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     

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.     

A History of Dry Cleaners and Sources of Solvent Releases from Dry Cleaning Equipment

Approximately 25, 000-35, 000 dry cleaning facilities currently operate in the U.S. The release of perchloroethylene and other solvents from these establishments represents a major source of soil and groundwater contamination. The manner in which dry cleaning solvents escape from dry cleaning plants is, for all practical purposes, identical for chlorinated and petroleum hydrocarbon solvents and is related to one of the following events: the catastrophic failure of a component of the dry cleaning system, the improper installation, operation or maintenance of the dry cleaning equipment or a combination of all of these causes. Acceptable customs, codes and regulations can also dictate what is authorized for operation of a dry cleaning facility in a particular community, geographic area during a particular time frame. Environmental litigation dealing with the origin of a solvent release from dry cleaners tends to focus on the design and manufacture of dry cleaning industry machines such as washers, washer extractors, tumblers, solvent filters, water separators, stills and spotting boards. A thorough analysis of the daily operations of dry cleaners often reveals that poor maintenance, failure to follow the manufacturer's instructions and the actions of the operator are the most likely causes of soil and groundwater pollution. In order to forensically evaluate the most probable origins of a solvent release and to examine issues regarding liability, a thorough understanding of the history of dry cleaning and a detailed analysis of the operation and maintenance of the dry cleaning equipment are necessary. The discovery of solvent plumes in the vicinity of dry cleaning plants may suggest that the solvent source is the dry cleaning plant; however, the presence of these plumes does not necessarily indicate that the dry cleaning equipment was defectively designed or manufactured. A thorough review of the type of equipment used over the life of the dry cleaning plant and verifiable solvent mileage records frequently indicates that operators of the plant have disposed of solvent and contaminated solids into the municipal sewer or on ground surfaces.     

Radionuclides and trace elements in fish collected upstream and downstream of Los Alamos national laboratory and the doses to humans from the consumption of muscle and bone

Abstract

The purpose of this study was to determine radionuclide and trace element concentrations in bottom‐feeding fish (catfish, carp, and suckers) collected from the confluences of some of the major canyons that cross Los Alamos National Laboratory (LANL) lands with the Rio Grande (RG) and the potential radiological doses from the ingestion of these fish. Samples of muscle and bone (and viscera in some cases) were analyzed for ³H, ⁹⁰Sr, ¹³⁷Cs, ^totU, ²³⁸Pu, ^239,240Pu, and ²⁴¹Am and Ag, As, Ba, Be, Cr, Cd, Cu, Hg, Ni, Pb, Sb, Se, and Tl. Most radionuclides, with the exception of ⁹⁰Sr, in the muscle plus bone portions of fish collected from LANL canyons/RG were not significantly (p<0.05) higher from fish collected upstream (San Ildefonso/background) of LANL. Strontium‐90 in fish muscle plus bone tissue significantly (p<0.05) increases in concentration starting from Los Alamos Canyon, the most upstream confluence (fish contained 3.4E‐02 pCi g^‐1 [126E‐02 Bq kg^‐1]), to Frijoles Canyon, the most downstream confluence (fish contained 14E‐02 pCi g^‐1 [518E‐02 Bq kg^‐1]). The differences in ⁹⁰Sr concentrations in fish collected downstream and upstream (background) of LANL, however, were very small. Based on the average concentrations (±2SD) of radionuclides in fish tissue from the four LANL confluences, the committed effective dose equivalent from the ingestion of 46 lb (21 kg) (maximum ingestion rate per person per year) of fish muscle plus bone, after the subtraction of background, was 0.1 ± 0.1 mrem y^‐1 (1.0 ± 1.0 μSv y^‐1), and was far below the International Commission on Radiological Protection (all pathway) permissible dose limit of 100 mrem y^‐1 (1000 μSv y^‐1). Of the trace elements that were found above the limits of detection (Ba, Cu, and Hg) in fish muscle collected from the confluences of canyons that cross LANL and the RG, none were in significantly higher (p<0.05) concentrations than in muscle of fish collected from background locations.     

