B,N和Ce共掺杂TiO2催化剂光催化活性研究

采用溶胶-凝胶法制备出B,N和Ce共掺杂TiO2光催化剂,并用XRD、SEM等表征了其结构特征。以酸性大红染料溶液的光催化降解为探针反应,考察了制备条件对共掺杂TiO2催化剂活性的影响。结果表明,在400℃,当B,N和Ce的原子比为1∶2∶0.1,焙烧3 h时,光催化剂活性最大,大红染料的降解率达到98%。     

B,N和Ce共掺杂TiO_2催化剂光催化活性研究

采用溶胶-凝胶法制备出B,N和Ce共掺杂TiO2光催化剂,并用XRD、SEM等表征了其结构特征。以酸性大红染料溶液的光催化降解为探针反应,考察了制备条件对共掺杂TiO2催化剂活性的影响。结果表明,在400℃,当B,N和Ce的原子比为1∶2∶0.1,焙烧3 h时,光催化剂活性最大,大红染料的降解率达到98%。     

漂浮型可见光复合光催化剂B-N-TiO_2/EP的制备、表征及其光催化性能

以膨胀珍珠岩为漂浮型载体,采用溶胶凝胶法制备B和N共掺杂的B-N-TiO_2/EP可见光催化材料和单一N掺杂的N-TiO_2/EP可见光催化材料。应用X射线粉末衍射(XRD)、扫描电镜(SEM)、紫外-可见(UV-Vis)光谱、N2吸脱附(BET)、X射线光电子能谱(XPS)等手段对催化剂进行表征。并以可见光为光源,评价了该催化剂催化降解罗丹明B的活性,考察了不同B掺杂量对该催化材料性能的影响。实验结果表明,与N-TiO_2/EP相比,B-N-TiO_2/EP吸收光谱发生了明显的红移,可见光吸收强度更大。B的掺杂可以抑制TiO_2晶型从锐钛矿向金红石的转变。B0.57-N-TiO_2/EP对罗丹明B降解效果最好,可见光条件下反应3 h,罗丹明B去除率高达93%以上,B0.57-N-TiO_2/EP催化材料重复利用4次仍有75%的去除率,显示了较好的稳定性和重复利用性。     

锰掺杂WO3-TiO2复合光催化剂的制备及其性能研究

溶胶-凝胶和浸渍相结合的方法制备锰掺杂WO3-TiO2复合光催化剂,RXD表征,考察WO3和Mn2 掺入量、焙烧温度、焙烧时间及催化剂用量对光催化降解甲基橙的影响.结果表明,500℃焙烧2 h,掺杂量n(Mn2 )∶n(wo3)∶n(TiO2)=0.8∶1∶100时,光催化活性最高,光催化降解甲基橙溶液,120 min后,降解率达90%,比单纯TiO2的光催化活性提高81%.     

沸石负载N、Fe^3＋共掺杂TiO2催化剂制备及表征

以人造沸石为载体,采用溶胶\|凝胶法对N、Fe3+共掺杂TiO2进行负载化研究,探讨了焙烧温度、载体粒度、负载次数等因素对负载型光催化剂结构和催化活性的影响.研究了模拟太阳光下负载型光催化剂对活性染料Sumifix TQ\|Blue的降解性能,采用X 射线衍射(XRD)、扫描电镜 (SEM)和紫外-可见光漫反射吸收光谱(UV\|Vis DRS)等方法对催化剂进行了表征.结果表明,以60～80目人造沸石为载体,400 ℃下焙烧2 h、负载3次的负载型光催化剂(N/Fe3+/TiO2\|沸石催化剂)对Sumifix TQ\|Blue具有较高的降解率;N、Fe3+共掺杂发挥了两者的协同作用,增强了TiO2的紫外光吸收的同时也使其光吸收范围拓展到可见光区;而多孔材料沸石的引入也进一步提高了催化剂的催化活性.     

