An enzyme-linked immunosorbent assay for the determination of dioxins in contaminated sediment and soil samples

A 96-microwell enzyme-linked immunosorbent assay (ELISA) method was evaluated to determine PCDDs/PCDFs in sediment and soil samples from an EPA Superfund site. Samples were prepared and analyzed by both the ELISA and a gas chromatography/high resolution mass spectrometry (GC/HRMS) method. Comparable method precision, accuracy, and detection level (8 ng kg(-1)) were achieved by the ELISA method with respect to GC/HRMS. However, the extraction and cleanup method developed for the ELISA requires refinement for the soil type that yielded a waxy residue after sample processing. Four types of statistical analyses (Pearson correlation coefficient, paired t-test, nonparametric tests, and McNemar's test of association) were performed to determine whether the two methods produced statistically different results. The log-transformed ELISA-derived 2,3,7,8-tetrachlorodibenzo-p-dioxin values and log-transformed GC/HRMS-derived TEQ values were significantly correlated (r=0.79) at the 0.05 level. The median difference in values between ELISA and GC/HRMS was not significant at the 0.05 level. Low false negative and false positive rates (<10%) were observed for the ELISA when compared to the GC/HRMS at 1,000 ng TEQ kg(-1). The findings suggest that immunochemical technology could be a complementary monitoring tool for determining concentrations at the 1,000 ng TEQ kg(-1) action level for contaminated sediment and soil. The ELISA could also be used in an analytical triage approach to screen and rank samples prior to instrumental analysis.     

A Concentric Analysis of the Impact of Urbanization on the Threatened European Tree Frog in an Agricultural Landscape

Abstract:  Pond-breeding amphibians are affected by site-specific factors and regional and landscape-scale patterns of land use. Recent anthropogenic landscape modifications (drainage, agriculture intensification, larger road networks, and increased traffic) affect species by reducing the suitable habitat area and fragmenting remaining populations. Using a robust concentric approach based on permutation tests, we evaluated the impact of recent landscape changes on the presence of the endangered European tree frog ( Hyla arborea ) in wetlands. We analyzed the frequency of 1 traffic and 14 land-use indices at 20 circular ranges (from 100-m up to 2-km radii) around 76 ponds identified in western Switzerland. Urban areas and road surfaces had a strong adverse effect on tree frog presence even at relatively great distances (from 100 m up to 1 km). When traffic measurements were considered instead of road surfaces, the effect increased, suggesting a negative impact due to a vehicle-induced effect. Altogether, our results indicate that urbanization and traffic must be taken into account when pond creation is an option in conservation management plans, as is the case for the European tree frog in western Switzerland. We conclude that our easy-to-use and robust concentric method of analysis can successfully assist managers in identifying potential sites for pond creation, where probability of the presence of tree frogs is maximized.     

1999年委内瑞拉阿维拉山北坡入海型泥石流

委内瑞拉阿维拉山呈东一西走向，北坡濒临加勒比海．１９９９年１２月１６日，阿维拉山北坡２０多条沟谷暴发泥石流，使沿海的城镇、村庄、港口、公路及各种设施遭到毁灭性破坏，造成数万人死亡，直接经济损失超过刀亿美元．泥石流发生在森林植被良好的山区，具低频率和群发性特征，规模大，直接入海．分析这次泥石流灾害，对我国的防灾减灾工作具有启示意义．     

High-throughput screening of dioxins in sediment and soil using selective pressurized liquid extraction with immunochemical detection

A high-throughput screening method using selective pressurized liquid extraction (SPLE) and enzyme-linked immunosorbent assay (ELISA) for monitoring dioxins in sediment and soil is described. SPLE conditions were developed by extracting sediment or soil together with alumina, 10% AgNO₃ in silica, and sulfuric acid impregnated silica (acid silica) using dichloromethane (DCM) as the solvent at 100 °C and 2000 psi. Post-extraction cleanups were not required for ELISA. Two reference sediments (National Institute of Standards and Technology SRM 1944 and Wellington Laboratories WMS01) were analyzed by the SPLE–ELISA method. The ELISA utilized a polyclonal antibody and 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD) as the calibrant. Recoveries of ELISA-derived TCDD equivalents (EQ) relative to the expected gas chromatography/high resolution mass spectrometry (GC/HRMS) derived dioxin toxic equivalent (TEQ) values were 116 ± 11% for SRM 1944 and 102 ± 13% for WMS01. ELISA TCDD EQs were consistent with the dioxin TEQs as measured by GC/HRMS for 25 soil/sediment samples from seven different contaminated sites. The ELISA had an approximate method detection limit of 10 pg g⁻¹ with a precision of 2.6–29% based on the relative percentage difference (%RPD) for duplicate samples. Estimated sample throughput for the SPLE–ELISA was three times or more than that of the GC/HRMS method employing PLE with a multi-column cleanup.     

