BiVO_4微结构协同作用下的可见光响应型photo-Fenton反应

将可见光催化材料引入photo-Fenton反应,对合成条件进行了调控对比研究。以聚乙烯基吡咯烷酮(PVP)作为表面活性剂,采用醇/水热合成法制备了尺寸约为0.3~0.6μm细小条状结构的Bi VO4/Fe3O4材料,并通过调节反应液p H值调控产物的晶相组成及形貌。采用X射线衍射(XRD)、扫描电子显微镜(SEM)、紫外-可见漫反射光谱(UV-Vis DRS)、低温氮气吸附-脱附对样品进行表征,并在可见光照射下,评估了Bi VO4微结构协同作用时Photo-Fenton反应对罗丹明B(Rh B)的降解效果。研究结果表明,p H=7条件下制备的单斜白钨矿型的Bi VO4/Fe3O4具有最为规整的微结构,表现出最大的比表面积以及最佳的光催化活性。Bi VO4微结构与Fenton反应的协同作用显示出优越的可见光降解性能,对有机染料降解所用时间大幅缩短,60 min内可将99%的Rh B降解,具有更加高效的可见光吸收效率以及光催化活性。     

BiVO_4催化剂的离子液体辅助水热合成及其可见光催化活性

采用溴化1-丁基-3-甲基咪唑([Bmim]Br)离子液体辅助水热合成法制备了光催化剂Bi VO4。以高压氙灯作为可见光源,亚甲基蓝为目标污染物,考察反应温度、p H、反应时间和离子用量等制备条件对Bi VO4的可见光催化活性的影响,确定了最佳制备条件。并采用XRD、SEM和UV-Vis漫反射等分析手段对催化剂的晶相、形貌和光学特性进行了表征。结果表明,在离子液体加入量为2 m L、p H=4、反应温度为180℃、反应时间为4 h的条件下,制得的Bi VO4催化剂的可见光光催化活性最高。制得的Bi VO4为单斜相,呈分散的、大小均匀的片状,在200~500 nm范围有一个较宽的强吸收平台,具有良好的可见光催化活性,在可见光照射下对浓度为5 mg/L的亚甲基蓝的光催化脱色率达97%以上。     

纳米钒酸铋/偕胺肟纤维的制备及光催化性能

以Bi(NO3)3和NH4VO3作为原料,偕胺肟纤维作为配体,采用液相法合成钒酸铋/偕胺肟纤维(Bi VO4/AOCF),通过X射线粉末衍射(XRD)、扫描电子显微镜(SEM)、能谱(EDS)等手段对样品进行了表征分析,结果显示,颗粒状的Bi VO4均匀分布在纤维表面,并以配位键的形式与纤维结合。以罗丹明B为模拟污染物来考察Bi VO4/AOCF的光催化活性,实验结果表明,Bi VO4/AOCF有着很好的光催化活性,并且在酸性条件下的催化活性更好。催化剂对活性黄、亚甲基蓝和甲基橙也表现出很好的光催化活性,且可以重复使用多次,光催化反应过程符合一级反应动力学。     

BiPO_4稀土掺杂改性及其可见光光催化性能

以Bi(NO_3)_3·5H_2O、NH_4H_2PO_4和稀土氧化物为原料,在乙二醇介质中采用溶剂热法制备了不同稀土元素(Ln=Sm、Pr、Tb)掺杂的Bi PO4光催化剂(记为Bi PO4-Ln,包含Bi PO4-Sm、Bi PO4-Pr和Bi PO_4-Tb)。通过X-射线衍射法(XRD)、扫描电子显微镜(SEM)、X-射线光电子能谱(XPS)和紫外可见漫反射光谱(UV-Vis DRS)对制备的催化剂进行了表征。以染料罗丹明B(rhodamine B,Rh B)及小分子水杨酸(salicylic acid,SA)为目标化合物,研究了在可见光激发下(λ≥420 nm)Bi PO4-Ln对目标污染物的光催化降解特性,结果表明,Bi PO4-Ln相较纯Bi PO4,其光吸收范围从紫外光扩大到可见光区域,在3种Bi PO_4-Ln催化剂中,Bi PO4-Sm对Rh B的吸附能力最强且其光催化活性较强,通过测定其在可见光下降解Rh B过程中产生的活性物种,发现Bi PO4-Ln在氧化降解Rh B的过程中主要涉及到·OH及O-2·的氧化机理。     