Cu/La共掺杂TiO2光催化氧化水中的氨氮

采用水解-沉淀法制备了Cu/La共掺杂纳米TiO2催化剂,利用XRD、XPS和BET技术对其进行表征,并考察了在紫外灯下,共掺杂TiO2对氨氮的光催化氧化工艺条件。物相结构和比表面积测试结果表明,共掺杂催化剂具有较好的锐钛矿晶型,孔径分布为4～8 nm,Cu/La共掺杂TiO2La以La3+,Cu是以Cu2+、Cu+的形式掺杂进入TiO2的晶格。光催化实验表明:所得改性光催化剂对氨氮的去除及焦化废水的处理均具有较高的催化活性。     

碘掺杂TiO2可见光光催化性能研究

在低于100℃温度条件下,采用溶胶-凝胶法以钛酸正丁酯为钛源,碘酸钾为碘源,制备了I掺杂纳米TiO2催化剂(I-TiO2),运用X-射线衍射(XRD)、透射电镜(TEM)及X-射线光电子能谱(XPS)等对催化剂进行表征,结果表明,TiO2及I-TiO2催化剂均为锐钛矿,I吸附并包裹在TiO2表面或以间隙进入的形式存在,并未进入TiO2晶格。通过在可见光照射下(λ>420 nm)以罗丹明B(Rhodamine B,RhB)的光催化降解为探针反应研究了在不同条件下制备催化剂的催化性能,结果表明,掺杂比为nI:nTi=0.05∶1,焙烧温度为400℃,降解介质条件pH=7时,I-TiO2光催化活性明显优于未掺杂的TiO2。光催化降解过程通过红外光谱(IR),总有机碳(TOC)跟踪测定,比较了TiO2掺杂前后降解RhB和对氯苯酚(4-CP)的光催化特性差异;同时采用苯甲酸荧光光度法跟踪测定体系中的氧化物种,表明在可见光下,I-TiO2光催化体系中产生.OH高活性氧化物种从而氧化降解目标化合物。     

漂浮型可见光催化剂Fe-N-TiO_2/FP-CTS的制备及其对溶解性柴油的降解

以漂珠为载体,用壳聚糖对漂珠进行改性,并采用溶胶凝胶法,制备了Fe-N共掺杂改性TiO2的漂浮型可见光催化剂(Fe-N-TiO2/FP-CTS),使用X射线衍射(XRD)、紫外可见分光光谱(UV-Vis)、N2吸附-脱附(BET)和扫描电子显微镜(SEM)等分析进行表征。研究结果表明,用壳聚糖改性漂珠可以增加复合光催化剂的比表面积和孔容;相较于N-掺杂TiO2/FP复合光催化剂,Fe-N共掺杂更能促进对复合光催化剂可见光的吸收;光催化4 h后,Fe-N-TiO2/FP-CTS对溶解性柴油的降解率达到61.7%,明显优于Fe-N-TiO2/FP和N-TiO2/FP。当初始pH=5,柴油乳化剂浓度=120 mg/L时,复合光催化剂对溶解性柴油的光催化降解效果最佳。     

Pd/N共掺杂TiO_2的制备及其光催化降解苯酚的研究

将纳米管钛酸浸入含尿素和金属(Pd)硝酸盐的乙醇溶液中,乙醇超声挥发后所得样品先在空气气氛、600℃下煅烧,再在H2气氛、400℃下热还原制备得到Pd/N共掺杂TiO2光催化剂(Pd/N-TiO2)。利用光电子能谱(XPS)仪研究了催化剂表面N、Pd元素的化学态。结果表明,N元素以Ti—O—N形式存在,Pd元素以单质金属状态存在。考察了Pd/N-TiO2的紫外光光催化降解苯酚的活性,与单纯TiO2光催化剂和N掺杂TiO2光催化剂相比,Pd/N-TiO2活性明显提高。研究了催化剂用量、苯酚初始浓度和pH、O2流量以及外加双氧水等条件对紫外光光催化降解苯酚的活性的影响,得到光催化降解苯酚的最佳工艺条件:苯酚初始质量浓度为120mg/L,催化剂用量为0.10g/L,苯酚溶液初始pH为8,O2流量为80mL/min,加入适量双氧水。     

微乳液法合成掺硫纳米TiO_2及其光催化性能研究

以钛酸四丁酯为钛源,硫脲为掺硫前驱物,采用聚乙二醇辛基苯基醚（Triton X-100）/正己醇/环己烷/氨水的微乳液体系合成了掺硫的纳米TiO2粉体;对其结构进行了表征,以甲基橙为目标降解物考察了其光催化性能。烧结温度通过影响TiO2的晶型转变和颗粒尺寸来影响其光催化性能,随着烧结温度的升高,TiO2的光催化性能先是提高,然后迅速降低;在600℃烧结2 h时催化剂的降解性能达到最佳。掺杂硫可提高TiO2的光催化活性,随着掺杂量的增加,催化剂对甲基橙的降解率先快速增加然后缓慢降低,当掺杂量为S/Ti（摩尔比）=0.01∶1时TiO2的光催化降解效果最好。催化剂在用量较小时迅速提高TiO2的光催化降解性能,而后随着用量的增大反而降低,当催化剂用量为1.5 g/L时,对甲基橙的降解效果最好。     

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.     

