高铁酸钠电化学合成条件的研究

利用含铁材料为阳极,铜为阴极,NaOH溶液为电解液,于隔膜电解槽中电解制备高铁酸钠.探索了该工艺所必需的各种参数和反应条件,确定了隔膜材料,并对Na2FeO4浓度和电流效率的非一致性变化作出了解释.研究结果表明:在阳极距离为1.3 cm(极距2.3 cm)、阳极电解液浓度为14 mol/L,阴极电解液浓度为4 mol/L、温度为35℃、电压为8～9 V时,电解2 h后得到的Na2FeO4浓度为18.7g/L,电流效率为20%.     

PTFE/C三相电极氧阴极还原法生产过氧化氢

设计了隔膜体系电解槽,制作了聚四氟乙烯(PTFE)/碳黑三相气体扩散电极,系统研究了隔膜、电流密度、电极间距、初始溶液酸度、电解质、空气量和时间等因素对过氧化氢累积产生浓度和电流效率的影响。结果表明,在有隔膜体系,电流密度为70 m A/cm2,电极间距为1 cm,初始p H=0.5,电解质为0.10 mol/L Na2SO4溶液,空气量为40 m L/min的条件下,电解时间1 h时过氧化氢累积浓度最高可至20 096.05 mg/L,此时对应的电流效率为63.37%。在确定的最佳条件下,进行电解液循环实验,1 h时电流效率升高到98.4%,12 h之后,过氧化氢累积浓度为46 042.43 mg/L。实验原位产生的高浓度酸性过氧化氢溶液可以直接应用于Fenton试剂。     

电-Fenton法处理4-氯酚废水

采用电解法对4-氯酚废水进行了处理。以活性炭纤维(ACF)为阴极，铁为阳极，并向阴极不断通入空气，电解过程中生成的H2O2与阳极溶解的Fe^2 形成Fenton(芬顿)试剂，Fenton试剂在电解的过程中可以产生大量活性羟基 OH，能够很好地氧化降解废水中的4-氯酚。在最佳试验条件下：室温，氯酚浓度为50mg／L，电解时间为60min，pH值为4．5，电流密度为15．38A／m^2，Na2SO4浓度为3g／L时，4-氯酚去除率为85．70％。     

电-Fenton法处理4-氯酚废水

采用电解法对 4 氯酚废水进行了处理。以活性炭纤维 (ACF)为阴极 ,铁为阳极 ,并向阴极不断通入空气 ,电解过程中生成的H2 O2 与阳极溶解的Fe2 + 形成Fenton(芬顿 )试剂 ,Fenton试剂在电解的过程中可以产生大量活性羟基·OH ,能够很好地氧化降解废水中的 4 氯酚。在最佳试验条件下 :室温 ,氯酚浓度为 5 0mg/L ,电解时间为 6 0min ,pH值为4 5 ,电流密度为 15 38A/m2 ,Na2 SO4浓度为 3g/L时 ,4 氯酚去除率为 85 70 %。     

隔膜电解法回收利用电厂锅炉EDTA清洗废水研究

以涂Ir/Sn钛网板作阳极,以不锈钢网板作阴极,采用隔膜电解法处理电厂锅炉EDTA清洗废水.实验结果表明,电流、阴极电解液初始pH值和Fe/EDTA摩尔比对粉末铁析出速率影响较大,粉末铁电解析出的适宜条件是电解电流为1.0 A、阴极电解液初始pH值为5.6、阴极电解液Fe/EDTA摩尔比足够高.采用隔膜电解结合反渗透膜系统处理电厂锅炉EDTA清洗废水,可同时高效回收纳米级粉末铁和EDTA.     

