炻器餐饮具的抗菌研究

以一种特种陶瓷--炻器为载体,分别用负载TiO2光催化薄膜和添加抗菌剂的方法进行炻器餐饮具的抗菌研究.结果表明,在紫外光和日光下,表面负载了TiO2膜的炻器灭菌率分别为90%和88%,均高于未负载TiO2膜的炻器,且灭菌率随光强的增加而提高.复合银盐显示了很好的杀菌效果,当釉表层银含量为0.2%时,24 h内对所有细菌的灭菌率为94.6%、总大肠菌群为96.9%.复合锌盐也有一定的灭菌效果,当釉表层锌含量为1.1%时,24 h内对所有细菌的灭菌率为56.8%,总大肠菌群为59.3%.但将TiO2粉末加入炻器表层的釉中,却未显示灭菌作用.对掺杂的炻器表面层成分和掺杂后Ag 、Zn2 的溶出量进行了测定,对灭菌结果和机理也进行了讨论.     

银钛共负载型光催化材料降解甲基橙废水

以膨胀珍珠岩为载体，采用溶胶凝胶法对其进行负载，制备出不同类型的光催化材料（TiO2．EP、Ag＋-TiO2-EP），并在模拟日光条件下，研究其对甲基橙溶液的降解效果。结果表明，浸渍3次且担载0．04％Ag＋的负载型TiO2光催化活性最高，在光催化剂用量为0．3g，20mL初始浓度为10mg／L甲基橙溶液光照4h后降解率可达81．6％，且甲基橙的光催化降解服从一级动力学方程。回收3次后仍有较强的活性，其2h降解率为24．8％。     

掺碘二氧化钛薄膜自组装制备、表征及光催化性能

通过自组装技术在低温液相反应体系中制备出大尺寸纳米二氧化钛及其掺碘薄膜。使用XRD、TEM、荧光发射光谱仪、激光拉曼光谱仪等手段对样品进行表征，发现掺I^5＋后的二氧化钛薄膜在可见光区也表现出明显的响应，而且合成的I^5＋／TiO2纳米薄膜在TEMggNT其晶型显示为金红石型，并且碘掺杂后样品的拉曼光谱强度减弱，峰位蓝移且宽化。掺杂I^5＋原溶液浓度为2mmol／L时，其可见光下光催化效果最优，5h后降解率可达到95％，较未掺杂的TiO2纳米薄膜提高了40％，I^5＋掺杂明显提高了TiO2对甲基橙溶液的光催化降解效率。     

光催化三维蜂窝陶瓷网净化室内空气的研究

先制备钛酸溶胶和掺杂Fe3 的钛酸溶胶,用溶胶-凝胶法分别将其负载于具有一定厚度的矩形蜂窝陶瓷三维网载体上,再用程序升温法煅烧.得到复合纳米TiO2光催化三维蜂窝陶瓷网.经扫描电镜(SEM)测定,三维蜂窝陶瓷网体上负载膜的厚度为300～400 nm,TiO2的粒径为15～20 nm.将光催化三维蜂窝陶瓷网置于光处理箱体内,在紫外光强、循环风量一定的条件下,对容积为72.6 m3和81.4 m3房间进行空气净化.结果表明,无论掺Fe3 与否的TiO2光催化三维蜂窝陶瓷网都有净化效果,其中以掺Fe3 的效果最好:当甲醛起始浓度为0.404 mg/m3,18 h的去除率为99.5%;当起始细菌总数为924 cfu/m3,24 h后的灭菌率为99.5%.     

Ce掺杂纳米TiO2光催化剂的制备及降解甲醛的研究

介绍了溶胶-凝胶法制备Ce离子掺杂纳米TiO2的工艺流程。采用X射线衍射（XRD）、紫外可见分光光度法（UV-Vis）等方法表征了Ce掺杂TiO2的相组成、紫外可见漫反射率与掺杂量的关系。结果表明，掺杂的TiO2在520℃．650℃焙烧2h呈锐钛矿结构，在520℃焙烧2h的TiO2的晶粒尺寸大约为20nm，而掺杂Ce后其晶粒尺寸均减小，大约为12nm。UV-Vis吸光度分析表明，掺Ce后吸收带边明显发生红移，但随着Ce掺杂浓度的增大，其对可见光的吸收影响不大。光催化降解反应表明，未掺杂Ce的TiO2反应2h后对甲醛的没有降解作用，而Ce掺杂TiO2反应2h后甲醛降解率达15％。     

