固相净化气相色谱法测定水产品中多种有机磷农药残留

建立了水产品中8种有机磷农药残留同时测定的方法,选择乙腈提取,ENVI-C18串联PSA固相萃取柱净化,经丙酮/正己烷混合溶液（体积比1∶1）洗脱,洗脱液氮吹浓缩后采用气相色谱外标法定量。8种有机磷农药在0.050 mg/L～1.00 mg/L范围内线性良好,检出限在1.8 μg/kg～2.5 μg/kg之间,3个添加水平加标样品平行测定的相对标准偏差为1.1%～5.7%,回收率为69.8%～116%。     

污水处理厂进出水及其受纳水体中典型PPCPs的污染特征

以对乙酰氨基酚为目标物,利用固相萃取(SPE)-高效液相色谱(HPLC)法测定了该药物在泰安市污水处理厂进出水和地表水体中的含量。结果表明,对乙酰氨基酚在污水处理厂进水中均被检出,质量浓度为0.9~238μg/L,表明生活污水为污水处理厂该药物活性成分的来源,出水中质量浓度为ND~8.3μg/L,去除率较高,其中生物降解是主要的降解机制。在泮河中的质量浓度为ND~3.59μg/L,与国内外其他地表水体相比,处于同一个数量级,且污水厂排水口下游水体中目标物浓度高于上游,反映出污水处理厂排放可能是其受纳水体中PPCPs的主要来源之一。     

The Use of Atmospheric Dispersion Models in Risk Assessment Decision Support Systems for Pesticides

In the evaluation of potentially adverse effects oforganic chemicals such as pesticides on theenvironment the atmosphere may play an important role.After its release to the atmosphere the chemical willbe transported/dispersed in the atmosphere and finallyit will be removed either by atmospheric-chemicaldestruction or by deposition to the underlying soil orsurface water. In a risk assessment decision supportsystem both ambient concentrations and depositionfluxes must be known to evaluate the risk of directexposure (inhalation) or the risk of soil and watercontamination caused by deposition. This paperdiscusses the use of atmospheric dispersion models insuch risk assessment decision support systems.     

中国环境监测信息产品的主要问题及发展方向

基于中国环境监测信息产品的发展现状,针对信息产品生产流程的监测数据生成、监测数据加工、信息产品服务3个阶段分别指出存在的主要问题,并提出未来需全面提升环境监测信息产品的科学性、准确性、敏感度、服务对象满意度以及信息供给普惠度。     

2,5,6,9,10-Pentabromocyclododecanols (PBCDOHs): a new class of HBCD transformation products

Pentabromocyclododecanols (PBCDOHs) are potential environmental transformation products of hexabromocyclododecanes (HBCDs). They are also potential stage one metabolites of biological HBCD transformations. Herein, we present analytical evidence that PBCDOHs are also constituents of technical HBCDs and flame-proofed polystyrenes (FP-PSs). PBCDOHs are possibly formed during the synthesis of technical HBCD, presumably during the bromination of cyclododecatrienes in aqueous isobutanol together with isobutoxypentabromocyclododecanes (iBPBCDs), which have been identified in these materials recently. Of the 64 stereoisomers possible, eight pairs of enantiomers, named α-, β-, γ-, δ-, ε-, ζ-, η-, and θ-PBCDOHs were separated with a combination of normal-, reversed- and chiral-phase LC. Crystal structure analysis revealed the stereochemistry of the α-PBCDOH pair of enantiomers, which was assigned to (1S,2S,5R,6S,9S,10R)-2,5,6,9,10-pentabromocyclododecanol and its enantiomer. Mass spectrometric data are in accordance with the expected isotope patterns. On a C₁₈-RP-column, the polar PBCDOHs eluted before the HBCD and iBPBCD classes of compounds. PBCDOHs were also found in FP-PS materials. The stereoisomer patterns varied considerably in these materials like those of HBCDs and iBPBCDs. Expanded polystyrenes were rich in late-eluting stereoisomers, similar to technical HBCD mixtures. Extruded polystyrenes contained more of the polar, faster-eluting isomers. The presented chromatographic and analytical methods allow a stereoisomer-specific search for PBCDOHs in biota samples, which might have experienced metabolic HBCD transformation reactions. Besides this potential source, it has to be recognized that PBCDOHs are by-products in technical HBCDs and in flame-proofed polystyrenes. Therefore, it is likely that PBCDOHs and iBPBCDs are released to the environment together with HBCD-containing plastic materials.     