Bi-Ti-O体系的制备、表征及性能

采用溶胶-活性炭浸渍法制备了Bi-Ti-O体系光催化剂,并以XRD、SEM、UV-Vis DRS对其进行表征。以在紫外光照射下对甲基橙的降解评价其光催化活性,分别考察了不同Bi/Ti比及煅烧温度的影响。实验表明,其光催化性能由粒径、吸光性能等共同影响。煅烧温度的提高使其在紫外区吸光性能有所下降,光催化活性相应降低。随着Bi含量的增加,在500℃时其禁带宽度有增加趋势,其形貌也发生了较大变化。而温度的升高,也使样品逐渐烧结团聚,降低了其光催化活性。在Bi/Ti比为5∶5和7∶3,煅烧温度为500℃时,由于Bi2O3、Bi2Ti2O7和Bi4Ti3O12三相共生共存,其混晶效应使得在紫外区的吸收明显增强,相应地提高了光催化活性。     

新型可见光催化剂BiVO4降解中成药制药废水

以Bi(NO3)3.5H2O和NH4VO3为原料,采用水热法制备了新型可见光BiVO4催化剂,并用X-射线衍射(XRD)、扫描电子显微镜(SEM)、红外光谱(IR)和紫外-可见光漫反射光谱(UV-vis DRS)对产品进行了结构表征,并将其应用于光催化降解中成药制药废水降解反应中,通过正交实验和单因素分析,考察了催化剂用量、空气流量、溶液pH值和助氧化剂H2O2对制药废水COD去除率、脱色率的影响。实验结果表明,水热产品属于单斜晶系BiVO4,其带隙能为2.41 eV,并具有良好的可见光催化活性。对于经10倍稀释的制药废水,BiVO4添加量为2 g/L,通氧量为120 L/h,助氧化剂H2O2添加量为1 mL,不改变废水pH值,在400 W金属卤化物灯离液面11 cm照射反应180 min的条件下,制药废水的COD去除率为94.3%,脱色率为95.6%,得到了较好的降解。     

新型可见光催化剂BiVO4降解中成药制药废水

以Bi（NO3）3.5H2O和NH4VO3为原料,采用水热法制备了新型可见光BiVO4催化剂,并用X-射线衍射（XRD）、扫描电子显微镜（SEM）、红外光谱（IR）和紫外-可见光漫反射光谱（UV-vis DRS）对产品进行了结构表征,并将其应用于光催化降解中成药制药废水降解反应中,通过正交实验和单因素分析,考察了催化剂用量、空气流量、溶液pH值和助氧化剂H2O2对制药废水COD去除率、脱色率的影响。实验结果表明,水热产品属于单斜晶系BiVO4,其带隙能为2.41 eV,并具有良好的可见光催化活性。对于经10倍稀释的制药废水,BiVO4添加量为2 g/L,通氧量为120 L/h,助氧化剂H2O2添加量为1 mL,不改变废水pH值,在400 W金属卤化物灯离液面11 cm照射反应180 min的条件下,制药废水的COD去除率为94.3%,脱色率为95.6%,得到了较好的降解。     

水滑石与磷酸银可见光催化剂的活性对比研究

本文合成了具备水滑石结构(LDH)的Zn-Cr LDH、Zn-Ti LDH以及Ag3PO43种半导体光催化剂,并对它们的催化性能进行对比研究。XRD和SEM分析表明,Zn-Cr LDH、Zn-Ti LDH具有层状结构而Ag3PO4呈纳米球状结构。UV-Vis分析表明,Ag3PO4和Zn-Cr LDH能够吸收可见光(>420 nm)。在可见光照射与添加AgNO3作为电子受体的条件下,Zn-TiLDH几乎没有光催化活性,而Ag3PO4的光催化活性高于Zn-Cr LDH。Ag3PO4在光解水实验中180 min内氧气产量约1.2mL,而Zn-Cr LDH约为0.65 mL。光催化降解有机污染物实验中,在Ag3PO4催化作用下,120 min内亚甲基蓝(MB)被完全降解,在240 min内46%的对硝基酚(PNP)被降解,而Zn-Cr LDH相应的去除率分别为61%和27%。     

