负载型TiO2/活性炭光催化灭活大肠杆菌(E.coli)的研究

以大肠杆菌(Escherichia coli JM 109)为研究对象,通过细菌的灭活实验研究负载型TiO2/活性炭(TiO2/AC)的灭菌性能,并利用XRD、BET和SEM对材料的晶型、晶粒尺寸、比表面积和吸附在材料上的细菌分布形态及数量进行分析.结果表明吸附在TiO2/AC上的大肠杆菌数比吸附在活性炭和TiO2都多.TiO2/AC对E.coli光催化灭活率比TiO2粉末和P25高,制备材料的热处理温度500℃和光催化反应中光强40 W都分别使TiO2/AC的光催化活性达到最大,在光催化灭活E.coti过程中,KH2PO4使催化剂活性降低程度比NaHCO3大,而两者使TiO2/AC催化活性降低程度比TiO2小,但NaHCO3对催化活性的影响是可逆的.     

Ag+-TiO2/AC复合材料的可见光吸附-光催化协同作用

采用水热法制备活性炭负载银掺杂纳米TiO2复合材料(Ag+-TiO2/AC),对样品进行了TEM、XRD、FT-IR和UV-Vis表征,分析了Ag+-TiO2/AC的微结构、吸收谱特性和掺杂银离子后的半导体带隙变化,并研究了其在可见光下对甲基橙溶液(MO)的降解性能。结果表明,水热法不需要高温处理即可得到高活性的锐钛矿相纳米TiO2,Ag+掺杂和AC负载均明显提高TiO2光催化剂的光催化活性,在可见光下光照180 min,0.2 g/L的Ag+-TiO2/AC对10 mg/L的甲基橙溶液的降解率为73.7%,主要由于存在持续的活性炭局域强吸附-TiO2光催化降解协同作用,明显提高了甲基橙的降解效率。     

介孔TiO2的制备及光催化降解有机染料的研究

以十六烷基三甲基溴化胺为模板剂,用溶胶-凝胶法制备了介孔TiO2,用x射线衍射、透射电子显微镜、热重/差热分析及氮气吸附等方法对其进行了分析表征,并用偶氮染料阳离子红X-GRL为目标污染物分析了它的光催化活性.实验结果表明,450℃热处理后的介孔TiO2是锐钛矿型的,平均孔径为18 nm.氮气吸附曲线呈典型的介孔材料Ⅳ型吸附等温线特征.由于介孔TiO2具有较大的比表面积,因此表现出比非介孔TiO2高的光催化活性.     

参杂负载型纳米TiO2降解橙黄G的光催化活性及其动力学研究

采用溶胶-凝胶法和浸渍-焙烧法制备了掺杂Sn（Ⅳ）的TiO2／AC光催化剂，以偶氮染料橙黄G为目标降解物，对光催化反应条件进行了优化。结果表明：利用Sn（IV）掺杂量为2．5at．％的TiO2／AC光催化剂，在进水浓度50mg／L，催化剂的用量12．5g／i，pH值2．0，H2O2 1．5mL／L。主波长为365nm的300W高压汞灯光照条件下，反应60rain，橙黄G的光催化去除率可达99．1％。该反应符合Langmuir-Hinshelwood动力学方程，其速控步为吸附反应。共存阴离子SO4^2-和H2PO4^-，对橙黄G的光催化降解反应均有一定的抑制作用。     

掺Ni^2＋的TiO2颗粒光催化性能的研究

通过溶胶．凝胶法制备掺杂Ni^2＋的纳米TiO2，并用XRD和TEM进行了表征，发现Ni^2＋的掺杂减小了TiO2颗粒的粒径，Ni2＋／TiO2晶型为锐钛型。通过对目标物罗丹明B的光催化降解实验，发现Ni^2＋的掺杂提高了TiO2的光催化活性，其降解罗丹明B的反应遵从一级反应动力学方程，Ni^2＋惨杂量为1．2％时的光催化活性最高。     

TiO_2/AC复合催化剂的制备及其对六氯苯的光催化降解性能研究

以颗粒活性炭（AC）和钛酸丁酯为原料,采用微波辐射法制备TiO2/AC复合光催化剂,并对制备的催化剂进行了表征;采用该催化剂对六氯苯进行光催化降解,确定了六氯苯降解的最佳工艺条件,并就几种外加试剂对TiO2/AC光催化降解六氯苯的强化作用进行了探讨。结果表明,制备的催化剂中TiO2均匀分布在活性炭表面、呈单一的锐钛矿晶型,晶粒生长完善。该催化剂催化降解六氯苯的最佳工艺条件为：pH值为5、TiO2负载量为18.2%、TiO2/AC投加量为0.4 g/L、反应时间为60 min。在此条件下,六氯苯降解效率达90.3%。添加适量的H2O2、AgNO3、K2S2O8、KIO4和KMnO4均能提高TiO2/活性炭对六氯苯的光催化降解效率。5种外加试剂的适宜添加量分别为0.3%、1.0、1.0、0.1和0.1 mmol/L,对TiO2/AC光催化效率的强化作用大小顺序为：H2O2〉AgNO3〉K2S2O8〉KMnO4〉KIO4。     

纳米Bi2O3/TiO2复合光催化剂的制备及性能研究

以光催化效果为评价标准,采用超声波作用下水解法制备Bi2O3／TiO2复合光催化剂,考察了水解条件和Bi2O3掺入量等制备条件对复合光催化剂性能的影响。结果表明,与传统制备方法相比,该方法操作简单、快速;当水和乙醇的比例为4：1时所得样品的光催化活性最好;Bi2O3的掺入拓宽了TiO2对光的吸收范围,提高了TiO2的光催化活性,掺入量（Bi2O3）为0．25％复合光催化剂催化活性最高;复合光催化剂对多种水溶性染料均具有较好的处理效果。     

