焦炭负载改性纳米TiO2阳光催化降解染料模拟废水的初步研究

以焦炭为载体，Na2SiO3为粘结剂，制备了负载型铁改性纳米TiO3光催化剂，并研究了该催化剂在太阳光照射下降解亚甲基兰染料废水的效果，通过正交和单因素优化试验，探讨了影响染料废水降解效果的主要因素，研究结果表明，影响降解因素的大小次序是：煅烧时间〉铁掺杂量〉Na2SiO3质量百分比〉煅烧温度。本光催化剂制备的最佳制备条件是：以20％的Na2SiO3溶液为粘结剂，掺杂2％的Fe，400℃煅烧温度下煅烧3h。以太阳光为光源，亚甲基兰染料废水的降解率可达到87．1％。     

混晶TiO_2微纳米管的制备及其对亚甲基蓝染料的光催化降解性能研究

以偕胺肟纤维为模板纤维,通过优化TiCl4浓度、煅烧温度和煅烧时间制备了混晶TiO_2微纳米管,并考察了其对亚甲基蓝的光催化降解性能。结果表明,制备的混晶TiO_2微纳米管中含有锐钛矿和金红石两种晶相。其最佳制备条件:TiCl4摩尔浓度为0.022mol/L、煅烧温度为600℃、煅烧时间为30min。混晶TiO_2微纳米管对亚甲基蓝具有较好的光催化降解性能,太阳光源下降解5h,降解率可达89.44%。     

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。     

ZnO/TiO_2光催化剂的制备及太阳光催化降解苯酚的研究

以溶胶-凝胶法和等体积浸渍法制备了ZnO/TiO_2光催化剂(分别表示为SG-w%ZnO/TiO_2、JZ-w%ZnO/TiO_2,其中w%为ZnO占TiO_2的质量分数),采用X射线衍射(XRD)、红外光谱(IR)、紫外—可见吸收光谱(UV-Vis)和扫描电子显微分析镜(SEM)-能量弥散X射线谱(EDS)表征了各光催化剂的物相结构,考查了光催化剂制备方法、ZnO掺杂量、焙烧温度、苯酚初始浓度、降解时间对太阳光催化降解苯酚活性的影响,并探讨了太阳光催化降解苯酚的反应机理。结果表明:(1)500℃下煅烧2h制备的SG-0.5%ZnO/TiO_2、JZ-0.5%ZnO/TiO_2中TiO_2均以锐钛矿相存在,ZnO掺杂有利于提高光催化剂的太阳光催化性能。(2)在太阳光照射4h、光催化剂用量为2g/L、苯酚初始质量为10 mg/L的条件下,JZ-0.5%ZnO/TiO_2对苯酚的降解率可达61%,优于商用TiO_2(P25)。     

铁碳微电解填料制备及其对亚甲基蓝的降解

针对传统铁碳微电解工艺中填料易板结的问题,在较低的烧结温度800℃条件下,将铁、活性炭、粘结剂和催化剂按一定配料比混合烧结4 h制备了一种铁碳微电解填料。将印染废水中的染料成分亚甲基蓝作为目标污染物,探究溶液pH、铁碳材料添加量和亚甲基蓝起始浓度等反应条件对亚甲基蓝降解效率的影响。在pH=3,铁碳投加量30 g·L~(-1),亚甲基蓝浓度10 mg·L~(-1)的条件下,亚甲基蓝的去除率达到55%左右;相同条件下对于微电解填料的循环使用实验中亚甲基蓝的去除率能维持在50%以上,证明了该微电解填料具有连续运行的能力。另外,通过微电解与芬顿反应联用的初步实验发现联用效果对于亚甲基蓝的降解率能大幅度提升至90%以上,证明微电解与芬顿反应联用具有较大的应用潜力。     

具有可见光活性的氮掺杂TiO_2光催化剂的制备及光催化性能

采用浓氨水处理Ti(SO4)2溶液,然后经过滤、干燥、煅烧制备了一种氮掺杂TiO2光催化剂TiO2-XNX,其最佳煅烧温度为400℃。对该光催化剂的XRD谱图进行分析,结果表明,TiO2-XNX的晶型为锐钛矿相。紫外—可见吸收光谱表明,该光催化剂在可见光区具有明显的吸收。甲基橙溶液的降解实验结果表明,制备的TiO2-XNX光催化剂具有可见光(波长λ400nm)活性。     

氧化锌纳米材料的制备及其光催化性能

以醋酸锌为原料,丙烯酰胺为单体,N,N’-亚甲基双丙烯酰胺为网络剂,过硫酸铵为引发剂,采用高分子网络凝胶法制备得到纳米Zn O粉末。用制得的粉体对染料废水进行光催化降解实验,并用XRD、TEM、XPS等测试技术对其进行表征。分析结果表明,单体和网络剂质量占溶液质量3%、煅烧温度为700℃时制备的纳米Zn O光催化效果最好,高压汞灯下反应1 h,活性黄、亚甲基蓝和酸性大红的脱色率分别达到94.3%、92.2%和88.6%。     

Fe/TiO2光催化降解水溶液中的4-氯苯酚

以TiO2-P25及FeC2O4为前驱物制备了Fe3 掺杂TiO2光催化剂--Fe/TiO2.X射线衍射结果表明,500 ℃煅烧温度下的Fe/TiO2主要是锐态矿晶型,当掺Fe3 量为0.5%(质量分数,下同)时,Fe3 以取代掺杂形式进入TiO2晶格,而当掺Fe3 量达5.0%时,则出现α-Fe2O3的特征衍射峰;900 ℃煅烧温度下的Fe/TiO2则均为金红石晶型,掺Fe3 量达2.0%～5.0%时,出现Fe2TiO5的特征衍射峰.4-氯苯酚的光催化实验结果表明,煅烧温度及Fe3 掺杂量对Fe/TiO2的光催化活性有显著影响,以煅烧温度500 ℃及掺Fe3 量0.5%的Fe/TiO2为光催化剂,反应80 min,4-氯苯酚的降解率达100%,总有机碳去除率约95%.     

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%。     

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.