Enantiomeric separation of metolachlor and its metabolites using LC-MS and CZE

The stereoisomers of metolachlor and its two polar metabolites [ethane sulfonic acid (ESA) and oxanilic acid (OXA)] were separated using liquid chromatography-mass spectrometry (LC-MS) and capillary zone electrophoresis (CZE), respectively. The separation of metolachlor enantiomers was achieved using a LC-MS equipped with a chiral stationary phase based on cellulose tris(3,5-dimethylphenyl carbamate) and an atmospheric pressure chemical ionization source operated under positive ion mode. The enantiomers of ESA and OXA were separated using CZE with gamma-cyclodextrin (gamma-CD) as chiral selector. Various CZE conditions were investigated to achieve the best resolution of the ESA and OXA enantiomers. The optimum background CZE electrolyte was found to consist of borate buffer (pH=9) containing 20% methanol (v/v) and 2.5% gamma-CD (w/v). Maximum resolution of ESA and OXA enantiomers was achieved using a capillary temperature of 15 degrees C and applied voltage of 30 kV. The applicability of the LC-MS and CZE methods was demonstrated successfully on the enantiomeric analysis of metolachlor and its metabolites in samples from a soil and water degradation study that was set up to probe the stereoselectivity of metolachlor biodegradation. These techniques allow the enantiomeric ratios of the target analytes to be followed over time during the degradation process and thus will prove useful in determining the role of chirality in pesticide degradation and metabolite formation.     

Toxicity and repellency of hot pepper extracts to spider mite, Tetranychus urticae Koch

Increasing concern about persistence and environmental impact of synthetic pesticide residues require development of biodegradable and environmentally safe alternatives. The potential of using fruit extracts of hot pepper as alternatives to synthetic acaricides for controlling the two-spotted spider mite, Tetranychus urticae Koch, is explored in this study. Twenty-four Capsicum accessions (Solanaceae) were screened for their toxicity and repellency to the spider mites. Crude extracts from fruits of C. chinense, C. frutescens, C. baccatum, C. annuum, and C. pubescens were prepared in methanol and tested for their acaricidal properties. Spider mite mortality was greatest (45%) when fruit extract of accession Grif-9169 (C. annuum) was used. Results from diving board bioassays indicated that mites avoided filter paper strips treated with hot pepper extracts from accessions PI-596057 (C. baccatum), PI-195299 (C. annuum), and Grif- 9270 (C. annuum). This investigation suggests that methanolic extracts of these three accessions may have a great potential for repelling spider mites and should be field-tested on a large-scale to assess their value in managing populations of spider mites, which could reduce reliance on synthetic acaricides. An attempt was made to correlate repellency with chemical constituents of fruit extracts of the most repellent accessions to identify chemical sources of repellency. Capsaicin and dihydrocapsaicin, the pungent components of pepper fruit, were not correlated with toxicity or repellency, indicating that these are not likely related to the toxicity or repellency of the pepper fruit extracts. Other, unidentified chemicals are likely responsible for toxicity and repellency to the two-spotted spider mite.     

Determination of extremely low (236)U/(238)U isotope ratios in environmental samples by sector-field inductively coupled plasma mass spectrometry using high-efficiency sample introduction

A method by inductively coupled plasma mass spectrometry (ICP-MS) was developed which allows the measurement of (236)U at concentration ranges down to 3 x 10(-14)g g(-1) and extremely low (236)U/(238)U isotope ratios in soil samples of 10(-7). By using the high-efficiency solution introduction system APEX in connection with a sector-field ICP-MS a sensitivity of more than 5,000 counts fg(-1) uranium was achieved. The use of an aerosol desolvating unit reduced the formation rate of uranium hydride ions UH(+)/U(+) down to a level of 10(-6). An abundance sensitivity of 3 x 10(-7) was observed for (236)U/(238)U isotope ratio measurements at mass resolution 4000. The detection limit for (236)U and the lowest detectable (236)U/(238)U isotope ratio were improved by more than two orders of magnitude compared with corresponding values by alpha spectrometry. Determination of uranium in soil samples collected in the vicinity of Chernobyl nuclear power plant (NPP) resulted in that the (236)U/(238)U isotope ratio is a much more sensitive and accurate marker for environmental contamination by spent uranium in comparison to the (235)U/(238)U isotope ratio. The ICP-MS technique allowed for the first time detection of irradiated uranium in soil samples even at distances more than 200 km to the north of Chernobyl NPP (Mogilev region). The concentration of (236)U in the upper 0-10 cm soil layers varied from 2 x 10(-9)g g(-1) within radioactive spots close to the Chernobyl NPP to 3 x 10(-13)g g(-1) on a sampling site located by >200 km from Chernobyl.     

How do transformational leaders foster positive employee outcomes? A self‐determination‐based analysis of employees' needs as mediating links

Although followers' needs are a central aspect of transformational leadership theory, little is known about their role as mediating mechanisms for this leadership style. The present research thus seeks to integrate and extend theorizing on transformational leadership and self‐determination. In particular, we propose that the satisfaction of followers' basic needs (autonomy, competence, and relatedness) mediates the relationship between transformational leadership and employee outcomes (job satisfaction, self‐efficacy, and commitment to the leader). We tested this model in two studies involving employees from a broad spectrum of organizations in Germany (N = 410) and in Switzerland (N = 442). Results revealed largely consistent patterns across both studies. The need for competence fulfillment solely mediated the link between transformational leadership and occupational self‐efficacy; the need for relatedness fulfillment solely mediated the link between transformational leadership and commitment to the leader. The mediating pattern for the link between transformational leadership and job satisfaction varied slightly across studies. In Study 1, only the need for autonomy fulfillment was a significant mediator, whereas in Study 2, all three needs mediated this relationship. Taken together, our study integrates theorizing on transformational leadership and self‐determination by corroborating that need fulfillment indeed is a central mechanism behind transformational leadership. Copyright © 2012 John Wiley & Sons, Ltd.     

环境促进发展:人、地球、繁荣

在联合国环境署新出版的<全球环境展望3>中提出的严酷事实揭示了我们这个神奇的蓝色星球的现状以及我们要恢复其健康和自然财富所亟需的坚定选择 .     

Polychlorierte Naphthaline

Measurements show that PCN may occur in industrial waste and residues in the mg/kg range. Investigations were carried out with optimized parameters for GC and MS using two different GC/MS-systems. Chromatograms were obtained for a variety of chlorination degrees using capillary columns of different polarities. It is proposed to quantify PCN using relevant single compounds comparable to the analysis of polychlorinated biphenyls.