气-固流化床光催化氧化甲苯的研究

在自制的流化床光催化反应装置中研究了中低浓度（28～140 mg/m^3）甲苯的气相光催化降解过程,考察了光照时间、初始浓度、表观气速和催化剂负载量等因素对甲苯光催化降解率的影响规律.结果表明,紫外灯照射约1.5 h,甲苯的转化率达最大值,甲苯初始浓度越低,维持此最大值的时间越久;在一定低浓度范围内（28～55 mg/m^3）,甲苯的转化率不随浓度变化,符合一级反应动力学,浓度进一步增加,则甲苯的转化率下降;表观气速和催化剂负载量的最佳值分别为3.3Umf和0.19 g TiO2/g SiO2.     

TiO2/EP光催化降解水体中微污染磺胺嘧啶的研究

制备了膨胀珍珠岩（EP）为载体的TiO2催化剂（TiO2/EP）,对使用较为广泛的抗生素磺胺嘧啶（SDZ）进行了光催化降解研究,探讨了TiO2的负载量、溶液的初始浓度、初始pH、无机离子（HCO3^-、SO4^2-和Cl^-）和腐殖酸（HA）对SDZ降解效果的影响。结果表明：SDZ的光催化降解符合一级反应动力学方程;当TiO2最佳负载量为20 wt%,SDZ浓度为5 mg/L,pH=6.7,紫外光照射强度为1 000μW/cm^2,反应时间为45 min时,SDZ的降解率达到96%;HCO3^-在低浓度时能促进SDZ的光催化降解,高浓度时促进作用不明显;SO4^2-和Cl^-对SDZ的光催化降解有轻微的抑制作用;HA对SDZ光催化降解有显著的抑制作用,浓度越高,抑制作用越强。UV-TiO2/EP是一种去除水体中微污染SDZ的有效方法。     

TiO_2/EP光催化降解水体中微污染磺胺嘧啶的研究

制备了膨胀珍珠岩(EP)为载体的TiO2催化剂(TiO2/EP),对使用较为广泛的抗生素磺胺嘧啶(SDZ)进行了光催化降解研究,探讨了TiO2的负载量、溶液的初始浓度、初始pH、无机离子(HCO3-、SO42-和Cl-)和腐殖酸(HA)对SDZ降解效果的影响。结果表明:SDZ的光催化降解符合一级反应动力学方程;当TiO2最佳负载量为20 wt%,SDZ浓度为5 mg/L,pH=6.7,紫外光照射强度为1 000μW/cm2,反应时间为45 min时,SDZ的降解率达到96%;HCO3-在低浓度时能促进SDZ的光催化降解,高浓度时促进作用不明显;SO42-和Cl-对SDZ的光催化降解有轻微的抑制作用;HA对SDZ光催化降解有显著的抑制作用,浓度越高,抑制作用越强。UV-TiO2/EP是一种去除水体中微污染SDZ的有效方法。     

新型管状光催化反应器降解VOCs特性

以一种新型折流式管状光催化反应器为研究对象,选择甲醛、苯和甲苯为目标污染物,以紫外光源、催化剂负载量和反应器内循环流量为关键影响因素,利用非密闭型环境舱,分析了反应器降解室内VOCs特性。结果表明,在254 nm和365 nm紫外光源照射下,VOCs的总衰减系数随初始浓度的增加而增大,且254 nm紫外光源照射下的总衰减系数更大。365 nm紫外光源照射时,VOCs的反应有效度随催化剂负载量的增加而增大;254 nm紫外光源照射时,反应有效度受催化剂负载量变化的影响很小。VOCs的转化率随循环流量的增加而增大,而反应速率受循环流量的影响较小;相同的循环流量下,转化率和反应速率均随着VOCs初始浓度增加而增大。由于增设肋片,折流式管状反应器比传统无肋片管状反应器的洁净空气量提升60%,且反应有效度更接近0.5,说明前者的传质-反应速率更加匹配,降解性能明显更优。     

固定化催化剂TiO2膜光催化降解三氯乙醛的研究

研究了负载于玻璃上的固定化催化剂TiO2膜光催化降解水中三氯乙醛的效果,探讨了TiO2膜光催化降解三氯乙醛的机理,考察了溶液pH值和三氯乙醛初始浓度埘TiO2膜光催化降解三氯乙醛的影响,并研究了固定化催化剂TiO2膜光催化降解三氯乙醛的动力学.结果表明,固定化催化剂TiO2膜光催化降解水中三氯乙醛的效果良好,当三氯乙醛初始浓度为2.25 mg/L时,在紫外光照时间3 h下,三氯乙醛的降解率高达100%.在相司紫外光照时间下,三氯乙醛的光催化降解率随着三氯乙醛初始浓度的增大而下降.在溶液pH=6.5时,三氯乙醛的降解效率最高.固定化催化剂TiO2膜光催化降解三氯乙醛的反应遵循一级反应动力学,反应速率常数随三氯乙醛初始浓度的增大而减小.     

