Solar-driven photocatalytic treatment as sustainable strategy to remove pesticide residues from leaching water

Environmental Science and Pollution Research - We have demonstrated the potential leaching of eight compounds, one insecticide (flonicamid) and seven fungicides (myclobutanil, penconazole,...     

Abatement of spinosad and indoxacarb residues in pure water by photocatalytic treatment using binary and ternary oxides of Zn and Ti

The photodegradation of indoxacarb, a broad spectrum foliar insecticide and spinosad, a natural insecticide containing two active ingredients, spinosyn A (major component) and spinosyn D (minor component), was studied in aqueous suspensions of binary (ZnO and TiO₂) and ternary (Zn₂TiO₄ and ZnTiO₃) oxides under artificial light (300–460 nm) irradiation. As expected, the influence of the semiconductor materials on the degradation of both was very significant in all cases. Photocatalytic experiments showed that the addition of semiconductors in tandem with Na₂S₂O₈ as electron acceptor strongly improved the removal of indoxacarb and spinosad in water compared with the photolytic tests. The reaction rates significantly increased, especially for the ZnO/Na₂S₂O₈ and TiO₂/Na₂S₂O₈ systems. The first-order equation (monophasic model) satisfactorily explained the disappearance process, although it offered no explanation for the small concentrations remaining in the process.     

光催化反应器在污水处理中的研究现状与发展趋势

根据光催化反应的光源不同 ,将多相光催化反应器分为聚光式反应器和非聚光式反应器。本文主要介绍了国内外近年来有关污水处理中的光催化反应器研制与应用的进展情况 ,同时展望其发展趋势。论述了适用于工业化光催化反应器的特点及今后的发展方向     

预氯化工艺去除水中氰化物、硫化物及水合肼等还原性污染物研究

以较常见的预氯化为技术手段,考察了预氯化工艺去除饮用水中氰化物、硫化物以及水合肼等还原性污染物的效果和影响因素.结果表明:(1)实验条件下氰化物浓度随有效氯投加量的增加而下降,并在有效氯投加量＞5.0 mg/L时降低到低于《生活饮用水卫生标准》(GB5749-2006)中限值(0.05mg/L),在有效氯投加量＞6.0...     

以玉米芯为外加碳源的SBBR脱氮特性

针对低碳氮比生活污水总氮去除效果不佳的问题,以玉米芯作为SBBR生物载体和外加碳源,开展同步硝化反硝化脱氮特性研究。主要考察了碳源投加比及曝气时间对脱氮效果的影响。在最佳碳源投加比为1:80、最适曝气时间为5.5 h时,出水COD、TN、NH3-N分别为48.95、6.25和1.01 mg/L,满足城镇污水厂一级A排放标准。研究表明,采用玉米芯为外加碳源,可实现固体碳源释碳与反硝化需碳的平衡,有效增强低碳氮比污水的脱氮效果,同时能够保证出水COD满足排放标准。     

Cu2O光催化降解水中对硝基苯酚的研究

用CuCl水解法制备Cu2O粉末,用透射电镜(TEM)和X衍射(XRD)对Cu2O粒子进行了表征.在仿太阳光源的照射下,研究了Cu2O对水中难降解有机污染物对硝基苯酚的光催化降解效果.结果表明,在8 h内,对硝基苯酚几乎完全降解.在催化剂用量为0.2 g时,对浓度为22.4 mg/L的200mL对硝基苯酚溶液有良好的降解效果.降解反应符合一级反应动力学.     

改善反应器内部光照条件对TiO2光催化去除H2S的影响

在不同紫外光照强度和不同催化剂质量条件下,研究了TiO2对H2S光催化氧化去除效率和特征。结果表明,H2S去除率随紫外光照强度增大而增大,而在用空白玻璃珠替代部分负载有TiO2的玻璃珠（TiO2-GB）后,TiO2-GB所占比例为60%（TG60%）时具有最佳的光催化氧化效率。在H2S浓度为1 062 mg·m-3,流速100 mL·min-1条件下反应90 h后,TG60%的H2S去除率依然能达到64.79%,高于相同条件下TG100%的42.03%,产物为S6与S0。通过研究反应器内部紫外光强度分布,发现单纯增大外部紫外灯功率并不能有效增大反应器内部光强,而随空白玻璃珠所占比例增大,反应器内部光照条件得到有效改善。因此,单纯增强紫外线强度或增加TiO2催化剂用量均不能达到最理想的光利用效率,而是要将两者综合考虑。实验结果表明,与填充物全为TiO2-GB的情况相比,TG60%在不提高能耗的前提下,减少了催化剂的用量,而H2S的光催化去除率反而提升。     