FeOOH/g-C3N4异质光催化剂耦合过硫酸盐降解环丙沙星

采用原位沉淀法制备了FeOOH/g-C3N4异质光催化剂,并通过耦合过一硫酸盐(PMS)建立了多反应耦合型高级氧化体系,在此体系下考察了其对环丙沙星(CIP)的去除性能.在催化剂/可见光/PMS反应体系下,相对于g-C3N4,FeOOH/g-C3N4的催化性能明显提高,其中5％ FeOOH/g-C3N4表现出最优异的催化性能,表明FeOOH的耦合提高了g-C3N4的光催化活性,且光催化+PMS活化体系加速了污染物的降解.此外,分别考察了FeOOH负载量、催化剂投加量、pH等因素对CIP降解性能的影响.结果 表明:在催化剂投加量为0.4 g·L-1、pH为9.0时,5％ FeOOH/g-C3N4对CIP的降解率达到72.34％.使用XRD、TEM、XPS、UV-vis DRS等分析方法对催化剂进行了表征,FeOOH的复合显著增强了g-C3N4的光吸收能力,提高了其光催化活性.最后,基于实验数据与活性物种捕获实验,初步提出了FeOOH/g-C3N4对CIP催化降解的可能机理.     

微波辅助光催化降解高浓度活性黑

利用改装的家用微波炉、微波无极灯和TiO2催化剂研究了水中高浓度活性黑的光催化降解.系统考察了TiO2投加量、pH、微波无极灯数量对微波辅助光催化处理效果的影响,得出微波辅助光催化的最佳操作条件,并在最佳条件下对活性黑的脱色及矿化效果进行研究.结果表明,TiO2投加量存在最佳值2 g/L,降低pH和增加微波无极灯数量均可提高活性黑的降解率.在TiO2的投加量为2 g/L,pH =3,微波无极灯数量为3的最佳光催化条件下,400 mg/L的活性黑溶液反应180 min时可实现完全脱色,反应300 min时,TOC去除率高达89.1％.     

Evaluation of trichloroethene recovery processes in heterogeneous aquifer cells flushed with biodegradable surfactants

The ability of two biodegradable surfactants, polyoxyethylene (20) sorbitan monooleate (Tween 80) and sodium dihexyl sulfosuccinate (Aerosol MA), to recover a representative dense non-aqueous-phase liquid (DNAPL), trichloroethene (TCE), from heterogeneous porous media was evaluated through a combination of batch and aquifer cell experiments. An aqueous solution containing 3.3% Aerosol MA, 8% 2-propanol and 6 g/l CaCl(2) yielded a weight solubilization ratio (WSR) of 1.21 g TCE/g surfactant, with a corresponding liquid-liquid interfacial tension (IFT) of 0.19 dyn/cm. Flushing of aquifer cells containing a TCE-DNAPL source zone with approximately two pore volumes of the AMA formulation resulted in substantial (>30%) mobilization of TCE-DNAPL. However, a TCE mass recovery of 81% was achieved when the aqueous-phase flow rate was sufficient to displace the mobile TCE-DNAPL toward the effluent well. Aqueous solutions of Tween 80 exhibited a greater capacity to solubilize TCE (WSR=1.74 g TCE/g surfactant) and exerted markedly less reduction in IFT (10.4 dyn/cm). These data contradict an accepted empirical correlation used to estimate IFT values from solubilization capacity, and indicate a unique capacity of T80 to form concentrated TCE emulsions. Flushing of aquifer cells with less than 2.5 pore volumes of a 4% T80 solution achieved TCE mass recoveries ranging from 66 to 85%, with only slight TCE-DNAPL mobilization (<5%) occurring when the total trapping number exceeded 2 x 10(-5). These findings demonstrate the ability of Tween 80 and Aerosol MA solutions to efficiently recover TCE from a heterogeneous DNAPL source zone, and the utility of the total trapping number as a design parameter for a priori prediction of DNAPL mobilization and bank angle formation when flushing with low-IFT solutions. Given their potential to stimulate microbial reductive dechlorination at low concentrations, these surfactants are well-suited for remedial action plans that couple aggressive mass removal followed by enhanced bioremediation to treat chlorinated solvent source zones.     