Malathion-induced sublethal toxicity on the intestine of cricket frog (Fejervarya limnocharis)

The effect of malathion [diethyl(dimethoxythiophosphorylthio)succinate] at sublethal concentration (0.006 ppm) on intestinal parameters of cricket frog (Fejervarya limnocharis) was studied for 24 hrs to 240 hrs of exposure and remarkable histopathological alterations were observed. The study on intestinal parameters revealed acute pathological conditions in the intestinal wall. The toxic effect became evident as the cytoplasm of the cells disintegrated and the cells became empty and vacuolated. The cell membranes were also ruptured. Degenerative changes of the absorptive surface (villi) of the intestine in the different periods of exposure were pronounced. Severe atrophic nature (necrotic mucosa) of the intestine began from 48 hrs onwards to 96 hrs of exposure.     

Radionuclides in deer and elk from Los Alamos national laboratory and the doses to humans from the ingestion of muscle and bone

Abstract

This paper summarizes radionuclide concentrations (³H, ⁹⁰Sr, ¹³⁷Cs, ²³⁸Pu, ^239,240Pu, ²⁴¹Am, and ^totU) in muscle and bone tissue of mule deer (Odocoileus hemionus) and Rocky Mountain elk (Cervus elaphus) collected from Los Alamos National Laboratory (LANL), Los Alamos, New Mexico, lands from 1991 through 1998. Also, the committed effective dose equivalent (CEDE) and the risk of excess cancer fatalities (RECF) to people who ingest muscle and bone from deer and elk collected from LANL lands were estimated. Most radionuclide concentrations in muscle and bone from individual deer (n = 11) and elk (n = 22) collected from LANL lands were either at less than detectable quantities (where the analytical result was smaller than two counting uncertainties) and/or within upper (95%) level background (BG) concentrations. As a group, most radionuclides in muscle and bone of deer and elk from LANL lands were not significantly higher (p<0.10) than in similar tissues from deer (n = 3) and elk (n = 7) collected from BG locations. Also, elk that had been radio collared and tracked for two years and spent an average time of 50% on LANL lands were not significantly different in most radionuclides from road kill elk that have been collected as part of the environmental surveillance program. Overall, the upper (95%) level net CEDEs (the CEDE plus two sigma for each radioisotope minus background) at the most conservative ingestion rate (50 lbs of muscle and 13 lbs of bone) were as follows: deer muscle = 0.22 mrem y^‐1 (2.2 μSv y^‐1), deer bone = 3.8 mrem y^‐1 (38 μSv y^‐1), elk muscle = 0.12 mrem y^‐1 (1.2 μSv y^‐1), and elk bone = 1.7 mrem y^‐1 (17 μSv y^‐1). All CEDEs were far below the International Commission on Radiological Protection guideline of 100 mrem y^‐1 (1000 μSv y^‐1), and the highest muscle plus bone net CEDE corresponded to a RECF of 2E‐06, which is far below the Environmental Protection Agency upper level guideline of 1E‐04.     

Nitrogen leaching and acidification during 19 years of NH₄NO₃ additions to a coniferous-forested catchment at Gårdsjön, Sweden (NITREX)

The role of nitrogen (N) in acidification of soil and water has become relatively more important as the deposition of sulphur has decreased. Starting in 1991, we have conducted a whole-catchment experiment with N addition at Gårdsjön, Sweden, to investigate the risk of N saturation. We have added 41 kg N ha⁻¹ yr⁻¹ as NH₄NO₃ to the ambient 9 kg N ha⁻¹ yr⁻¹ in fortnightly doses by means of sprinkling system. The fraction of input N lost to runoff has increased from 0% to 10%. Increased concentrations of NO₃ in runoff partially offset the decreasing concentrations of SO₄ and slowed ecosystem recovery from acid deposition. From 1990-2002, about 5% of the total N input went to runoff, 44% to biomass, and the remaining 51% to soil. The soil N pool increased by 5%. N deposition enhanced carbon (C) sequestration at a mean C/N ratio of 42-59 g g⁻¹.     

