微波无极紫外光催化降解茜素绿的性能研究及产物分析

以微波无极紫外灯为光源,P25型Ti O2为催化剂,研究了微波反应器中茜素绿(AG)的光催化降解性能,考察了染料初始浓度及p H对降解效率的影响,利用ESI电子喷雾质谱和离子色谱测定了茜素绿降解的中间产物,并对产物的可生化性进行了分析。结果表明,微波/紫外/二氧化钛体系拓宽了染料浓度和p H的适用范围。降解后生成了大量小分子物质,可生化性得到了大幅度的提高,BOD5/COD值从反应前的0.0959增加到了0.40。     

直接红染料的臭氧脱色与中间产物研究

以直接红B模拟染料废水为研究对象，考察了臭氧化过程中染料溶液的吸光度和TOC的变化，同时利用离子色谱仪和GC/MS对染料的降解过程进行了分析，最后用发光细菌法检测了染料溶液急性毒性的变化。结果表明，臭氧对染料的降解符合一级反应动力学，20 min时对染料的脱色率达到99.2%；反应40 min后TOC减少32.55%，染料分子有97.8%的S被氧化为SO^2-₄，偶氮键被臭氧化为N₂，分子中的仲胺基小部分转化成游离NH⁺₄和NO^-₃；在臭氧化过程前期新生成的醛类和酰胺类物质使溶液急性毒性迅速上升，25 min后溶液毒性开始逐渐下降。     

铁屑还原及微波铁屑诱导氧化降解偶氮染料历程的研究

研究了铁屑内电解还原及微波诱导氧化降解偶氮染料的反应历程,采用胶束毛细管电泳法对跟踪了2种不同降解方法下的中间产物变化.实验结果表明,染料的偶氮键(-N=N-)易被铁屑内电解还原,反应过程中有中间产物苯胺生成.微波诱导铁屑氧化偶氮染料的反应过程中未检测到其他芳环类化合物生成,在微波辐照2 min时脱色率已达90%以上,TOC去除率也高达78%,矿化较为彻底;在微波辐照铁屑诱导氧化降解污染物的同时,也使铁屑自身得以活化再生,提高了铁屑的内电解能力.     

辉光放电电解等离子体降解水中阳离子红XL-GRL

针对染料废水色度高、难生物降解等问题,提出了用辉光放电电解等离子体(GDEP)技术降解染料废水阳离子红XL-GRL的方法。研究了放电电压、溶液浓度对脱色率的影响;测定了GDEP产生的活性物质以及降解过程中溶液的电导率、pH和TOC去除率的变化;分析了降解中间产物成分。结果表明,在600 V电压下,GDEP产生了HO?、H?、O?等高活性物质,他们可使染料分子在130 min内的脱色率达到93.32%,在120 min内TOC去除率达到了65.80%。降解过程中产生了大量带电离子及酸性中间产物。推测可能的降解机理是,阳离子红XL-GRL分子在HO·作用下双键断裂,生成酚类等产物,接着继续降解为中间产物醌,并进一步氧化为小分子有机酸,最终矿化为CO_2、H_2O和简单的无机离子。GDEP在有机染料废水处理方面具有一定的应用前景。     

臭氧化降解结晶紫溶液的机理

采用臭氧化法对模拟废水中难生物降解的结晶紫染料进行降解实验研究,藉助紫外光谱、红外光谱、气相色谱、化学需氧量和总有机碳的检测结果对反应机理进行了初步探讨。实验结果表明,当溶液初始质量浓度0.88 mmol/L,臭氧投加量9.06×10-5mol/min,调节初始溶液pH为10.0,控制反应温度298 K,反应120 min后,结晶紫溶液COD去除率达到97.0%。分析表明,结晶紫染料降解的中间产物主要是对氨基苯酚、丁烯二酸、乙酸等有机小分子物质,最终产物为水和二氧化碳。     

电催化氧化处理三唑类杀菌剂模拟废水

以三环唑和丙环唑为特征污染物,研究了Ti O2-NTs/Sn O2-Sb/Pb O2电极电催化氧化处理模拟废水中三唑类杀菌剂的机理。实验结果表明,电催化氧化对废水中三唑类杀菌剂的降解符合一级动力学关系,且降解速率为:丙环唑三环唑。利用气相色谱-质谱联用仪(GC-MS)和离子色谱仪(IC)对电催化氧化降解三环唑和丙环唑溶液产生的中间产物和最终产生的有机酸和无机离子进行检测分析,推断出废水中三唑类杀菌剂电催化氧化的降解路径。通过斑马鱼实验得出电催化氧化对废水中三环唑急性毒性的削减幅度较大,对丙环唑的削减幅度较小。     

