钯修饰碳纳米管电极电催化氧化三氯生

采用钯修饰多壁碳纳米管(MWCNTs)电极电催化氧化降解三氯生,考察了极板间距、电流密度、离子强度、pH、初始浓度和电解时间对三氯生去除效率的影响,并探讨了其反应动力学。结果表明:钯修饰多壁碳纳米管(MWCNTs)电极电催化氧化降解三氯生的最佳条件为:三氯生初始浓度为50 mg/L,电流密度约为10 mA/cm2,极板间距为1 cm,pH为11,电解质Na2SO4浓度为1 000 mg/L。此条件下,反应时间为3 h时三氯生的去除率可达到99%以上,三氯生的降解为零级反应。     

电催化氧化技术处理制革综合废水

选择DSA电极中的钛基掺硼金钢石膜电极(Ti/BDD),用于制革综合废水的电催化氧化处理研究,考察了在不同的电流密度、电压、电解质、pH值和电解时间等因素对COD去除率和电流效率的影响。结果表明,控制电流密度为30mA/cm2,电压为8.0 V,电解质(NaCl)浓度为2.0 g/L,pH为4.0,电催化氧化处理2 h后,废水的COD和NH4+-N的去除率分别达到了83.6%和90.3%,BOD/COD为0.45,比能耗为35.34 kWh/kg COD,电流效率为37%。     

三维电催化氧化技术处理草铵膦农药废水

选用石墨板作为三维电催化装置的阳极、不锈钢板作为阴极,以活性炭颗粒作为粒子电极进行反应,研究了三维电催化氧化技术处理草铵膦农药废水的效果;并考察了电流密度、极板间距、电解时间、初始浓度、pH值和粒子电极用量等因素对其处理效果的影响。实验结果表明,在废水初始浓度为300 mg·L~(-1),反应时间为90 min,极板间距为4 cm,pH值为5,电流密度为31.5 m A·cm-2,粒子电极的用量为3.08 g·L~(-1)的条件下,废水的COD去除率为83.48%。三维电催化氧化技术通过减小粒子间距改善电荷传质效果;电流效率的提高也促使废水的处理效果显著提升。     

RuO_2-IrO_2/Ti阳极电催化降解偶氮染料甲基橙模拟废水

以自制Ti基Ru O2-Ir O2镀层形稳电极为阳极,采用电催化氧化处理偶氮染料甲基橙模拟废水。以硫酸钠为支持电解质,在自然p H条件下分别考察了电解时间、电极间距、电流密度和电解质浓度等因素对甲基橙去除率的影响,并分析其原因。实验结果表明,在自然p H、电极间距为1.0 cm、电流密度为30.0 m A/cm2、电解质硫酸钠浓度为20.0 g/L、电解1.0h,甲基橙去除率高达90.0%以上。因此,电催化氧化法作为一种高效、简便的染料废水处理技术,具有一定的应用潜力。     

RuO2-IrO2-SnO2/Ti阳极电催化氧化苯酚的研究

以RuO2-IrO2-SnO2/Ti钛网电极为阳极,RuO2-IrO2/Ti钛网电极为阴极,构建了电催化氧化体系,同时以苯酚为底物、硫酸钠为电解质,考察了不同pH、极板间距、电流密度和苯酚初始浓度对苯酚去除率的影响。结果表明,在pH为6.5、极板间距为1.0cm、电流密度为50mA/cm2、苯酚初始质量浓度为1 000mg/L的最佳实验条件下,取硫酸钠质量浓度为20g/L的苯酚模拟废水250mL,120min时苯酚去除率可以达到98.4%。     

含中间层的DSA电极电催化氧化硝基苯废水的研究

为了提高难降解有机废水的可生化性,以及更高效地去除废水中的特征污染物,同时避免二次污染,利用自制的含锡锑中间层的钌钯氧化物涂层电极对有机废水中的硝基苯进行处理,并利用SEM、XRD等方法对电极中间层、表层进行微观表征。微观测试表明,基体、中间层、表层之间结合力较强,有利于增强电极寿命;水处理实验表明,电催化氧化反应体系适合高浓度有机废水的处理,由于该反应体系需要外加电解质加强传质,这在实际运用中为废水中盐度的处理提供了一种新的途径,当电流密度为20 mA/cm²、电解质浓度为10 g/L、pH=5、极板间距=2 cm时,电催化氧化体系对硝基苯具有较高的去除效率。     

O_3/ACF体系降解废水中的三烯丙基异氰脲酸酯

三烯丙基异氰脲酸酯(TAIC)生产废水具有有机物浓度高、难降解的特点,常规的处理方法对其处理效果普遍较差。本研究采用O_3/ACF协同催化氧化技术,以三烯丙基异氰脲酸酯(TAIC)生产废水为研究对象,分析了O_3/ACF催化降解TAIC废水的作用机理,并考察了ACF(活性炭纤维)用量、O_3浓度、pH、TAIC初始浓度及ACF使用次数对处理效果的影响。实验结果表明:通过投加叔丁醇和双氧水的对比分析,验证了反应过程中·OH自由基的存在;在ACF投加量为1.2 g·L~(-1),TAIC初始浓度200 mg·L~(-1),pH 7.0,臭氧浓度2 g·h-1,反应40 min后,TAIC的去除率为93.54%。     

吸附-电化学氧化耦合处理对氯苯酚废水及动力学

以毡状活性炭纤维为阳极,不锈钢为阴极,吸附-电化学氧化耦合降解对氯苯酚废水进行了研究。考察了吸附或耦合电化学氧化过程、电流密度、支持电解质硫酸钠浓度和活性炭纤维重复使用对废水COD去除率的影响,结果表明,采用吸附-电化学氧化耦合方法,当电流密度7.6 mA/cm2支持电解质（硫酸钠）浓度为1 g/L,处理时间为180 min,4-CP废水COD去除率可达97.09%。毡状活性炭纤维对4-CP的静态吸附过程符合Langmiu吸附等温方程。建立了吸附-电化学氧化COD去除动力学模型,动力学模型参数表明,对于COD的去除,电化学氧化作用比吸附作用大。     

吸附-电催化氧化降解气态氯苯

采用高接触面积微孔曝气的方式,以吸附性多孔导电材料活性炭纤维（ACF）为电极,吸附电催化氧化两步联动降解气态氯苯,实现了在电解质水溶液中对高浓度非水溶性气态挥发性有机废气的有效处理。正交实验和单因素分析实验结合,确立最佳实验条件并着重考虑pH值、鼓气速率、电解电压、电解质浓度等因素对去除率的影响。在最佳实验条件下,气相中氯苯去除率达到74.3%（20℃）和72.9%（10℃）     

电催化氧化处理变性木薯淀粉生产综合废水研究

采用DSA电极电催化处理变性木薯淀粉生产综合废水,研究了槽电压,电流密度,支持电解质,pH值,电解时间等因素对其中COD去除率的影响.在选定的实验条件下,槽电压8 V,电流密度为40 mA/cm2,支持电解质为0.1g/L的NaCl,pH值为8.5～9.0,电解2 h,废水中COD的去除率达88.3%.     

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.