微米级负载型TiO2催化剂在光催化-膜分离反应器中的应用

基于光催化．膜分离三相流化床反应器的结构特点及膜分离特性，以微米级MCM-41分子筛为载体，采用原位生成法制备微米级负载型TiO2催化剂。针对微米级负载型TiO2催化剂在光催化一膜分离反应器中的分布特性、悬浮特性、分离特性及膜污染特性进行研究。结果表明，曝气量一定的情况下，微米级负载型TiO2催化剂在光催化一膜分离反应器中具有良好的悬浮特性，且优于纳米TiO2。随着催化剂投加量的增加，悬浮浓度也随之增加。光催化反应器底部曝气0．3m。／h、催化剂投加量为1g／L时为宜。膜分离器中催化剂悬浮浓度明显低于光催化反应器；该微米级催化剂与纳米TiO2相比具有不粘附、不堵塞膜孔等优良特性，能够有效降低膜污染，延长分离膜使用寿命。膜底曝气为0．1m3／h时，反应器连续运行5h（未加反冲洗）后，微米级负载型TiO2催化剂和纳米TiO2对膜组件的污染程度分别为膜通量衰减率4．3％和37．4％。反应器连续运行72h，膜组件依然具有很好的分离特性。     

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。     

纳米TiO2薄膜在不同陶瓷表面的负载及其光催化性能研究

利用2种不同表面处理的陶瓷作为载体，用溶胶凝胶法在其表面进行了纳米TiO2光催化薄膜的负载。采用X射线衍射法（XRD）、X射线光电于能谱仪（XPS）和扫描电镜（SEM）对薄膜的粒径、横断面及表面组成进行了表征和分析，结果表明，TiO2的平均粒径约为15nm，釉面陶瓷TiO2薄膜分布均匀，膜厚约为300nm；无釉陶瓷TiO2薄膜分布不均，膜层不明显；2种载体中的一些基质离子在TiO2薄膜有渗透。苯酚的降解实验表明，以2种不同表面处理的陶瓷为载体的TiO2薄膜对苯酚的降解均符合一级反应动力学，就催化活性而言，TiO2／釉面陶瓷〉TiO2／无釉陶瓷，分析认为基质渗透的Ca^2＋有降低TiO2光催化活性的作用；该薄膜对实际生产多菌灵废水具有催化降解作用。重复降解实验20次，TiO2／釉面陶瓷和TiO2／无釉陶瓷对苯酚的去除率仅分别降低9％和6％。     

TiO2/Ti及其改性处理聚乙二醇模拟废水

采用溶胶-凝胶法制备TiO2/Ti负载体系,并以聚乙二醇2000（PEG-2000）为模拟废水对其光催化性能进行研究。实验表明,TiO2/Ti的最佳负载条件为镀膜层数8层、pH值为3、焙烧温度700℃、焙烧时间2 h,掺杂Fe3＋、Ag＋、La3＋、Pt4＋4种金属离子均可有效提高TiO2/Ti对PEG-2000模拟废水的处理效果,在Ag＋掺杂量为0.3%、焙烧温度800℃时,2.5h反应后的COD去除率达到了79.5%。XRD分析表明,金属离子的加入抑制了TiO2由锐钛矿相向金红石相转化。GC-MS分析表明,PEG-2000的光催化是大分子分解为小分子然后被矿化的过程。     

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。     

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.     

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.     

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.     

Radionuclides in deer and elk from Los Alamos national laboratory and the doses to humans from the ingestion of muscle and bone

Abstract

This paper summarizes radionuclide concentrations (³H, ⁹⁰Sr, ¹³⁷Cs, ²³⁸Pu, ^239,240Pu, ²⁴¹Am, and ^totU) in muscle and bone tissue of mule deer (Odocoileus hemionus) and Rocky Mountain elk (Cervus elaphus) collected from Los Alamos National Laboratory (LANL), Los Alamos, New Mexico, lands from 1991 through 1998. Also, the committed effective dose equivalent (CEDE) and the risk of excess cancer fatalities (RECF) to people who ingest muscle and bone from deer and elk collected from LANL lands were estimated. Most radionuclide concentrations in muscle and bone from individual deer (n = 11) and elk (n = 22) collected from LANL lands were either at less than detectable quantities (where the analytical result was smaller than two counting uncertainties) and/or within upper (95%) level background (BG) concentrations. As a group, most radionuclides in muscle and bone of deer and elk from LANL lands were not significantly higher (p<0.10) than in similar tissues from deer (n = 3) and elk (n = 7) collected from BG locations. Also, elk that had been radio collared and tracked for two years and spent an average time of 50% on LANL lands were not significantly different in most radionuclides from road kill elk that have been collected as part of the environmental surveillance program. Overall, the upper (95%) level net CEDEs (the CEDE plus two sigma for each radioisotope minus background) at the most conservative ingestion rate (50 lbs of muscle and 13 lbs of bone) were as follows: deer muscle = 0.22 mrem y^‐1 (2.2 μSv y^‐1), deer bone = 3.8 mrem y^‐1 (38 μSv y^‐1), elk muscle = 0.12 mrem y^‐1 (1.2 μSv y^‐1), and elk bone = 1.7 mrem y^‐1 (17 μSv y^‐1). All CEDEs were far below the International Commission on Radiological Protection guideline of 100 mrem y^‐1 (1000 μSv y^‐1), and the highest muscle plus bone net CEDE corresponded to a RECF of 2E‐06, which is far below the Environmental Protection Agency upper level guideline of 1E‐04.     

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.