Chloroaromatic pollutants in mussels incubated in two finnish watercourses polluted by industry

Concentrations of different chlorinated compounds were measured in mussels incubated in two polluted watercourses, a river (the River Kymijoki) and a lake (Lake Vanaja) for four weeks in summer 1995. The sum concentrations of polychlorinated phenols (PCP) and biphenyls (PCB) were both about 1 μg/g lipid weight (lw) in Lake Vanaja mussels, while in the River Kymijoki mussels PCPs were non-detectable and PCBs were measured 120 ng/g lIw. The concentrations of toxic polychlorinated dibenzo-p-dioxin (PCDD) and dibenzofuran (PCDF) congeners ranged between <17 and 370 pg/g Iw in Lake Vanaja mussels and between <38 and 11,000 pg/g lw in the River Kymijoki mussels. Polychlorinated diphenyl ethers (PCDE) were detected in the mussels incubated in the River Kymijoki (0.4–1.1 ng/g Iw), but not in those incubated in Lake Vanaja. Polychlorinated phenoxyanisoles (PCPA) were measured 33 ng/g lw and polychlorinated phenoxyphenols (PCPP) 300 ng/g lw in the mussels incubated in the River Kymijoki. PCPAs were also detected in reference samples, which were sediment and pike from the River Kymijoki and Baltic salmon, seal and white-tailed sea eagle.     

The variation of street air levels of PAH and other mutagenic PAC in relation to regulations of traffic emissions and the impact of atmospheric processes

The occurrence of particle associated PAH and other mutagenic PAC was determined in 1996 in the street air of Copenhagen. In addition, particle extracts were tested for mutagenicity. The measurements were compared with previous measurements in 1992/1993. The levels had decreased in this period. The decrease was caused by an implementation of light diesel fuels for buses and the exchange of older petrol-driven passenger cars with catalystequipped new ones. About 65% of the reduction was caused by the application of the light diesel fuels. Under special conditions, chemical processes in the atmosphere produced many more mutagens than the direct emissions. The concentrations of S-PAC and N-PAC were 10 times lower than those of PAH, while the levels of oxy-PAH were in the same order of magnitude as those of PAH. Benzanthrone, an oxy-PAH, is proposed to be formed in the atmosphere in addition to direct emissions. Benzo(a)pyrene, often applied as an air quality criteria indicator, was photochemically degraded in the atmosphere. A strong increase in the mutagenic activities was observed to coincide with a depletion of benzo(a)pyrene.     

Teratological effects of pesticides in vertebrates: a review

Abstract

In the last decades, the use and misuse of pesticides in the agriculture have increased, having a severe impact on ecosystems and their fauna. Although the various effects of pesticides on biodiversity have been already documented in several studies, to our knowledge no consistent overview of the impact of pesticides in vertebrates, both terrestrial and aquatic, is available. In this review, we try to present a concise compilation of the teratogenic effects of pesticides on the different classes of vertebrates – mammals, birds, reptiles, amphibians and fish.     

Book review

The Pesticide Manual ‐ A World Compendium, 8th Edition, C.R. Worthing, Editor and S.B. Walker, Assistant Editor, British Crop Protection Council, BCPC Publications Sales, Bear Farm, Binfield, Bracknell, Berkshire RG12 5QE, England. 1987, 1100 pp., UK £50; Overseas £56. ISBN 0–948404–01–9.     

Patterns of volatile metabolites and nonvolatile trichothecenes produced by isolates of <Emphasis Type="Italic">Stachybotrys,Fusarium, Trichoderma,Trichothecium</Emphasis> and <Emphasis Type="Italic">Memnoniella</Emphasis>

We reported previously that trichodiene, a volatile trichothecene derivative, was produced by a Stachybotrys isolate, also known to produce highly cytotoxic, non-volatile, macrocyclic trichothecenes (satrotoxins). We investigated the relationship between the production of trichodiene and various non-volatile trichothecenes for several molds. Volatile metabolites were concentrated by adsorption on Tenax TA and analyzed by GC/MS, while non-volatile metabolites were separated by HPLC, derivatized and analyzed by GC/MS. Stachybotrys chartarum isolates producing macrocyclic trichothecenes secreted significantly larger amounts of trichodiene and other sesquiterpenes than isolates which only produced simple trichothecenes. The amounts of secreted trichodiene were relatively small in all cases. With the exception of Memnoniella, which excreted small amounts of sesquiterpenes, the other isolates produced varying amounts of sesquiterpenes, including trichodiene, as well as simple tricothecenes, no detectable trichodiene, but large amounts of griseofulvin derivatives. In Stachybotrys there is apparently a correlation between trichodiene and macrocyclic trichothecene production. In the remaining isolates, there was no simple relationship between trichodiene and non-volatile trichothecene synthesis. Trichodiene is produced in larger amounts by Stachybotrys isolates, which also produce satratoxins, but it will be difficult to utilize this metabolite to detect toxic isolates in buildings due to the relatively small amounts excreted.     

