Evaluation of a multiresidue method for pesticides in cereals using supercritical fluid extraction and gas chromatographic detection

Supercritical fluid extraction (SFE) was evaluated to be applied for residue analysis of 22 gas chromatography/electron capture detector-nitrogen phosphorus detector (GC/ECD-NPD) amenable pesticides in rice, wild rice and wheat. Samples were extracted with supercritical carbon dioxide at 200 atm pressure and 50°C temperature, using methanol as a static modifier. Mean recoveries obtained with the proposed SFE method at two spiking levels with four replicates per level are compared with those obtained with an ethyl acetate-based solvent extraction/gel permeation chromatography (GPC) clean up method. Both methods gave consistent high recoveries for almost all the pesticides from all the commodities with overall mean recoveries higher than 70% with relative standard deviations lower than 20%. Remarkable exceptions were captafol and dimethoate, for which low and/or non-reproducible recoveries were obtained with the SFE method. Residue levels determined with both methods in nine different incurred samples of wheat, containing some of the studied pesticides, were very similar, but, in all cases, slightly higher levels were determined with the SFE method.     

Degradation of Metolachlor in Crude Extract of Aspergillus Flavus

Abstract

Crude enzyme from a soil fungus, Aspergillus flavus, was isolated from a field soil following repeated applications of metolachlor [2-Chloro-N-(methoxy-1-methylethyl)-2′-ethyl-6′-methyl acetanilide]. Metolachlor hydrolysis by the crude enzyme extract was determined by enzyme assay. The tests were performed in phosphate buffer, pH 7.5, and the reaction was carried out at two herbicide concentrations (20 and 100 μg mL^?1) and two crude extract volumes (0.2 and 0.5 mL of the homogenized crude extract mixture). The rate of metolachlor degradation was found faster in samples containing higher volume of crude extract, (T _1/2, 5.7 h) for both concentrations of the herbicide. The activities of enzymes responsible for dechlorination coupled with hydroxylation, N-dealkylation, and breaking of amide linkage were found responsible in the degradation.     

An alternative supercritical fluid extraction system for aqueous matrices and its application in pesticides residue analysis

Abstract

Supercritical fluid extraction (SFE) is a rapid and convenient method for the isolation of organic compounds from environmental samples. This paper describes a supercritical carbon dioxide (CO₂) extraction system that uses a newly designed extraction cell to recover organic compounds from an aqueous matrix. Analysis of the extracts by gas chromatography‐electron capture detector (GC‐ECD) indicated that the herbicide trifluralin (2,6‐dinitro‐N,N‐dipropyl‐4‐trifluoromethylaniline) could be quantitatively extracted by using the SFE system proposed with small amounts of sample. The percentage of recovery obtained with the SFE system described was twice as high as the result obtained using a conventional solid‐phase extraction technique. Extraction by SFE was completed in a short period of time using a simple and low‐cost home‐made system that did not require the use of organic solvents.     

Influence of herbicide glyphosate on growth and aflatoxin B1 production by Aspergillus section Flavi strains isolated from soil on in vitro assay

The effect of six glyphosate concentrations on growth rate and aflatoxin B₁ (AFB₁) production by Aspergillus section Flavi strains under different water activity (a_W) on maize-based medium was investigated. In general, the lag phase decreased as glyphosate concentration increased and all the strains showed the same behavior at the different conditions tested. The glyphosate increased significantly the growth of all Aspergillus section Flavi strains in different percentages with respect to control depending on pesticide concentration. At 5.0 and 10 mM this fact was more evident; however significant differences between both concentrations were not observed in most strains. Aflatoxin B₁ production did not show noticeable differences among different pesticide concentrations assayed at all a_W in both strains. This study has shown that these Aspergillus flavus and A. parasiticus strains are able to grow effectively and produce aflatoxins in high nutrient status media over a range of glyphosate concentrations under different water activity conditions.     

