水中痕量有机磷农药的高效液相色谱/质谱分析

农药对饮用水以及饮用水源的污染在西方发达国家是一项极为关注的课题。有机磷农药作为农药中的一大类,至今仍是世界上生产和使用最多的农药品种。因此,饮用水以及饮用水源中痕量有机磷农药残留的状况受到人们关注。水中痕量有机磷农药的分析方法正在不断地改进,针对ＧＣ／ＭＳ测定某些有机磷农药时存在热分解以及在气相色谱柱上发生吸附的不足。结合高灵敏度、高选择性的质谱鉴定器,本文主要介绍最新的ＨＰＬＣ／ＡＰＩＭＳ方法在水中痕量有机磷农药测定方面的进展和应用。     

蔬菜中有机磷农药残留研究及对策

以西安市为例，研究了蔬菜中有机磷农药的残留问题，分析了不同农药在蔬菜中的残留特征以及不同品种蔬菜、不同类型蔬菜中农药残留的特征，讨论了蔬菜中农药残留量超标的原因及相关对策。     

白糖为共基质处理有机磷农药废水的试验研究

有机磷农药废水是一种极难处理的高浓度有机废水,因为该废水含有大量的难降解有机物,其中的有机磷对微生物代谢具有很强的抑制作用。采用高效好氧生物反应器(HCR)对有机磷农药废水进行处理试验,对比研究了以白糖为共基质和有机磷农药废水为单基质的两种不同条件下,系统中活性污泥的特性及系统对有机磷农药废水COD去除效果的变化规律。结果表明,白糖为共基质可大大提高HCR系统中活性污泥的活性和系统对有机磷农药废水COD的去除效果。     

一种有机磷农药单克隆抗体的制备及其特性研究

合成与有机磷农药化学结构相近似的一类半抗原,制备该类半抗原的特异性单克隆抗体,建立酶免疫分析方法,并对4种有机磷农药(毒死蜱、甲基对硫磷、辛硫磷及三唑磷)进行检测.结果显示,此方法对部分有机磷农药灵敏度高,可以简便、快速地检测具有特定结构的有机磷农药,检测灵敏度与被检有机磷农药的化学结构相关.     

常见拟除虫菊酯和有机磷农药对鱼类的急性及其联合毒性研究

以崇明岛前卫村中心湖中鲫鱼、鲤鱼、鲢鱼及泥鳅作为实验动物.进行了氯氰菊酯(原药和商品)、氰戊菊酯(原药和商品)、毒死蜱(原药和商品)、甲氰菊酯(商品)、溴氰菊酯(商品)、辛硫磷(商品)以及乙酰甲胺磷(商品)7种供试农药对实验鱼种的急性毒性及联合毒性实验,并检测了前卫村中心湖水体中18种有机磷农药和4种拟除虫菊酯农药,其中检出了1种有机磷农药(毒死蜱)和3种拟除虫菊酯农药(氰戊菊酯、氯氰菊酯、甲氰菊酯).结果表明,在单一农药急性毒性实验中,鲤鱼对供试农药表现较敏感,其次是鲫鱼和鲢鱼,而泥鳅对农药的耐药性最强;7种供试农药中,拟除虫菊酯农药相对于有机磷农药表现出较高的急性毒性,其实验鱼种的半数致死浓度(LC60)皆在μg/L级;对拟除虫菊酯农药(氯氰菊酯,氰戊菊酯)与有机磷农药(辛硫磷、乙酰甲胺磷)进行的联合毒性实验结果表明,除了暴露时间为24、48 h时氰戊菊酯与辛硫磷混配对鲢鱼的毒性实验表现为协同作用外,其余皆为拈抗作用.     

采用气相色谱法测定土壤中有机磷农药

建立了一种用GC-FPD测定土壤中的5种有机磷农药的测定方法,经索氏提取,GPC净化浓缩后直接进样分析。用保留时间定性,外标法定量。5种有机磷农药的回收率为86.5%～103.2%,精密度(以相对标准偏差表示)为2.47%～5.70%;检测限为0.000 1～0.000 2 mg/kg。该方法准确度和灵敏度高,前处理简单,可同时测定土壤中的5种有机磷农药。     

多相催化-臭氧氧化法处理模拟有机磷农药废水

实验通过臭氧氧化法来降解模拟废水中的有机磷农药，将其转化为无害物质，并试验研究了在废水中加入2种自制的催化剂对降解结果的影响。采用气相色谱法测定水中有机磷农药的量。结果表明，只用臭氧处理的情况下1周后有机磷的去除率为78．03％；在催化剂A存在下，去除率可达93．85％；在催化剂B存在下，去除率可达为88．35％。结果表明，臭氧氧化法对此类污水：具有较好的降解作用，尤其在有催化剂存在的情况下处理效果更好，在室温和中性介质中均属于一级反应。     

多相催化-臭氧氧化法处理模拟有机磷农药废水

实验通过臭氧氧化法来降解模拟废水中的有机磷农药,将其转化为无害物质,并试验研究了在废水中加入2种自制的催化剂对降解结果的影响。采用气相色谱法测定水中有机磷农药的量。结果表明,只用臭氧处理的情况下1周后有机磷的去除率为78.03%;在催化剂A存在下,去除率可达93.85%;在催化剂B存在下,去除率可达为88.35%。结果表明,臭氧氧化法对此类污水具有较好的降解作用,尤其在有催化剂存在的情况下处理效果更好,在室温和中性介质中均属于一级反应。     

有机磷农药残留检测技术研究进展

综述了近年来有机磷农药残留检测技术的研究进展,其检测方法主要有色谱法、降解酶法、化学发光技术和生物传感技术.详细介绍了几种生物传感器(如酶传感器、微生物传感器、免疫传感器、压电传感器、纳米传感器和液晶型化学传感器)在有机磷农药检测中的应用,并展望了这一领域的发展趋势.     

我国有机磷农药废水的生化法处理研究进展

农药废水的污染已受到国内外环保工作者的重视 ,我国也不例外。各种处理方法层出不穷 ,而生化法是各处理方法中的重要方法 ,本文仅就我国生化法处理有机磷农药废水的研究进展作一概述     

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.     

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.     

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.     

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.