CdS-TiO2/MWCNTs结构表征及其光催化性能

采用溶胶-凝胶法,制备了多壁碳纳米管（MWCNTs）负载的双组分复合半导体光催化剂CdS-TiO2/MWCNTs。通过透射电镜（TEM）、比表面分析（BET）、X射线衍射（XRD）和紫外-可见吸收光谱（UV-vis）等分析方法对光催化剂进行了结构表征,并考察了CdS-TiO2/MWCNTs对甲苯降解的光催化性能。结果表明：纳米活性粒子CdS-TiO2均匀负载于MWCNTs上,比表面积、光吸收阈值和强度增大,活性粒子间以及活性粒子与载体之间具有协同作用,有利于光催化性能的提高,CdS-TiO2/MWCNTs在主波长为254 nm紫外光照射下对甲苯的降解效果较好,去除率可达55.3%。     

汉沙黄/TiO_2光催化剂的制备及其光催化活性

采用溶剂热合成法制备了一种新型的汉沙黄/TiO2复合物光催化剂,利用多种手段SEM、XRD、FT-IR对催化剂的样品形貌、结构进行表征。分别以罗丹明B、亚甲基蓝、中性红为目标降解物,考察了可见光下溶液pH值对催化剂的吸附性能和催化活性的影响。结果表明,敏化后的TiO2对光的响应由紫外区扩展到可见区,催化活性优于纯TiO2,对上述3种染料的吸附率分别为19.2%、29.2%和43.2%,降解率分别为98.6%、92.5%和97.8%。制备的汉沙黄/TiO2光催化剂稳定性好,重复使用率高,在印染废水处理中具有很好的应用前景。     

LiFePO_4非均相Fenton法处理亚甲基蓝染料的研究

采用水热法制备出LiFePO4催化剂,通过电子显微镜（SEM）、X射线衍射（XRD）和傅立叶红外光谱（FTIR）对其进行表征,并将其作为非均相Fenton催化剂处理亚甲基蓝（MB）染料溶液。实验结果表明,在催化剂用量为4 g/L,H2O2浓度为0.04 mol/L,pH值为3,温度为50℃,反应时间为60 min的条件下,浓度为500 mg/L的亚甲基蓝脱色率达99%。根据实验结果,讨论了LiFePO4作为非均相Fenton催化剂对亚甲基蓝的降解机理。     

陶瓷负载Ag、Ce共掺杂TiO_2光催化剂降解甲基橙的研究

以陶瓷为载体,采用溶胶-凝胶法制备了银离子和铈离子共掺杂TiO2的负载型光催化剂——T-AC/陶瓷,研究了pH值、双氧水用量、催化剂用量、紫外灯强度、废水的初始浓度等因素对T-AC/陶瓷光催化剂降解甲基橙染料废水的影响。结果表明,当pH为2、双氧水用量为0.5 mL/100 mL、催化剂用量为3 g/L、紫外灯功率为20 W、废水初始浓度为10mg/L时,甲基橙的降解率可达85.9%,并且甲基橙的光催化降解属于一级动力学方程,T-AC/陶瓷催化剂有较高的活性和稳定性,在废水处理中具有较好的应用前景。     

陶瓷负载Ag、Ce共掺杂TiO2光催化剂降解甲基橙的研究

以陶瓷为载体,采用溶胶-凝胶法制备了银离子和铈离子共掺杂TiO2的负载型光催化剂——T-AC/陶瓷,研究了pH值、双氧水用量、催化剂用量、紫外灯强度、废水的初始浓度等因素对T-AC/陶瓷光催化剂降解甲基橙染料废水的影响。结果表明,当pH为2、双氧水用量为0.5 mL/100 mL、催化剂用量为3 g/L、紫外灯功率为20 W、废水初始浓度为10mg/L时,甲基橙的降解率可达85.9%,并且甲基橙的光催化降解属于一级动力学方程,T-AC/陶瓷催化剂有较高的活性和稳定性,在废水处理中具有较好的应用前景。     