臭氧光催化降解水中甲醛的研究

研究比较了3种光化学方法对水中低浓度甲醛的降解效果,考察了初始pH值、甲醛浓度和臭氧投加速率等因素对臭氧光催化(TiO_2/UV/O_3)降解甲醛的影响。结果表明,紫外臭氧(UV/O_3)、光催化(TiO_2/UV)和TiO_2/UV/O_3对甲醛的降解均符合表观一级反应动力学,TiO_2/UV/O_3降解甲醛的一级表观速率常数大于TiO_2/UV与UV/O_3之和,说明臭氧、光催化有明显的协同作用。pH值对臭氧光催化降解甲醛的速率几乎没有影响;甲醛初始浓度增加,表观反应速率常数下降,但甲醛的绝对去除量仍随初始浓度的增加而显著增加;臭氧投加速率增加,降解速率增加。甲醛降解的主要中间产物为甲酸,但甲酸在臭氧光催化反应过程中也快速降解而被矿化,说明臭氧光催化是一种能安全有效去除甲醛的方法。     

壳聚糖/纳米CdS复合颗粒可见光光催化降解猩红B动力学研究

采用仿生矿化法制备了壳聚糖/纳米CdS复合颗粒光催化剂,并用于可见光光催化降解猩红B染料模拟废水,研究了猩红B初始浓度、pH、催化剂投加量和催化剂重复使用次数等因素对猩红B光催化降解的影响.X射线衍射(XRD)分析表明,壳聚糖能有效负载CdS纳米微晶.采用Langmuir-Hinshelwood模型描述壳聚糖/纳米CdS复合颗粒可见光光催化降解猩红B反应动力学行为,在猩红B初始质量浓度较低(≤20 mg/L)时,光催化降解过程符合假一级动力学方程.降低猩红B初始浓度和溶液pH都可显著增大光催化降解速率常数;催化剂投加量小于0.7 g/L时,光催化降解速率随其增加而增大,但催化剂投加量过大会使光催化降解速率减小;催化剂重复使用第5次时,猩红B光催化降解速率常数仍为第1次使用时的63.4%.     

低温等离子体联合技术降解甲苯气体的研究

以自制的纳米钛酸钡基介电材料为催化剂,以电工陶瓷拉西环为载体,利用介质阻挡放电产生的低温等离子体对常压下流动态含甲苯的空气进行处理,研究了电场强度、空塔气速、甲苯初始浓度及不同填料情况下甲苯的降解及臭氧产生情况,初步探讨了等离子体联合技术降解甲苯的机制,并进行了产物分析.实验结果表明,甲苯降解率随电场强度的提高而上升,随空塔气速和甲苯初始浓度的增加而降低;随反应器内填料变化,甲苯降解率表现为催化剂填料》普通填料》无填料,其降解率最高可达95%.当电场强度》13.0 kV/cm时,臭氧浓度因受到过量的高能电子攻击而发生分解,表现为臭氧浓度随电场强度的继续增加而降低,故最佳电场强度为13.0 kV/cm.当9.0 kV/cm＜电场强度＜13.0 kV/cm,臭氧产量表现为催化剂填料＞普通填料＞无填料,纳米钛酸钡基介电材料大大增强了臭氧的产量.     

微波辅助光催化降解阿特拉津的表观动力学

以内分泌干扰物阿特拉津为目标物,建立循环流化床微波辅助光催化体系,研究其微波辅助光催化降解规律。表观动力学研究发现,当阿特拉津初始浓度较低时,其在微波辅助光催化体系中的降解符合表观一级反应动力学特征。降解反应速率常数与阿特拉津初始浓度呈负线性相关,与紫外光强呈正线性相关,与催化剂浓度呈抛物线性相关。表观反应速率常数kobs=3.95×10-4c-0.27030I1.2224W0.3283,该模型计算值与实验值吻合较好,平均相对偏差仅为0.5%,可用于预测微波辅助光催化降解低浓度有机污染物的反应规律。     

溶胶-凝胶法制备颗粒状催化剂低温SCR脱硝性能

采用溶胶凝胶法制备了Mn-Ce/Ti O2催化剂,并将其用于低温NH3选择催化还原NO的反应(NH3-SCR),考察了反应温度、空速、氧气浓度、氮氧化物浓度和氨氮比等反应条件对催化剂性能的影响。结果表明,NO入口浓度为800~1 600 mg/m3时,催化剂活性受NO初始浓度的影响较小。反应温度和氨氮比对NO转化率影响显著,100~150℃温度范围内,NO转化率随温度升高快速上升;当[NH3]/[NO]1.1时,随着[NH3]/[NO]的增加,NO转化率很快上升。反应体系中适当的O2浓度可促进NO还原为N2。空速大于10 000 h-1时,NO转化率随着空速的增大而降低。     

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.     

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.     

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.     

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.     

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.     

Knowledge transfer initiative between molecular biologists and environmental researchers and regulators

A Natural Environment Research Council (NERC) funded Knowledge Transfer (KT) workshop was held in the United Kingdom (UK) to identify the needs and opportunities in the application of molecular biology and ‘omics’ techniques to environmental monitoring and risk assessment. Attendees highlighted a lack of effective communication between end-users and researchers as well as difficulties with data interpretation as reasons behind the slow uptake of molecular biology and omics techniques. A number of promising areas in which new techniques could be implemented at a practical level in the very near future were identified, thereby raising the profile of these recent technologies and providing vital proof of concept work. Molecular taxonomy, bacterial source tracking and pre-screening of chemicals for potential toxicities were all viewed as areas in which omics and molecular techniques could have immediate value, with the aim of reducing cost, increasing efficiency and providing more comprehensive data of improved quality.