Variations in sensitivity of two populations of Corophium Orientale (Crustacea: Amphipoda) towards cadmium and sodium laurylsulphate

The aim of this work was to monitor the sensitivity of two populations of Corophium orientale (Crustacea: Amphipoda) living at the outfall of two rivers (Magra and Serchio), comparing their responses towards two different toxicant solutions. Sensitivity was monthly checked performing the 96h-LC₅₀ static water only test with Cd(NO₃)₂ and SDS. If no significant differences were found between the two populations, they could have been employed without distinction to perform sediment toxicity bioassays. As regard to Cd, an increasing in LC₅₀ values from summer to winter was evident in each population (Serchio River: August 2003  =  1,36 mg/l, February 2004  =  7,23 mg/l; Magra River: August  =  1,21 mg/l, April  =  5,01 mg/l). This pattern was correlated to the droop of temperatures in winter period. The responses of the two populations towards the cadmium were compared using the ANOVA. The analysis showed any significant differences between the populations (p  =  0.12). The pattern of sensitivity towards SDS for the population living on Magra River was similar to the same pattern found for Cd; as regard to the population living on Serchio River, data were not enough to describe the annual pattern. Anyway, statistical analysis was performed and no significant differences were found between the two populations (p  =  0.34).     

Simultaneous determination of acidic pesticides in vegetables and fruits by liquid chromatography—tandem mass spectrometry

A sensitive and efficient method has been developed for the simultaneous determination of 73 multi-class acidic pesticides, such as phenoxy acid and sulfonylurea herbicides, in vegetables and fruits. The sample preparation procedure was carefully optimized for the efficient removal of co-extracted matrix components. The method involves extraction of acidic pesticides with acetonitrile containing hydrochloric acid, removal of water from crude extract by salting out, and sequential cleanup by octadecylsilyl silica gel and silica gel columns. For samples containing high amounts of pigments, such as spinach, additional cleanup using a graphitized carbon column was performed prior to liquid chromatography–mass spectrometry (LC–MS/MS) analysis. Recovery tests were performed for five times for each sample of cabbage, spinach, potato, eggplant, orange, and apple fortified at 0.01 mg kg?1. Out of the 73 tested pesticides, 70 for cabbage, 67 for spinach, 69 for potato, 67 for eggplant, 64 for orange, and 70 for apple were within the range of 70–120%, with relative standard deviations below 25%. Nitenpyram and pyrasulfotole showed low recoveries for all the samples tested, probably due to low recoveries from silica gel column. The developed method effectively removed co-extracted matrix components and was highly selective, with no interfering peaks found in the chromatograms of blank samples. The overall results indicate that the developed method is suitable for the quantitative analysis of acidic pesticide residues in vegetables and fruits.     

Application of a LC–MS/MS method for multi-mycotoxin analysis in infant formula and milk-based products for young children commercialized in Southern Brazil

ABSTRACT

An analytical method based on liquid chromatography–tandem mass spectrometry (LC–MS/MS) was validated and applied for the analysis of aflatoxin M₁ (AFM₁), ochratoxin A (OTA) and deoxynivalenol (DON) in infant formula and milk-based products for young children commercialized in Brazil. A total of 38 samples were evaluated, including 12 infant formula, 14 follow-on formula and 12 samples of milk-based products. AFM₁ was detected in 12 (32%) samples, and seven (18%) samples contained AFM₁ levels above the method limit of quantification in a concentration range between 0.013 and 0.067 ng mL^?1 (0.026 ± 0.019). Two samples of milk-based products exceeded the maximum level (ML) fixed by the European Union for AFM₁ in baby foods, however, all samples were in agreement with the levels established by the Brazilian regulation. OTA and DON were not detected in any of the analyzed samples.     

Evaluation of pressurized liquid extraction for the determination of neonicotinoid pesticides in green onion

Abstract

A pressurized liquid extraction (PLE) method was presented for the determination of six neonicotinoid pesticides, acetamiprid, clothianidin, dinotefuran, imidacloprid, thiacloprid, and thiamethoxam in green onion. The critical parameters of PLE, e.g. extraction solvent, temperature, pressure, number of cycles, and static extraction time, were optimized by test on the spiked green onion with six neonicotinoids and the incurred green onion applied with four commercial neonicotinoid insecticide formulations (acetamiprid, dinotefuran, imidacloprid, and thiamethoxam). As a result, the recoveries of six neonicotinoids obtained by one cycle PLE with acetonitrile at 140?°C and 50?bar for 10?min were 94.7–99.5%. These results were acceptable according to the validation guideline for testing method of agricultural chemicals in food by Ministry of Health, Labour, and Welfare in Japan. PLE was also validated by the test on the incurred green onion. The analytical values of four neonicotinoids obtained by PLE were good agreement with those obtained by solid–liquid extraction with homogenizer, which is employed for Japanese official method for the analysis of pesticide residues in food (the ratios of analytical values obtained by PLE to those obtained by solid–liquid extraction were 99.7–101.2%). These results indicate that PLE is applicable for the determination of neonicotinoids in green onion.     