Leaching of seven pesticides currently used in cotton crop in Mato Grosso State—Brazil

This study aimed to evaluate the leaching of pesticides and the applicability of the Attenuation Factor (AF) Model to predict their leaching. The leaching of carbofuran, carbendazim, diuron, metolachlor, α and β endosulfan and chlorpyrifos was studied in an Oxisol using a field experiment lysimeter located in Dom Aquino – Mato Grosso. The samples of percolated water were collected by rain event and analyzed. Chemical and physical soil attributes were determined before pesticide application to the plots. The results showed that carbofuran was the pesticide that presented a higher leaching rate in the studied soil, so was the one representing the highest contamination potential. From the total carbofuran applied in the soil surface, around 6 % leached below 50 cm. The other pesticides showed lower mobility in the studied soil. The calculated values to AF were 7.06E-12 (carbendazim), 5.08E-03 (carbofuran), 3.12E-17 (diuron), 6.66E-345 (α-endosulfan), 1.47E-162 (β-endosulfan), 1.50E-06 (metolachlor), 3.51E-155 (chlorpyrifos). AF Model was useful to classify the pesticides' potential for contamination; however, that model underestimated pesticide leaching.     

Endosulfan in China 2—emissions and residues

Background, aim, and scope  Endosulfan is one of the organochlorine pesticides (OCPs) and also a candidate to be included in a group of new persistent organic pollutants (UNEP 2007). The first national endosulfan usage inventories in China with 1/4° longitude by 1/6° latitude resolution has been reported in an accompanying paper. In the second part of the paper, we compiled the gridded historical emissions and soil residues of endosulfan in China from the usage inventories. Based on the residue/emission data, gridded concentrations of endosulfan in Chinese soil and air have been calculated. These inventories will provide valuable data for the further study of endosulfan. Methods  Emission and residue of endosulfan were calculated from endosulfan usage by using a simplified gridded pesticide emission and residue model—SGPERM, which is an integrated modeling system combining mathematical model, database management system, and geographic information system. By using the emission and residue inventories, annual air and soil concentrations of endosulfan in each cell were determined. Results and discussion  Historical gridded emission and residue inventories of α- and β-endosulfan in agricultural soil in China with 1/4° longitude by 1/6° latitude resolution have been created. Total emissions were around 10,800 t, with α-endosulfan at 7,400 t and β-endosulfan at 3,400 t from 1994 to 2004. The highest residues were 140 t for α-endosulfan and 390 t for β-endosulfan, and the lowest residues were 0.7 t for α-endosulfan and 170 t for β-endosulfan in 2004 in Chinese agricultural soil where endosulfan was applied. Based on the emission and residue inventories, concentrations of α- and β-endosulfan in Chinese air and agricultural surface soil were also calculated for each grid cell. We have estimated annual averaged air concentrations and the annual minimum and maximum soil concentrations across China. The real concentrations will be different from season to season. Although our model does not consider the transport of the insecticide in the atmosphere, which could be very important in some areas during some special time, the estimated concentrations of endosulfan in Chinese air and soil derived from the endosulfan emission and residue inventories are in general consistent with the published monitoring data. Conclusions  To our knowledge, this work is the first inventory of this kind for endosulfan published on a national scale. Concentrations of the chemical in Chinese air and agricultural surface soil were calculated for each grid cell. Results show that the estimated concentrations of endosulfan in Chinese air and soil agree reasonably well with the monitoring data in general. Recommendations and perspectives  The gridded endosulfan emission/residue inventories and also the air and soil concentration inventories created in this study will be updated upon availability of new information, including usage and monitoring data. The establishment of these inventories for the OCP is important for both scientific communities and policy makers.