UV／TiO2薄膜体系光降解酞酸酯研究

采用自制玻璃负载TiO2薄膜，研究了UV-Vis／TiO2以及UV／TiO2／H2O2体系对2种酞酸酯DBP和DEHP的光催化降解情况。研究结果表明，TiO2在暗处对酞酸酯没有降解作用；UV／TiO2体系能有效光降解DBP和DEHP，TiO2具有明显的光催化作用，增强因子分别为，fDBP=2．06，fDEHP=1．53；在一定浓度范围内DBP在UV／TiO2体系中的降解速率与其初始浓度成负一级动力学关系；UV／TiO2／H2O2体系对DBP的光降解能力远大于UV／TiO2和UV／H2O2体系，H2O2能显著提高TiO2的光催化活性。     

膨胀珍珠岩负载TiO2光催化脱色性能的研究

以钛酸四丁酯为原料，膨胀珍珠岩为载体，用溶胶—凝胶法制备可漂浮于水面的负载型TiO2。利用该负载型TiO2对罗丹明B(RB)进行光催化脱色实验，结果表明，浸渍3次的负载型TiO2光催化活性最高，催化剂最佳用量为500mg／100mL RB，经5h光照，对100mL浓度为1mg／L和2．5mg／LRB脱色率分别为76．67％和47．27％；该催化剂使用寿命长，25h后催化剂脱色性能没有减弱，可重复使用；经8h光照，染料废水脱色效果好。     

无机抗菌剂在建筑涂料中的应用研究

研究了5种无机抗菌剂：锌型沸石抗菌剂、银型沸石抗菌剂、氧化锌晶须复合抗菌剂、纳米TiO2光催化抗菌剂和Ca10-x-yTixZny（PO4）6（OH）2复合抗菌剂在涂料中的应用.以对大肠杆菌（E.coli）的灭菌效果评价抗菌性能.结果表明：锌型抗菌涂料的抗菌效果较差,后4种类型抗菌涂料具有很好抗菌效果.但是,银型抗菌剂和氧化锌晶须复合抗菌剂在涂料中存在易引起涂料变色和难分散问题;纳米TiO2光催化型抗菌剂在涂料中易加快涂料老化;而Ca10-x-yTixZny（PO4）6（OH）2复合抗菌剂既具有良好的抗菌性能,又对涂料的基本性能没有影响,它能够应用到抗菌涂料中.     

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.     

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.     

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.     

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.     

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.     

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.     

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.     

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 in pinon pine (Pinus edulis) nuts from los alamos national laboratory lands and the dose from consumption

Abstract

One of the dominant tree species growing within and around the eastern portion of Los Alamos National Laboratory (LANL), Los Alamos, NM, lands is the pinon pine (Pinus edulis). Pinon pine is used for firewood, fence posts, and building materials and is a source of nuts for food—the seeds are consumed by a wide variety of animals and are also gathered by people in the area and eaten raw or roasted. This study investigated the (1) concentration of ³H, ¹³⁷Cs, ⁹⁰Sr, ^totU, ²³⁸Pu, ^{239, 240}Pu, and²⁴¹ Am in soils (0‐ to 12‐in. [31 cm] depth underneath the tree), pinon pine shoots (PPS), and pinon pine nuts (PPN) collected from LANL lands and regional background (BG) locations, (2) committed effective dose equivalent (CEDE) from the ingestion of nuts, and (3) soil to PPS to PPN concentration ratios (CRs). Most radionuclides, with the exception of ³H in soils, were not significantly higher (p < 0.10) in soils, PPS, and PPN collected from LANL as compared to BG locations, and concentrations of most radionuclides in PPN from LANL have decreased over time. The maximum net CEDE (the CEDE plus two sigma minus BG) at the most conservative ingestion rate (10 lb [4.5 kg]) was 0.0018 mrem (0.018 μSv); this is far below the International Commission on Radiological Protection (all pathway) permissible dose limit of 100 mrem (1000 μSv). Soil‐to‐nut CRs for most radionuclides were within the range of default values in the literature for common fruits and vegetables.     

Degradation and sorption of imidacloprid in dissimilar surface and subsurface soils

Degradation and sorption/desorption are important processes affecting the leaching of pesticides through soil. This research characterized the degradation and sorption of imidacloprid (1-[(6-chloro-3-pyridinyl)-methyl]-N-nitro-2-imidazolidinimine) in Drummer (silty clay loam) and Exeter (sandy loam) surface soils and their corresponding subsurface soils using sequential extraction methods over 400 days. By the end of the incubation, approximately 55% of imidacloprid applied at a rate of 1.0 mg kg^?1 degraded in the Exeter sandy loam surface and subsurface soils, compared to 40% of applied imidacloprid within 300 days in Drummer surface and subsurface soils. At the 0.1 mg kg^?1 application rate, dissipation was slower for all four soils. Water-extractable imidacloprid in Exeter surface soil decreased from 98% of applied at day 1 to > 70% of the imidacloprid remaining after 400 d, as compared to 55% in the Drummer surface soil at day 1 and 12% at day 400. These data suggest that imidacloprid was bioavailable to degrading soil microorganisms and sorption/desorption was not the limiting factor for biodegradation. In subsurface soils > 40% of ¹⁴C-benzoic acid was mineralized over 21 days, demonstrating an active microbial community. In contrast, cumulative ¹⁴CO₂ was less than 1.5% of applied ¹⁴C-imidacloprid in all soils over 400 d. Qualitative differences in the microbial communities appear to limit the degradation of imidacloprid in the subsurface soils.