纳米二氧化钛负载改性天然高分子材料的研究

对丝瓜络及纳米二氧化钛进行接枝改性处理,再以戊二醛为中间反应物进行丝瓜络及纳米二氧化钛的交联反应从而在丝瓜络表面形成纳米二氧化钛薄膜,制备复合光催化剂。通过傅立叶变换红外光谱仪(FTIR)及扫描电子显微镜(SEM)对样品结构、形貌进行了分析表征,表明纳米二氧化钛通过KH550的连接负载到了丝瓜络表面;室温下,以甲基橙为底物在365nm波长的紫外光照射下进行光催化降解试验,结果表明,复合光催化剂对甲基橙的催化降解率达到32.21%,且重复性光降解试验表明其可持续光降解能力较好。     

微生物燃料电池驱动的光电催化降解甲基橙

实验制备出了具有光催化性能的Cu2O纳米线电极,对比研究了Cu2O电极在光催化、微生物燃料电池驱动的电催化和微生物燃料电池驱动的光电催化反应过程中对甲基橙溶液的降解效果的影响。实验结果表明,微生物燃料电池驱动的光电催化反应对甲基橙的降解效果最好,当溶液p H为3、外加偏压为0.7 V、反应时间为40 min时,对甲基橙的降解率可以达到83%。实验首次利用微生物燃料电池作为外界驱动电压光电协同降解了甲基橙,证明在微生物燃料电池产生的较低电压也可以对光电极催化降解污染物的效率有提升。     

二氧化钛/碳纳米管/壳聚糖薄膜的制备及对苯的降解性能

研究了光催化降解挥发性有机化合物过程中催化剂二氧化钛/碳纳米管/壳聚糖薄膜的制备以及该催化剂对苯的光催化性能。首先采用溶胶-凝胶法制备纳米复合材料二氧化钛/碳纳米管,然后利用壳聚糖作为交联剂,制得二氧化钛/碳纳米管/壳聚糖复合材料催化薄膜。通过傅立叶红外光谱(FT-IR)、X射线衍射(XRD)透射电镜扫描(TEM)和紫外-可见光漫反射(UV-Vis)等技术分析了复合材料薄膜的组成、结构、形貌和对光的吸收性能,然后使用该催化剂对室内常见的污染物苯进行降解,并在同样的实验条件下,使用催化剂二氧化钛(P25)/壳聚糖对苯进行降解,对两者催化性能进行对比,结果表明,二氧化钛/碳纳米管/壳聚糖对苯有更强的吸附能力和更高的催化活性。     

TiO2/CdS复合半导体光催化剂降解甲基橙的实验研究

采用Sol-Gel法制备TiO2/CdS复合半导体光催化剂,以8 W-365 nm的紫外灯为光源、甲基橙溶液模拟染料废水、在自制的光催化反应器中研究TiO2/CdS的光催化活性和光催化降解甲基橙的特点和规律.结果表明,当CdS掺入量为0.5%(摩尔比)时,TiO2/CdS的光催化活性最高;当CdS的掺入量＞3.5%(摩尔比)时,TiO2/CdS光催化剂的光催化活性低于TiO2的光催化活性;对初始浓度为15 mg/L的甲基橙溶液处理2.5 h后,脱色率可达44%;甲基橙的光催化降解反应符合Y=A B1×X B2×X2动力学模型.     

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%.     

石墨烯/TiO_2复合物的制备及其光催化性能

为拓展二氧化钛(TiO_2)在可见光区的光响应范围,在140℃水热条件下制备了不同氧化石墨烯含量的石墨烯/二氧化钛(RGO/TiO_2)复合材料。利用X-射线粉末衍射仪(XRD)、扫描电子显微镜(SEM)等对材料进行了表征。以甲基橙为目标污染物,研究了在模拟太阳光和紫外光照下TiO_2和RGO/TiO_2对甲基橙的光催化降解性能。结果表明,TiO_2和GO复合后,TiO_2由原来单一的金红石型转变为金红石型和锐钛矿型并存,出现了混晶效应;在模拟太阳光的条件下,复合材料的催化活性均高于TiO_2本身;光照4 h后80 mg氧化石墨烯添加量制备的复合材料对甲基橙的光催化降解率达到69.58%,是TiO_2的1.65倍;在紫外光照1.5 h时,复合材料对甲基橙的降解率达到了70%。由此可知,石墨烯的存在能够促进TiO_2半导体中电子和空穴的有效分离,显著提高了TiO_2光催化剂对可见光的响应。     

Ag@AgCl/BiVO_4复合光催化剂的制备及光催化性能

以硝酸铋作为铋源,偏钒酸铵作为钒源,利用水热法合成钒酸铋前驱体,并以此作为载体,采用沉淀和光还原法将Ag@AgCl负载其上,制备了Ag@AgCl/BiVO_4复合光催化剂。同时,利用X射线粉末衍射仪、紫外-可见漫反射光谱、X射线光电子能谱对所制备的复合催化剂进行表征。结果表明,BiVO_4经过负载Ag@AgCl进行修饰后,对可见光的响应吸收更加明显,复合物的光催化活性有明显提高。通过可见光照射催化降解甲基橙的实验,可发现该复合光催化剂对甲基橙的降解效率较纯BiVO_4提高了约73%。     

负载工艺对ACF担载二氧化钛光催化性能的影响

采用分散液中添加环氧树脂黏结剂并进行热处理的方法,制备出活性炭纤维(ACF)担载二氧化钛光催化材料。并对光催化材料的表面形貌和孔结构进行表征,评价复合光催化材料对亚甲基蓝溶液的光催化降解性能。重点探讨了负载方式、负载时间以及光催化剂的添加量等方面对光催化活性的影响。研究表明,当采用浸渍方式、负载时间控制在15 min左右、光催化剂添加量达11 g/L时,ACF/TiO2光催化复合材料中光催化剂负载量最佳,在15%左右,对亚甲基蓝(初始浓度为50 mg/L)的降解效果最好,在2 h内可以达到90%。     

磷钨酸光催化降解甲基橙溶液的研究

以磷钨酸为光催化剂,在紫外灯照射下,对模拟染料废水甲基橙溶液进行光催化降解,并研究了催化剂加入量、pH值、甲基橙初始浓度和外加氧化剂H2O2对光催化降解效果的影响.结果表明,磷钨酸光催化剂加入量为300 mg/100 mL,pH=2.5时,甲基橙溶液的降解率明显高于其他pH值的降解率;在较低浓度下,甲基橙溶液的光催化降解反应符合一级动力学方程;外加氧化剂H2O2可提高光催化反应速率.     

Cu^2＋对TiO2光催化活性的影响

采用搅拌式光催化反应器，以中压汞灯作光源，甲基橙为模型化合物，考察了Cu^2 对TiO2光催化活性的影响。研究发现，在此反应体系中甲基橙的降解为一级反应，甲基橙的光催化降解速率与光强度成正比，TiO2光催化剂的投加量为150mg／L、Cu^2 的加入量为200μg／L时光催化效果最佳。     

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.