溴掺杂TiO2光催化剂的制备与性能研究

以KBr和Ti（SO4）2为原料,通过水热法制备了高催化活性的溴掺杂纳米TiO2（Br-TiO2）光催化剂,利用XRD、XPS、TEM、BET和UV-Vis DRS等测试手段对其进行了表征。通过苯酚降解实验评价了Br-TiO2的光催化活性。结果表明,700℃焙烧、溴与钛的摩尔比为0.35∶1时,Br-TiO2具有最佳光催化活性。该催化剂为晶体发育完整的锐钛矿相TiO2,粒径平均大小为50 nm,比表面积为16.81 m2/g,在紫外区的吸收得到加强,光催化能力优于Degussa P-25。确定了降解苯酚的最佳条件：催化剂投加量为0.5 g/L,苯酚初始浓度为10 mg/L,pH值为6.0。     

电生成Fenton试剂光催化降解孔雀石绿的研究

为了提高染料废水的处理效果,采用电生成Fenton试剂光催化氧化系统对孔雀石绿模拟印染废水进行了降解研究,通过与无光照时的对比实验发现:光照能明显加快电生成Fenton试剂对孔雀石绿印染废水的降解脱色速率,20 min内脱色率达到98%以上,40 min内COD去除率达到80%以上,同时通过红外光谱、紫外-可见光谱等手段研究了光照与电生成Fenton试剂的协同作用,初步探讨了电生成Fenton试剂光催化降解孔雀石绿印染废水的反应机理,很好地实现了光催化与电化学氧化降解技术的联合应用。     

Cu_2O/Bi_2MoO_6光催化剂的制备、表征与性质研究

通过溶剂热法成功合成了一系列不同掺杂比的Cu2O/Bi2MoO6复合纳米光催化剂,利用X射线衍射(XRD)、拉曼(Raman)光谱、透射电子显微镜(TEM)、X射线光电子能谱(XPS)和紫外—可见漫反射光谱(DRS)等手段对所得产物进行表征。以染料结晶紫为模拟污染物,研究了所合成产物的光催化性能。结果表明,Cu、Mo摩尔比为0.08的复合纳米光催化剂的光催化效率最高,可见光照射100min对结晶紫溶液的降解率可达95.60%。此外,探讨了Cu2O掺杂量对光催化剂性能的影响,提出了可能的光催化反应机制。     

GeO_2改性TiO_2催化超声降解活性红（M-3BE）染料废水的应用研究

制备了经GeO2改性的纳米TiO2,并用之作为超声降解活性红M-3BE反应的催化剂,研究了各种因素对制备的GeO2改性的纳米TiO2催化超声降解活性红染料废水的影响,并用XRD,SEM等手段对催化剂进行了表征。结果表明：GeO2改性的纳米TiO2作为催化剂,其对超声降解活性红染料废水的催化剂作用明显优于单纯以锐钛矿型T...     

Cu~(2+)-TiO_2/偕胺肟纤维的制备及其光催化降解性能

以偕胺肟纤维为配体和载体,常温下通过"配位-水解"方法,制备Cu~(2+)改性TiO_2/偕胺肟纤维复合材料(Cu~(2+)-TiO_2/AOCF)。采用XRD、SEM和EDS对Cu~(2+)-TiO_2/AOCF晶体结构、形貌和表面成分进行分析表征。结果表明,TiO_2纳米颗粒均匀分布在纤维表面,呈无定型态。以光催化降解活性黄染料的降解率为指标,优化了制备工艺条件,结果显示,Cu~(2+)-TiO_2/AOCF的最佳制备条件:氯化铜浓度c=1.5 mmol·L~(-1)、掺杂时间t=20 min、pH=3.0。对活性黄和甲基橙的光催化降解反应表明,当染料溶液pH=2.0、太阳光光源、催化剂用量为0.500 0 g·L~(-1)时,催化降解效率能达到95.7%。催化剂可重复使用6~8次且能保持光催化能力,2种溶液的催化降解反应均符合一级反应动力学特征。紫外可见光谱(UV-vis)和光致发光光谱(PL)分析表明,Cu~(2+)的改性降低了TiO_2禁带宽度,使其光谱响应范围变宽。     

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.     

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.     

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.     

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.