Modelling the extraction of soil contaminants with supercritical carbon dioxide

Extractions of volatile organic compounds (VOC’s) in contaminated soil from petroleum site were performed with supercritical carbon dioxide at different temperatures, pressures, extraction times, solvent flow rates, soil moisture contents and soil acidity. Three soil systems were investigated in order to compare the best parameters for extraction. A central composite rotatable design has been used to evaluate the influence of operation conditions on the extraction efficiency to generate model equations representing the types of soil. The results indicate that at least 70-80% of the initial amount of VOC’s can be removed at moderate temperatures even at very high moisture content. Supercritical extraction is best suited to silt type soils which have a low adsorption capacity. VOC’s recoveries from the artificial contaminated soil samples were higher in comparison with real contaminated soils. At moderate temperatures, the extraction efficiency for real soils is low because pollutants bind strongly to the soil.     

纳米TiO2薄膜光催化降解橡椀栲胶的研究

以Ti(OC4H9)4为原料,溶胶-凝胶法制备纳米TiO2 薄膜,用原子力显微镜(AFM)观察了纳米TiO2薄膜的形貌,X-射线衍射(XRD)考察相同条件下粉体的相结构.研究水中橡椀栲胶的光催化降解行为.结果表明,橡椀栲胶的降解可用Langmuir-Hinshelwood方程来描述,即浓度较高时,栲胶降解液的光催化降解符合零级动力学方程;浓度较低时,栲胶降解液的光催化降解符合一级动力学方程.外加H2O2对橡椀栲胶的光催化降解有极大的促进作用,但这种促进作用会因为光生电子效率的影响而有一个极限值.在远离橡椀栲胶溶液等电点的起始pH值条件下光催化降解效果较好,且在碱性条件下的降解速率高于酸性条件下的降解速率.     

水中除草剂阿特拉津的测定

采用二氯甲烷液液萃取-氮吹浓缩-丙酮定容去除干扰物,用气相色谱检测水中的阿特拉津,根据保留时间定性,外标法定量.本方法适用于水中阿特拉津的残留量分析,最低检测浓度为4.51×10-2 μg∕L.     

Using supercritical fluid extraction to measure the desorption and bioaccessibility of phenanthrene in soils

The aim of this paper was to measure the changing desorbable fraction and bioaccessibility of phenanthrene in two different soils with increasing soil-phenanthrene contact time using supercritical fluid extractions (SFE). Both soils were spiked with 100 mg kg⁻¹ phenanthrene and aged for 28 d. Desorption profiles were measured every 7 d using selective SFE conditions and the results were compared to ¹⁴C-phenanthrene mineralisation assays. Selective SFE showed significant differences in the rates and extents of desorption in the two soils, likely to be due to different organic matter composition. Post-extraction fitting of data yielded consistent SFE extraction times within ageing soils for bioaccessibility prediction.     

改进铁氧体共沉淀法去除污泥浸出液中的铜锌

采用改进铁氧体共沉淀法,用石灰乳溶液作中和剂,从污泥浸出液中去除铜、锌。实验结果表明,在混合液．pH为8．9、反应温度为室温、反应时间为1h、FeCl3和FeSO4初始浓度分别为0．1068mol／L和0．0534mol／L、n（Fe^3＋）：[n（Cu^2＋）＋n（Zn^2＋）]=10的最佳工艺条件下,浸出液中铜去除率为94．5％,锌去除率为98．0％。     

钻井废液的超临界水氧化处理及动力学分析

在反应温度为500～600℃、压力为25～30 MPa、停留时间为30～600 s的条件下,在连续式反应器中研究了钻井废液的超临界水氧化反应.结果表明:钻井废液的COD去除率可达90.00%以上;在600℃、停留时间为600 s时,钻井废液氧化后,剩余收集液的COD＜120 mg/L,满足《污水综合排放标准》(GB 8978-1996)中的二级标准.用幂函数方程描述了氧化剂过量时钻井废液超临界水氧化的反应动力学规律,反应速率常数与温度的关系符合Arrhenius公式,随停留时间的增加、温度的升高,有机物的去除率显著增加;反应速率常数随压力升高而增加,但反应速率常数的增幅随压力的升高而减小,反应活化体积不是常数.在25 MPa时,反应活化能和频率因子分别为(17 745.430 40±1 114.983 42)kJ/mol和1.152 3×10-4s-1模型计算值与实验值的误差在±15%以内.