Rate Constant Ratios During Nitrogen Dioxide Photolysis

Nitrogen dioxide is the light absorber in the hydrocarbon system leading to production of photochemical air pollution. Studies of the reactions involved are based on the kinetics of nitrogen dioxide photolysis and the values of the rate constants derived therefrom. The photolysis of nitrogen dioxide was investigated in the 2-20 ppm concentration range. The value of the bimolecular rate constant of the reaction between oxygen atoms and nitrogen dioxide was calculated to be 5.26 × 10⁹1 mole^–1 sec^–1, and thetermolecular rate constant of the reaction between oxygen atoms and nitrogen dioxide in presence of a third body is 4.24 × 10^–10 1²mole^–2 sec^–1. The rate constant for the reaction between oxygen atoms and nitric oxide in the presence of a third body was calculated to be 2.31 × 10¹⁰ 1²mole^–2 sec^–1. Nitrogen was used as the third body. In terms of order of magnitude these calculated rate constants are similar to previously reported values. However, in certain cases their use leads to an oxygen atom concentration which is 100% greater than previously calculated.     

稻田土壤种子库研究进展

土壤种子库是指存在于土壤表面和土壤中全部存活种子的总和。稻田土壤种子库是地上杂草产生的根本来源。我国是一个水稻种植大国,目前关于稻田土壤种子库的研究还不够全面和深入。研究稻田土壤种子库对于防治稻田草害具有重要指导意义,同时也是种子库研究领域的一个重要补充。取样方法和取样时间是研究土壤种子库的关键所在。而萌发法是最常见的判定方法。关于稻田土壤种子库大小的结论相差很大,从103~105 m-2不等。稻田土壤种子库中的杂草主要有19科55种,一般的稻田可检出10科或20种左右。种子的垂直分布格局主要受耕作强度的影响。70%~80%甚至更多的杂草种子分布在0~10 cm。稻田土壤种子库由于萌发、捕食、衰老和种子散布等原因具有季节动态。轮作制度、耕作方式、不同施肥处理以及除草方式等对稻田土壤种子库有重要影响。连续多年的田间管理会使种子库的大小、分布和物种组成产生年际变化。目前,需要加强长期定位研究,扩大研究区域和研究内容,重点研究杂草种子的休眠萌发机制和种子命运研究,为杂草治理提供更准确的信息。     

Evaluation of alternative approaches for screening contaminated sediments and soils for polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans

Traditional high resolution mass spectrometry (HRMS) analysis for polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/Fs) can be time consuming and expensive. Consequently, alternative methods are of great interest to regulatory agencies and others characterizing contaminated sites. One factor that hinders acceptance of alternative methods is a lack of performance information that assesses the alternative method's impacts on analytical results. The U.S. Environmental Protection Agency's Superfund Innovative Technology Evaluation Monitoring and Measurement Technologies Program (EPA SITE MMT) encourages the development and implementation of innovative and alternative monitoring methods by providing performance information on site characterization technologies. This paper presents a comparison of the results obtained from laboratory-based alternative approaches for screening sediment and soil samples for dioxin toxicity equivalents (TEQ(D/F)) to results obtained using traditional HRMS. The laboratory-based approaches included modifying the traditional HRMS analysis to make it more cost-effective (alternate 1613B), analyzing extracts that had been prepared for HRMS using low resolution mass spectrometry, and determining total organic carbon (TOC) content as an indicator of PCDD/F content. These comparisons demonstrated that TEQ(D/F) values generated using toxicity equivalency factors proposed by the World Health Organization in 1998 applied to alternate 1613B and LRMS analyses have a strong linear correlation to the TEQ(D/F) values derived in the same fashion from traditional HRMS analysis. These results would have placed >90% of the samples within the same concentration intervals using ranges of <0.05, 0.05-0.50, 0.50-5, and >5ng TEQ/g. Natural log transformed data for TOC had significantly weaker correlation to TEQ(D/F), indicating that TOC is not a reliable indicator of TEQ(D/F) concentrations.