含氯苯酚类化合物结构表征与毒性预测

将有机化合物中的不同非氢原子及非氢原子之间的关系参数化得到新的结构描述符,运用该描述符对部分含氯苯酚类化合物分子结构进行了参数化表征。采用偏最小二乘回归(PLS)方法构建了化合物结构与毒性(-lgIC₅₀)之间的关系模型,模型的建模相关系数(R²)为0.948,“留一法”交互检验的相关系数(Q²)为0.922,标准偏差(SD)为0.184。结果表明结构描述符能较好地表征化合物分子结构特征,所建模型稳定性好、预测能力强,对于酚类化合物QSAR研究具有一定的参考价值。     

Rapid and Sensitive LC/MS/MS Direct Injection Method for the Determination of Trace Level Corexit EC9500A Oil Dispersant in Seawater

A rapid and sensitive liquid chromatography tandem mass spectrometry (LC/MS/MS) method for the determination of trace dioctyl sulfosuccinate (DOSS) concentrations in seawater samples has been established. The method is well suited to aquatic environment impact monitoring following application of the dispersant Corexit EC9500A. Linearity of the method was demonstrated down to 0.05 ng/mL^?1 (0.05 µgL^?1) DOSS in seawater, with a 2.4% relative standard deviation precision for preparation replicates. A US EPA method limit of detection of <0.02 ng/mL^?1 (<0.02 µgL^?1) was calculated and specificity was confirmed by monitoring of two qualifier ions at 291.1 m/z and 227.1 m/z. These transitions were confirmed by QToF analysis to be associated with the DOSS precursor ion at 421.2 m/z. For application to seawater samples and samples containing oil particulates, a practical and repeatable calibration range of 0.5 ng/mL^?1 (0.5 µgL^?1) to 25.0 ng/mL^?1 (25.0 µgL^?1) DOSS is reported. The method was shown to have excellent precision and accuracy, with a consistent ≤1.6% relative standard deviation for system suitability standards at 0.5 ng/mL^?1 (0.5 µgL^?1) and linear weighted (1/x) regression coefficients of determination ≥0.995. The surfactant nature of the analyte is discussed in relation to detection limit and loss of analyte. Speculation of a relationship between DOSS in association or aggregation with divalent cations, such as Ca²⁺ present in salt water and hard water, is suggested. The consequent effects on cell ionic balance and membrane function are discussed.     

利用概率单位法估算EC50的研究（Estimation of Probit Methods on EC50）

以两组典型毒性数据为例,综合比较了5种常见概率单位模型计算程序在EC50估算上的差异,并在此基础上比较了3种不同置信区间的估算方法.在对照组受抑制率为零时,5种方法的参数估算结果一致;当对照组受抑制率不为零时,将对照组数据纳入整个计算过程的方法可以给出可靠的参数估算结果.3种不同置信区间估算方法的比较表明:在毒性数据分布对称性良好的情况下,基于Delta函数与Fieller定理的方法给出的结果相近,但后者可以在更广泛的情况下给出置信区间;相比而言,基于bootstrap重抽样的非参数方法获得的置信区间较窄,表现出更好的灵敏度.     

不同油类对虾蟹类幼体的胁迫效应

了解不同油类对虾蟹类幼体的急性毒性效应。曝油处理采用磁力搅拌器搅拌,一定时间的超声波乳化等操作,模拟溢油在海洋中风浪、涡动、湍流的乳化过程;设置阶梯浓度组,并在多个平行组急性试验的基础上,估算出8种油品对2种虾类和2种蟹类的半致死质量浓度LC50和安全质量浓度MPC,并运用程序编制溢油质量浓度与虾蟹类死亡率相关性的估算模型。经过分析,结果得到:各MPC值参差不齐,差距较大;燃料油普遍比原油的毒性效应大;相同生长阶段,蟹类比虾类抗油毒害性强、中国明对虾Fenneropenaeus chinensis比日本囊对虾Marsupenaeus japonicus抗油毒害性强、锯缘青蟹Scylla serrata比三疣梭子蟹Portunus trituberculatu抗油毒害性强。编制的溢油质量浓度与死亡率相关性的评估模型,简易方便直观,为渔业污染事故理赔提供了一定的参考价值,亦为海域的生态经济学评估提供了一种新的研究方法。     

异噻唑啉酮类化合物对三角褐指藻的抑制效应

研究了不同浓度异噻唑啉酮类化合物BIT(1,2-苯并异噻唑啉-3-酮)及其类似物X(N-丙酰基-1,2-苯并异噻唑啉酮-3-酮)对三角褐指藻生长的抑制效应.根据藻细胞生长、比生长速率、藻细胞密度比、藻细胞内色素含量变化结果表明,在实验所设定的浓度(0~3mg/L)范围内,BIT和X在高浓度下对三角褐指藻生长均具有一定的抑制效应,增加细胞生长的延滞期,但在低浓度下不明显,BIT的抑制效应优于X,但BIT和X的这种抑制作用均会随着处理时间的延长而减弱,藻细胞逐渐恢复快速增殖.根据Logistic曲线方程拟合获得的BIT和X对藻的96h半效应质量浓度(EC50)分别为1.95mg/L(R2=0.988, P=0.0013)和3.26mg/L(R2=0.908, P=0.0279),EC50值的大小进一步说明BIT比X对三角褐指藻的抑制作用强.     

硝基苯化合物对枯草芽孢杆菌的毒性及构效分析

以枯草芽孢杆菌(Bacillus subtilis)为实验生物,测定了12种硝基苯化合物对其种群生长抑制的12 h IGC₅₀(50% inhibitory growth concentration)值.应用lgP,1xv,I,1Ka,σ-和E_LUMO 6种物理化学描述符进行构效关系分析,建立QSAR模式,并且预测了6个相似化合物的毒性.