate may be limited in aquifers with low pH buffering capacity and reducible Mn oxides. Contaminants in this leachate present a greater risk to groundwater resources in these aquifers than methanogenic leachate.     

Behavior of selected priority organic pollutants in horizontal subsurface flow constructed wetlands: a preliminary screening

A discrete injection experiment was carried out in a constructed wetland to evaluate the behavior of selected priority pollutants. A horizontal subsurface flow pilot plant located in the NE of Spain was selected for this study. A total of eight European Priority Pollutants listed in the Water Framework Directive were considered, including a commonly used herbicide (mecoprop). The pollutants encompassed a variety of chemical classes and physicochemical properties. They included organochlorine, organophosphorus, phenols, chloroacetanilides, triazine, phenoxycarboxylic acid and phenylurea pesticides. A time series of composite effluent samples and discrete gravel bed samples from the wetland were analyzed. Response curves for all the pollutants injected from effluent concentrations were obtained and compared with the tracer (clofibric acid). On the basis of an analysis of the samples taken 21 days after the injection, priority pollutants were classified into four groups according to their removal efficiency. These groups were (i) the highly efficiently removed (>90%), namely lindane, pentachlorophenol, endosulfan and pentachlorobenzene; (ii) the efficiently removed (80-90%), namely alachlor and chlorpyriphos; (iii) poorly removed (20%), namely mecoprop and simazine; and (iv) recalcitrant to elimination, namely clofibric acid and diuron. Taking into account the poor accumulation of the injected contaminants in the gravel bed (0-20%), biodegradation and plant uptake are postulated as the most likely elimination pathways for the pollutants.     

Visualization by light transmission of oil and water contents in transient two-phase flow fields

The difficulty of determining transient fluid contents in a soil–oil–water system is hampering an understanding of the system's flow characteristics. In this paper, we describe a light transmission method (LTM) which can rapidly obtain oil and water contents throughout a large two-dimensional flow field of silica sand. By appropriately coloring the water with 0.005% FD&C blue #1, the hue of the transmitted light is found to be directly related to the water content within the porous media. The hue provides a high resolution measurement of the water and oil contents in transient flow fields (such as unstable flow). Evaluation of the reliability of LTM was assessed by checking the mass balance for a known water injection and its utility in visualizing a whole flow field was exemplified for unstable fingered flow by comparing fluid contents to those obtained with synchrotron X-ray radiation.     

Decolorization and decomposition of organic pollutants for reactive and disperse dyes using electron beam technology: effect of the concentrations of pollutants and irradiation dose

Dyeing wastewater was known to have strong color and refractory organic pollutants. In this study irradiation alone was used for dyes wastewater treatment. This paper studies the effect of the concentrations of pollutants to its removal at various dosages using electron beam technology. Irradiation was effective in removing the highly colored and refractory organic compounds. The color removal for initial concentrations of 255 CU, 520 CU, 990 CU and 1900 CU treated using irradiation at 0.5kGy were 61%, 48%, 28% and 16%, respectively. However, at the dose of 108kGy and higher, the color removal between 87% and 96% were recorded with no apparent trend. COD removal also reported similar trend but at relatively lower removal percentage. The COD removal at 0.5kGy for initial COD concentrations of 57mg/l and 515mg/l were 10% and 0%, respectively. At irradiation dose of 108kGy, the removal for initial COD concentrations of 57mg/l and 515mg/l were 37% and 13%, respectively. This showed that concentrations of pollutants and dose of irradiation applied to remove color and COD were dependent to each other.     

The photocatalytic degradation of methylene blue by green semiconductor films that is induced by irradiation by a light-emitting diode and visible light

This study develops a low-energy rotating photocatalytic contactor (LE-RPC) that has Cu-doped TiO₂ films coated on stainless-steel rotating disks, to experimentally evaluate the efficiency of the degradation and decolorization of methylene blue (MB) under irradiation from different light sources (visible 430 nm, light-emitting diode [LED] 460 nm, and LED 525 nm). The production of hydroxyl radicals is also examined. The experimental results show that the photocatalytic activity of TiO₂ that is doped with Cu²⁺ is induced by illumination with visible light and an LED. More than 90% of methylene blue at a 10 mg/L concentration is degraded after illumination by visible light (430 nm) for 4 hr at 20 rpm. This study also demonstrates that the quantity of hydroxyl radicals produced is directly proportional to the light energy intensity. The greater the light energy intensity, the greater is the number of hydroxyl radicals produced.

Implications: The CuO-doped anatase TiO₂ powder was successfully synthesized in this study by a sol–gel method. The catalytic abilities of the stainless-steel film were enhanced in the visible light regions. This study has successfully modified the nano-photocatalytic materials to drop band gap and has also successfully fixed the nano-photocatalytic materials on a substratum to effectively treat dye wastewater in the range of visible light. The results can be useful to the development of a low-energy rotating photocatalytic contactor for decontamination purposes.