铈离子光催化降解茜素绿的性能和机理

主要研究了简单铈离子（Ce3＋）在紫外光（uv）的作用下对蒽醌染料茜素绿（AG）的光催化降解效果和反应机理。结果表明，UV／Ce3＋体系能够有效降解AG，初始反应速率随AG浓度的倒数值和Ce3＋浓度的增加而线性增加，随初始溶液pH的增加先降低后增加，在酸性条件下有很高的TOC去除率。荧光探针实验表明，反应过程中可以产生·OH自由基。UV／Ce3＋体系对其他类型染料和对硝基苯酚都有较好的降解效果。     

四氧化三铁活化过硫酸盐降解活性黑5

采用水热合成法制备出了具有较高催化活性的催化剂四氧化三铁(Fe_3O_4),并利用Fe_3O_4活化过硫酸盐降解活性黑5,考察了初始pH、Fe_3O_4投加量、活性黑5初始浓度和过硫酸盐投加量对活性黑5降解效果的影响。结果表明,Fe_3O_4活化过硫酸盐降解活性黑5的最佳条件为初始pH 6、活性黑5初始质量浓度50mg/L、过硫酸盐投加量6mmol/L、Fe_3O_4投加量2.0g/L。在最佳条件下,反应180min,活性黑5的降解率达到80.2%,Fe_3O_4反复使用5次后,活性黑5的降解率仍能达到77%以上。活性黑5的降解途径为:偶氮键打开产生苯环中间产物和萘环中间产物,萘环中间产物逐步转化为邻苯二甲酸酐→邻苯二甲酸→苯甲酸;苯环中间产物逐步转化为对氨基苯磺酸→硝基苯和对氨基苯酚,对氨基苯酚转化为对苯二酚;最终被彻底氧化降解成CO_2、H_2O等无毒小分子物质。活性黑5在降解过程中对植物的毒性先升高后降低。     

铈离子光催化降解茜素绿的性能和机理简

主要研究了简单铈离子（Ce³⁺）在紫外光（UV）的作用下对蒽醌染料茜素绿（AG）的光催化降解效果和反应机理。结果表明，UV/Ce³⁺体系能够有效降解AG，初始反应速率随AG浓度的倒数值和Ce³⁺浓度的增加而线性增加，随初始溶液pH的增加先降低后增加，在酸性条件下有很高的TOC去除率。荧光探针实验表明，反应过程中可以产生·OH自由基。UV/Ce³⁺体系对其他类型染料和对硝基苯酚都有较好的降解效果。     

ZnIn_2S_4光催化降解水中痕量药物卡马西平的特性

采用水热合成法制备光催化剂Zn In2S4,考察其光催化降解水中痕量医药类物质卡马西平的特性。研究表明,卡马西平初始浓度100μg·L~(-1)、溶液pH 5~9、Zn In2S4投加量50 mg·L~(-1)与碘镓灯(350~450 nm)光照反应3 h后,卡马西平的去除率为90%。动力学分析表明,卡马西平的光催化降解符合一级反应动力学,添加催化剂时的反应速率常数是不加催化剂的2.85倍,催化剂明显提高了降解反应速率。催化剂循环使用2个周期后,卡马西平的去除率由90%降至70%并保持稳定,表明催化剂结构趋稳后仍具有较高的催化活性。羟基自由基(·OH)实验证实了卡马西平降解过程中·OH为主要活性物种,但卡马西平的矿化率却只有3%,由于反应后的溶液呈酸性,因此推测光催化过程中卡马西平与·OH作用后大都转化为酸性中间产物而未被彻底氧化。     

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.     

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.     

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.     

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.     

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.     

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.     

Sorption and predicted mobility of herbicides in Baltic soils

This study was undertaken to determine sorption coefficients of eight herbicides (alachlor, amitrole, atrazine, simazine, dicamba, imazamox, imazethapyr, and pendimethalin) to seven agricultural soils from sites throughout Lithuania. The measured sorption coefficients were used to predict the susceptibility of these herbicides to leach to groundwater. Soil-water partitioning coefficients were measured in batch equilibrium studies using radiolabeled herbicides. In most soils, sorption followed the general trend pendimethalin > alachlor > atrazine～ amitrole～ simazine > imazethapyr > imazamox > dicamba, consistent with the trends in hydrophobicity (log K_ow) except in the case of amitrole. For several herbicides, sorption coefficients and calculated retardation factors were lowest (predicted to be most susceptible to leaching) in a soil of intermediate organic carbon content and sand content. Calculated herbicide retardation factors were high for soils with high organic carbon contents. Estimated leaching times under saturated conditions, assuming no herbicide degradation and no preferential water flow, were more strongly affected by soil textural effects on predicted water flow than by herbicide sorption effects. All herbicides were predicted to be slowest to leach in soils with high clay and low sand contents, and fastest to leach in soils with high sand content and low organic matter content. Herbicide management is important to the continued increase in agricultural production and profitability in the Baltic region, and these results will be useful in identifying critical areas requiring improved management practices to reduce water contamination by pesticides.