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.     

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.     

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.     

Radionuclides and trace elements in fish collected upstream and downstream of Los Alamos national laboratory and the doses to humans from the consumption of muscle and bone

Abstract

The purpose of this study was to determine radionuclide and trace element concentrations in bottom‐feeding fish (catfish, carp, and suckers) collected from the confluences of some of the major canyons that cross Los Alamos National Laboratory (LANL) lands with the Rio Grande (RG) and the potential radiological doses from the ingestion of these fish. Samples of muscle and bone (and viscera in some cases) were analyzed for ³H, ⁹⁰Sr, ¹³⁷Cs, ^totU, ²³⁸Pu, ^239,240Pu, and ²⁴¹Am and Ag, As, Ba, Be, Cr, Cd, Cu, Hg, Ni, Pb, Sb, Se, and Tl. Most radionuclides, with the exception of ⁹⁰Sr, in the muscle plus bone portions of fish collected from LANL canyons/RG were not significantly (p<0.05) higher from fish collected upstream (San Ildefonso/background) of LANL. Strontium‐90 in fish muscle plus bone tissue significantly (p<0.05) increases in concentration starting from Los Alamos Canyon, the most upstream confluence (fish contained 3.4E‐02 pCi g^‐1 [126E‐02 Bq kg^‐1]), to Frijoles Canyon, the most downstream confluence (fish contained 14E‐02 pCi g^‐1 [518E‐02 Bq kg^‐1]). The differences in ⁹⁰Sr concentrations in fish collected downstream and upstream (background) of LANL, however, were very small. Based on the average concentrations (±2SD) of radionuclides in fish tissue from the four LANL confluences, the committed effective dose equivalent from the ingestion of 46 lb (21 kg) (maximum ingestion rate per person per year) of fish muscle plus bone, after the subtraction of background, was 0.1 ± 0.1 mrem y^‐1 (1.0 ± 1.0 μSv y^‐1), and was far below the International Commission on Radiological Protection (all pathway) permissible dose limit of 100 mrem y^‐1 (1000 μSv y^‐1). Of the trace elements that were found above the limits of detection (Ba, Cu, and Hg) in fish muscle collected from the confluences of canyons that cross LANL and the RG, none were in significantly higher (p<0.05) concentrations than in muscle of fish collected from background locations.     

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.     

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.     

Sorption and predicted mobility of herbicides in Baltic soils

This study was undertaken to determine sorption coefficients of eight herbicides (alachlor, amitrole, atrazine, simazine, dicamba, imazamox, imazethapyr, and pendimethalin) to seven agricultural soils from sites throughout Lithuania. The measured sorption coefficients were used to predict the susceptibility of these herbicides to leach to groundwater. Soil-water partitioning coefficients were measured in batch equilibrium studies using radiolabeled herbicides. In most soils, sorption followed the general trend pendimethalin > alachlor > atrazine～ amitrole～ simazine > imazethapyr > imazamox > dicamba, consistent with the trends in hydrophobicity (log K_ow) except in the case of amitrole. For several herbicides, sorption coefficients and calculated retardation factors were lowest (predicted to be most susceptible to leaching) in a soil of intermediate organic carbon content and sand content. Calculated herbicide retardation factors were high for soils with high organic carbon contents. Estimated leaching times under saturated conditions, assuming no herbicide degradation and no preferential water flow, were more strongly affected by soil textural effects on predicted water flow than by herbicide sorption effects. All herbicides were predicted to be slowest to leach in soils with high clay and low sand contents, and fastest to leach in soils with high sand content and low organic matter content. Herbicide management is important to the continued increase in agricultural production and profitability in the Baltic region, and these results will be useful in identifying critical areas requiring improved management practices to reduce water contamination by pesticides.