Effect of water composition on the photocatalytic removal of pesticides with different TiO2 catalysts

The objective of this work is double—firstly to explore the photocatalytic efficiency of five different commercial TiO₂ catalysts in the photodegradation of a mixture of pesticides classified by the EU as priority pollutants and secondly to analyze the correlation between their physicochemical properties and the inhibition of the studied photocatalytic process when natural water was employed. Photocatalytic efficiencies when ultrapure water was used seem to point out that surface area was not a prerequisite for the photodegradation of the selected mixture of pesticides. On the other hand, significant differences in total organic carbon (TOC) conversions were obtained with the two studied water compositions. On one side, Evonik materials appear to be mostly inhibited when natural water was employed, whereas on the other, it should be remarked that anatase Sigma-Aldrich (SA) and, particularly, Hombikat UV100 (HBK) materials presented a very limited photo-efficiency inhibition or even a higher initial rate of TOC removal when a natural water matrix was used, probably due to their specific surface properties (PZC, S _BET). Therefore, heterogeneous photocatalysis has proved to be a promising technology for the degradation of the selected mixture of pesticides where the final photo-efficiency of the five commercial titania catalysts studied here responds to a complex balance between its surface and structural properties.     

Biological denitrification in drinking water treatment using the seaweed Gracilaria verrucosa as carbon source and biofilm carrier.

Chemical and microbiological aspects were investigated with regard to biological denitrification of drinking water using the seaweed Gracilaria verrucosa as the carbon and energy substrate and as physical support for the microbial flora in semibatch, fixed-bed reactors. Complete removal of nitrate (100 mg/L) was readily achieved without accumulation of nitrite. Microbiological analysis indicated that the effluent of the reactor contained high numbers of bacteria (>10(6)/mL total count). Among the 44 bacterial strains isolated directly from the samples or isolated after enrichment at 37 degrees C, 25 different fatty acid profiles were found, indicating a complex microflora, including potential pathogens.     

Effects of copper fungicide residues on the microbial function of vineyard soils

The use of copper-based fungicides leads to an accumulation of copper (Cu) in vineyard soils, potentially causing adverse effects to the microbial function and fertility of the soil. This study used a soil microcosm approach to assess the effects of Cu accumulation on microbial function in vineyard soils. Surface soil samples were collected from 10 vineyards and a number of un-impacted reference sites in each of three different viticultural regions of Australia. The field-collected soils were transferred to microcosms and maintained for up to 93 days in the laboratory at 20–22 °C and 60 % of their maximum water-holding capacity. The microbial function of the soils was indicated by measuring phosphomonoesterase, arylsulfatase, urease, and phenol oxidase activities. In general, the vineyard soils had greater concentrations of Cu and lower enzyme activities than in the reference soils, although a weak negative relationship between Cu and enzyme activity could only be found for phosphomonoesterase activity. The results show that soil physical–chemical properties (i.e., organic carbon, pH) are greater determinants of soil enzyme activity than increased soil Cu concentration at the Cu concentrations present in vineyard soils.     

琼脂碳源生物反硝化去除水源水中硝酸盐

针对受硝酸盐污染的水源水,以琼脂为反硝化细菌的碳源和微生物载体,通过生物反硝化作用脱除水源水中的硝酸盐,并利用曝气生物滤池(BAF)去除琼脂反应器出水中残留的少量CODMn和NO2--N等污染物。实验结果表明,水源水自然接种的条件下,可以顺利启动琼脂反应器;在温度为25℃左右,琼脂反应器在进水NO3--N约25 mg/L、水力停留时间1.5 h时,能获得70%的硝酸盐氮去除率;曝气生物滤池在水力停留时间0.5 h、气水比2.8时,可控制最终出水的CODMn和NO2--N分别在5.0 mg/L和0.10 mg/L以下;琼脂反应器的脱氮效果与温度、进水NO3--N浓度及水力停留时间等有关。研究指出,琼脂反应器与曝气生物滤池构成的组合系统能较好地脱除水源水中的硝酸盐并且能控制最终出水水质,不会导致二次污染,从而获得合格的饮用水源水。     