Multiresidue analysis and evaluation of the matrix effect on 20 pesticides in Brazilian maize (Zea mays L.) flour

Abstract

Maize consists of a cereal widely used in the preparation of different food products. Brazil is one of the world's largest maize producers. Several types of pesticides have been applied in maize crop, which can lead to the contamination of the derived products. The present work aims at the validation of multiresidue method to analyze the matrix effect and level of pesticides in maize flour. Twenty residues were investigated in samples commercialized in the state of Ceará, Brazil. The method was satisfactorily validated, according to parameters recommended by European Union. About 55% of the pesticides had an intense negative matrix effect. Multiresidue analyzes showed the presence of traces of fenitrotion in 20% of maize flour samples. Detected levels were below maximum residue limits recommended for maize. The results indicate that maize products need continuous monitoring to ensure food security.     

类水滑石衍生复合氧化物催化水解羰基硫的研究

采用共沉淀法制备了一系列的类水滑石衍生复合氧化物催化剂,利用正交实验设计对催化剂的制备条件进行了优化,研究了金属组合、合成pH、M2+/M3+、二价金属比、焙烧温度和晶化温度等6个因素对羰基硫催化水解过程中催化剂硫容的影响。结果表明,金属组合、二价金属比和焙烧温度的影响极其显著(p=99%),晶化温度的影响显著(p=95%),合成pH与M2+/M3+对催化剂活性影响不显著(p=90%)。在设定实验条件下,金属组合取Co-Ni-Al、合成pH为9,M2+/M3+为3,二价金属比1,焙烧温度取350℃,晶化温度50℃时制得的催化剂具有最高的催化活性。对最佳制备条件下得到的催化剂进行了重复性实验以及XRD表征,结果表明制备的催化剂的硫容为7.10 g硫/g催化剂,Co3O4可能是其活性中心。     

3D-QSAR of fungal quorum-sensing inhibiting analogs of farnesol

Thirty-four analogs with variable antifungal activity were selected to develop models for establishing three-dimensional quantitative structure-activity relationships (3D-QSAR). Comparative molecular field analysis (CoMFA) and comparative similarity indices analyses (CoMSIA) were conducted on the group of analogs to determine the structural requirements for selectivity and potency in inhibiting biofilm formation and fungal growth. The best CoMFA model predicted a q² = 0.5 and an r² = 0.991, and revealed that electrostatic properties play a significant role in potency and selectivity. The best CoMSIA model combined electrostatics, hydrogen bond acceptor and donor, and hydrophobic fields with a q² = 0.664 r² = 0.952, S = 0.099, and F = 139.892. The analyses of the contour maps from both models provide significant insight into the structural necessities for a potent compound. Therefore, manipulating various chemical properties of the substituted groups on the farnesol chain can be used to enhance the fungicidal properties of the target compound.     

Kinetics and mechanism of the hydrolysis of thiamethoxam

The degradation of thiamethoxam [(EZ)-3-(2-chloro-1,3-thiazol-5-yl-methyl)-5-methyl-1,3,5-oxadiazinan-4-ylidene (nitro) amine] insecticide in buffers at different pH and temperature levels was investigated in laboratory studies. Acidic hydrolysis under conventional heating conditions and alkaline hydrolysis under both conventional heating and microwave conditions were carried out. Different hydrolysis products were found to form under alkaline and acidic conditions. Hydrolysis of thiamethoxam in acidic, neutral and alkaline buffers followed first-order reaction rate kinetics at pH 4, 7 and 9.2, respectively. Thiamethoxam readily hydrolyzed in alkaline buffer but was comparatively stable in neutral buffer solution. The main products formed under different conditions were characterized on the basis of infrared (IR), ¹H-NMR and Mass spectroscopy. The possible mechanisms for the formation of these hydrolysis products have also been proposed.     

Three-dimensional quantitative structure activity relationships of quorum-sensing and biofilm inhibitors in gram-negative bacteria

Thirty N-acyl homoserine lactone (AHL) analogs with variable antibacterial activity and displaying inhibition of biofilm formation were selected to develop models for establishing three-dimensional quantitative structure-activity relationships (3D-QSAR). Comparative molecular field analysis (CoMFA) and comparative similarity indices analysis (CoMSIA) were carried out to determine the optimum structural requirements for selectivity and potency of quorum-sensing and bacterial biofilm inhibition. The best CoMFA model predicted a q² value of 0.519 and an r² value of 0.984 and revealed that electrostatic and steric properties play a significant role in potency and selectivity. The CoMSIA model predicted a q² value of 0.411 and an r² value of 0.938 based on a combination of steric, electrostatic, and hydrophobic effects. The analysis of the contour maps from each model provide insight into the structural requirements for increasing the activity of a compound. Consequently, manipulating the chemical and physical properties of substituted acyl groups on the homoserine lactone moiety can provide important information toward enhancing the antibacterial properties of the target chemical compound.