组合阳极联合气体扩散阴极电催化降解苯胺

采用气体扩散电极为阴极,钛基氧化物（Ti／SnO2-Sb2O5-IrO2）和金属铁构成组合阳极,构建了新型电化学氧化体系用于降解有机污染物。利用该氧化体系,在不同实验条件下考察了苯胺降解的效果与降解过程的相关规律。结果表明,阴极电位、铁阳极通电时间以及苯胺初始浓度均显著影响苯胺的降解效果。当阴极电位为-0．7V,pH3．0,铁阳极通电时间20min时,电化学处理200mg／L苯胺480min,TOC的去除效率达到80．4％,矿化电流效率（MCE）为8．6％,显示了该氧化体系具有良好的有机物降解能力。此外,苯胺降解过程中氨氮和硝态氮浓度的变化表明,苯胺分子中的氮主要转化为NH4和NO3^-。     

电极材料对电解法处理循环式准好氧垃圾填埋场渗滤液效果的影响研究

分别用3种不同材料电极（不锈钢、Ti／Pt和Ti／RuO2-IrO2）作阳极、石墨电极作阴极在同一条件下分别对循环式准好氧填埋垃圾场渗滤液进行电解处理对比研究。研究结果表明，随着电解时间的变化，渗滤液中的COD、BOD5、BOD5／COD、重金属离子浓度、色度和pH值均会发生改变。当电解时间为10—20min时，用上述3种电极作阳极电解均会出现渗滤液COD、BOD5、BOD5／COD增大的现象；当电解时间为30—40min时，用Ti／RuO2-IrO2或Ti／Pt电极作阳极电解均可使渗滤液的色度降为0；当电解时间为120min时，分别用3种电极作阳极电解都可使渗滤液中的COD、BOD5和重金属得到有效的去除，其中用Ti／RuO2-IrO2电极作阳极电解对COD、BOD5的去除效果最好：用Ti／Pt电极作阳极电解对Pb^2＋的去除效果最好。     

铁阳极电化学对直接大红4BE模拟废水脱色

对铁阳极电化学处理直接大红4BE染料废水脱色率和脱色能耗的影响因素进行研究。考察了电流密度、染料溶液初始pH值、染料初始浓度和支持电解质Na2SO4浓度对脱色性能的影响。结果表明,电流密度、染料废水初始pH、染料初始浓度、支持电解质浓度对脱色率和脱色能耗产生较大影响。在电流密度1.667 mA/cm2、pH值6.54、染料浓度50mg/L、Na2SO4浓度0.01 mol/L、温度20℃、搅拌速度600 r/min、电解时间60 min条件下,脱色率达到92.1%,脱色能耗1.298 kWh/kg染料、铁阳极消耗量41 mg/400 mL染料模拟废水。     

电解絮凝法处理老龄垃圾渗滤液的实验研究

为考察简便低耗的电解材料处理效果,采用铸铁阳极电解絮凝法对老龄垃圾渗滤液进行了处理,通过正交实验和单因素实验考察了电解液浓度、电流密度、pH、极板间距对处理效果的影响.结果表明,电解絮凝法对该老龄垃圾渗滤液有较好的处理效果,当电流密度为50 mA/cm2、pH值为9、极板间距为2 cm、电解75 min后,COD和NH...     

膜电解法在线再生酸性蚀刻液及回收铜新技术

采用极化曲线法研究了酸性蚀刻液阴、阳极电化学行为,并构建了离子膜电解反应体系,考察了在线再生酸性蚀刻液及回收铜的效果。结果表明,阳极氧化过程发生浓差极化,存在极限电流密度,Cu＋含量越高,极限电流密度越大;阴极还原分4步反应进行,存在极限电流密度;强化溶液传质可有效提高阴、阳极极限电流密度,有利于避免电解过程中析出氯气和氢气;在线实验表明,通过监控阳极液ORP,可避免析出氯气;分步降低电流电解有利于避免析出氢气,形成致密的金属铜块;在电流为9～24A范围内分4步电解23．5h可再生酸性蚀刻液23．5L,同时电沉积回收510g铜,纯度高达99．98％。阴极电流效率达到95．2％,吨铜电耗3251kWh。电解过程中无氯气和氢气析出,无废液排放,表明膜电解法在线再生酸性蚀刻液具有良好的应用前景。     

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.     

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.     

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.     

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.     

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.