镧铁负载给水厂污泥复合材料在完全混合式反应器中的动态吸附除磷特征

采用共沉淀法制备出一种镧铁负载给水厂污泥复合材料(LaFe-DWTR),研究其在完全混合式反应器(CSTR)中对模拟废水和城市污水处理厂二沉池出水的除磷效果以及水力停留时间(HRT)、LaFe-DWTR投加量和水力学条件的影响。结果表明,当CSTR进水PO₄³⁻-P质量浓度为50 mg·L⁻¹,HRT为3 h,LaFe-DWTR投加量为2 g·L⁻¹,反应区采用搅拌时,LaFe-DWTR对PO₄^3--P的去除率稳定在99%以上,吸附量可达24.82 mg·g⁻¹。对于CSTR进水初始PO₄³⁻-P质量浓度为2 mg·L⁻¹的城市污水处理厂二沉池出水,在3 h HRT,0.14 g·L⁻¹投加量时,CSTR出水的PO₄³⁻-P质量浓度稳定在0.2 mg·L⁻¹左右,已达到《城市污水处理厂污染物排放标准》(GB 18918–2002)一级A标准的要求。     

以养殖固体废弃物发酵产物为碳源的SND系统的脱氮除磷效果

在连续低曝气的SBR装置中,采用人工模拟养殖废水培养成熟脱氮除磷污泥,研究了养殖固体废弃物发酵产物为碳源的养殖废水脱氮除磷效果。结果表明:在水力停留时间(HRT)为12 h,溶氧在0.04~1.5 mg/L之间,污泥经过25 d的驯化培养,反应器中形成了具有较高活性的同步硝化反硝化能力的污泥,以养殖固体废弃物发酵产物为碳源处理养殖废水,反应器中的COD、NO3--N和NH4+-N最大去除率分别能达到97.87%、94.95%和88.90%,且NO2--N完全不发生累积,其中C/N=7.35,即50 g湿重的养殖固体废弃物与2 L的养殖废水配比最佳,脱氮除磷效果最好,对TN的去除率在87%左右,能够较好完成同步脱氮除磷实现养殖固体废弃物的资源化利用,为循环水养殖系统零排放提供技术参考。     

Characterization of non-extractable residues of the fungicide dithianon in soil using 13C/14C-labelling techniques

The fate of the (14)C-labelled fungicide dithianon in soil is characterized by the formation of non-extractable, "bound" residues of approximately 63% of applied amount in 64 d. Humic acids containing these "bound" residues were isolated after conducting degradation studies of the active ingredient in an orthic luvisol under standardized conditions. In the same way, (13)C-labelled dithianon was incubated in an artificial soil which was produced by humification of (13)C-depleted straw in an incinerated soil. The "bound" residues of the (13)C-labelled dithianon in the humic acid fraction of the artificial soil were analyzed using (13)C-NMR techniques. There was no evidence of a covalent bonding of the residues to the humic substances. Results of polarity gradient high performance thin layer chromatography (AMD-HPTLC) of "bound" residues of the (14)C-labelled dithianon in the humic acid fraction indicate a sequestration process of metabolites into the humic substance as a possible binding mechanism.     

光照强度对光能自养生物膜去除低污染水体中硝态氮的影响研究

低污染水体存在C/N较低的特征,往往导致水体自净过程中反硝化碳源的不足.提出采用光能自养生物膜去除低污染水体中的硝态氮,研究不同光照强度对光能自养生物膜脱氮能力的影响,并验证了生物膜自行产生的胞外聚合物(EPS)及溶解性微生物产物(SMP)中多糖能否成为反硝化的碳源.结果表明,采用光能自养生物膜去除低污染水体中硝态氮具有良好的效果,光照强度的提高可以有效促进硝态氮的去除,在光暗比为12:12、水力停留时间为72 h时,1 500、3 000、4 500 lx光照强度下系统的硝酸盐去除率分别为37.1％、56.7％、62.5％,且随着光照强度增加硝酸盐去除速率逐渐提高;光照强度的增加可促进光能自养生物膜系统的EPS、SMP中多糖的产生,且光暗交替时EPS、SMP中多糖浓度呈“锯齿形”变化,在有光照时浓度明显上升,而在无光照时浓度下降;光能自养生物膜系统的EPS、SMP中的多糖可作为碳源被反硝化菌利用,而且在无外加碳源条件下,SMP中多糖对碳源的贡献大于EPS中的多糖.     