Observations on the influence of water and soil pH on the persistence of insecticides

Abstract

The pH‐disappearance rate profiles were determined at ca. 25°C for 24 insecticides at 4 or 5 pH values over the range 4.5 to 8.0 in sterile phosphate buffers prepared in water‐ethanol (99: 1 v/v). Half‐lives measured at pH 8 were generally smaller than at lower pH values. Changes in half lives between pH 8.0 and 4.5 were largest (>1000x) for the aryl carbamates, carbofuran and carbaryl, the oxime carbamate, oxamyl, and the organophosphorus insecticide, trichlorfon. In contrast, half lives of phorate, terbufos, heptachlor, fensulfothion and aldicarb were affected only slightly by pH changes. Under the experimental conditions described half lives at pH8 varied from 1–2 days for trichlorfon and oxamyl to >1 year for fensulfothion and cyper‐methrin. Insecticide persistence on alumina (acid, neutral and basic), mineral soils amended with aluminum sulfate or calcium hydroxide to different pH values and four natural soils of different pH was examined. No correlation was observed between the measured pH of these solids and the rate of disappearance of selected insecticides applied to them. These observations demonstrate the difficulty of extrapolating the pH dependent disappearance behaviour observed in homogeneous solution to partially solid heterogeneous systems such as soil.     

The chemical stability of formulations of some hydrolyzable insecticides in aqueous mixtures with hydrolysis catalysts

Abstract

The active ingredients in commercial formulations of malathion, oxamyl, carbaryl, diazinon, and chlorpyrifos diluted to “spray tank”; concentrations with buffered distilled or natural water of pH 4–9 were stable for at least 24 hr. Formulations of trichlorfon were not stable at pH 7 or above but disappearance rates were slower than for the pure chemical in homogeneous solution. Cupric ion was observed to be an effective catalyst for the hydrolysis of a variety of pure organophosphorus insecticides but did not catalyze hydrolysis of the active ingredients of the formulations examined. Increasing the dilution of the formulation increased the susceptibility of malathion, oxamyl, and carbaryl to hydrolysis.     

Organochlorine compounds in a three-step terrestrial food chain

The concentrations of 15 organochlorine chemicals (PCBs and pesticides) were studied in a Central European oak wood food chain system: Great tit (Parus major), caterpillars (Tortrix viridana, Operophtera brumata, Erannis defoliaria), and oak-leaves (Quercus robur). Juvenile tits receive organochlorines from the mother via egg transfer and, eventually to a greater extent, from the caterpillar food source during nestling period. The concentrations of PCB 153 (2,2′,4,4′,5,5′-hexachlorobiphenyl, the most abundant in this study) was found in leaf material at ca. 1 ng/g, in caterpillars 10 ng/g, and in bird eggs 170 ng/g on an average and on a dry mass basis.     

Knowledge transfer initiative between molecular biologists and environmental researchers and regulators

A Natural Environment Research Council (NERC) funded Knowledge Transfer (KT) workshop was held in the United Kingdom (UK) to identify the needs and opportunities in the application of molecular biology and ‘omics’ techniques to environmental monitoring and risk assessment. Attendees highlighted a lack of effective communication between end-users and researchers as well as difficulties with data interpretation as reasons behind the slow uptake of molecular biology and omics techniques. A number of promising areas in which new techniques could be implemented at a practical level in the very near future were identified, thereby raising the profile of these recent technologies and providing vital proof of concept work. Molecular taxonomy, bacterial source tracking and pre-screening of chemicals for potential toxicities were all viewed as areas in which omics and molecular techniques could have immediate value, with the aim of reducing cost, increasing efficiency and providing more comprehensive data of improved quality.