Solar photocatalytic treatment of landfill leachate using a solid mineral by-product as a catalyst

The treatment of municipal solid waste landfill leachate in a pilot plant made up of solar compound parabolic collectors, using a solid industrial titanium by-product (WTiO₂) containing TiO₂ and Fe(III) as a photocatalyst, was investigated. In the study evidence was found showing that the degradation performed with WTiO₂ was mainly due to the Fe provided by this by-product, instead of TiO₂. However, although TiO₂ had very little effect by itself, a synergistic effect was observed between Fe and TiO₂. The application of WTiO₂, which produced coupled photo-Fenton and heterogeneous catalysis reactions, achieved a surprisingly high depuration level (86% of COD removal), higher than that reached by photo-Fenton using commercial FeSO₄ (43%) in the same conditions. After the oxidation process the biodegradability and toxicity of the landfill leachate were studied. The results showed that the leachate biodegradability was substantially increased, at least in the first stages of the process, and again that WTiO₂ was more efficient than FeSO₄ in terms of increasing biodegradability.     

Investigation on the chemical structure of nonextractable residues of the fungicide cyprodinil in spring wheat using 13C-C1-phenyl-cyprodinil on 13C-depleted plants-an alternative approach to investigate nonextractable residues

13C-labelled cyprodinil was applied on 13C-depleted wheat plants with 27-fold field application rate. A control experiment applying same amounts of 14C-cyprodinil showed that main portions of the residues were detected in the cellulose (15% NER), hemicellulose (28.3% NER), and lignin fraction (23.3% NER). 16.7% were detected in water soluble polymers, 6% in both, pectin and protein fraction, and 4% in the starch containing fraction. Free cyprodinil was detectable by TLC in all fractions except lignin. A direct characterization of the residues in vivo by CP-MAS was not successful. Cell wall fractions were further analysed by liquid state NMR to determine the structure of the mobilized highly polymer/polar residues: Within lignin, where most of the residues were located at field application rate, neither intact cyprodinil nor its metabolites could not be detected. The 13C-label introduced was probably incorporated in the polymer as natural lignin monomers and thus are not considered as bound residues according to IUPAC definition.     

锆改性铝氧化物对水中磷的吸附特性

采用共沉淀法制备锆改性铝氧化物。在研究其对水中磷吸附特性的基础上,结合SEM-EDS、XRD、FTIR和XPS等表征手段,分析吸附剂的结构组成以及反应前后的表面基团变化,探讨吸附除磷的机理。结果表明：Power动力学模型和Langmuir等温线模型可以很好地描述锆改性铝氧化物对磷的吸附特征;在投加量为0.3 g·L-1、溶液pH为7时,磷的饱和吸附量为76.63 mg·g-1;pH=4~6时,吸附剂除磷效果较好,在偏碱性环境下,磷吸附量明显降低;Cl- 和SiO32-对磷的吸附有较强的抑制作用,且干扰效果随着阴离子浓度的升高而加强。通过材料表征结果可知,吸附剂呈无定型结构,表面含有丰富的羟基。该吸附剂的除磷机制主要为表面络合和离子交换作用。     

Enhanced performance of photocatalytic treatment of Congo red wastewater by CNTs-Ag-modified TiO2 under visible light

Environmental Science and Pollution Research - In order to improve the treatment efficiency of printing and dyeing wastewater, the carbon nanotubes-silver-modified-titanium dioxide (CNTs-Ag-TiO2,...     

基于异构载体的海产品暂养水的协同处理

针对海产品暂养水盐度高、低温环境下靶向菌难驯化、难富集等问题,构建了微生物驯化富集装置,采用玉米芯作为异构载体与碳源,在低温条件下,通过检测水质与微生物群落结构等指标,探究了海产品暂养水对优势菌种演替的推动作用以及微生物群落结构与异构载体的相关性,并对污染物降解与水处理效果进行了分析评价。结果表明：在低温条件下,海产品暂养水对微生物的驯化富集效果较佳;以属水平为例,经过驯化富集培养的菌液主要以假单胞菌属(Pseudomonas)、拟杆菌属(Bacteroides)和气单胞菌属(Aeromonas)为主,同时异构碳源的构造也对微生物的生长起到一定的促进作用;挂膜后的异构碳源对高盐暂养水的处理效果较佳,脱氮率达到(73.46±0.55)%,除磷率为(40.03±0.55)%,除沫率为(82.14±0.23)%。该装置在投入靶向菌与异构碳源后,提高了对高盐暂养水的处理能力;同时,玉米芯作为碳源供给,其缓释效果能够克服能量的过释并减少能耗,保证微生物的存活与运行。研究探讨了微生物与异构载体协同处理高盐暂养水的效果及其耦合效应,为高盐暂养水处理技术的创新与农用废弃物的回收利用提供了参考。