Comparative study of methods for the extraction of eleven organophosphorus pesticide residues in rice.

Several extraction methods are compared for the simultaneous analysis of organophosphorus pesticides in unpolished rice. Four stationary phases were used for the subsequent gas-liquid chromatographic (GLC) determination of the selected pesticides. Using 3 different GLC columns, 11 pesticides were completely separated and identified. The efficiency of the cleanup and the sensitivity of the analytical method were evaluated by using powdered unpolished rice samples fortified with the pesticides and also wheat and dried bean samples. Average recoveries ranged from 74.7% for disulfoton to 97.4% for malathion in unpolished rice and from 68.1% for disulfoton to 108.3% for malathion in other crops. The method described is applicable to the analysis of selected organophosphorus pesticide residues in unpolished rice, wheat, buckwheat, and dried beans.     

农药残留快速检测方法研究进展

在果蔬生产中,随着农药的大量和不合理使用,发展相应的农药残留检测技术已越来越受到社会的高度关注和重视,成为全球的焦点。该文概述了近年来果蔬农药残留快速检测方法的研究进展,主要包括酶抑制法、酶联免疫法、生物传感器法、近中红外光谱法、荧光光谱法、拉曼光谱法和核磁共振技术,详细介绍了上述方法的检测原理、研究现状及实际应用情况,分析了各方法的优缺点及研发难点,并对果蔬农药残留快速检测方法的发展趋势进行了展望。     

Chlorinated pesticide occurrence in the Uruguay River (Argentina-Uruguay)

Water samples, collected trimonthly along the Uruguay River between February 1988 and December 1989, were analyzed for alpha- and gamma-HCH, heptachlor and its epoxide, aldrin, dieldrin, and the o-p′ and p-p′ isomers of DDE, DDD and DDT to assess the present status of the contamination in this South American region. In general, chlorinated pesticides were encountered at very low concentrations. HCH isomers were the most commonly detected compounds with concentrations ranging from the detection limits to 10 ng L^?1. Heptachlor, heptachlor epoxide, aldrin, dieldrin, p-p′ DDE and p-p′ DDT were occasionally encountered while o-p′ DDE, p-p′ DDD, o-p′ DDD and o-p′ DDT were never detected. Compared to previous studies in the area, the present data seems to indicate that there was a decrease in the concentrations of these compounds.     

Partition chromatographic separation of pesticide residues from fats.

A simple, rapid, and efficient partitioning column consisting of acetonitrile on Florisil has been developed for the separation of pesticides from fish, beef, and butter fat. The efficiency of the cleanup column is between 97 and 100%. Nine pesticides having partition coefficients between n-hexane and acetonitrile of less than or equal to 0.05 were satisfactorily separated from fat with good recoveries. When the column was used to clean up temephos in a fish extract, 99.91% of the fat was eluted with 20 ml n-hexane with no loss of the pesticide.     

State programs for pesticide residues in foods

Two U.S. data collection and dissemination programs, FEEDCON and FOODCONTAM, are described. FEEDCON provides information on contamination levels in animal feeds of toxic chemical residues (pesticides, industrial chemicals, heavy metals, mycotoxins, natural plant toxins, salmonella, and therapeutic drug cross-contaminations). FEEDCON data are collected from approximately 40 state feed regulatory agencies, feed manufacturers, and related groups who subscribe ($100-$200 per year) to the program, which is sponsored by the Association of American Feed Control Officials. FOODCONTAM provides similar information, but is limited to pesticides, heavy metals and industrial chemicals (polychlorinated and polybrominated biphenyls, etc.) in human foods. Both programs have been developed and initiated under U.S. Food and Drug Administration contracts with the Mississippi State Chemical Laboratory. Program structures of both are outlined conceptually, and FOODCONTAM is described in detail. FOODCONTAM data-sharing program development is essentially complete, but expansion by incorporating FDA data with State Laboratory data is nearing reality.     

Organophosphorus pesticide residues in Mexican commercial pasteurized milk

A study was conducted to measure residues of 13 organophosphorus (OP) pesticides, widely used as dairy cattle ectoparasiticides or in crops used for animal feed, in homogenized and pasteurized Mexican milk samples. Four different milk brands with high distribution were collected biweekly during a 12 month period (n = 96) in supermarkets. OP pesticide residues were measured by gas chromatography with a flame photometric detector. Approximately 39.6% of the samples contained detectable levels of OP pesticide residues. Eight samples contained residues exceeding established maximum residue limits (MRL), and the OP pesticides present in these samples were dichlorvos (five samples), phorate, chlorpyrifos, and chlorfenvinphos (one sample, respectively). Average residues of 13 OP pesticides measured were below established MRLs ranging between 0.0051 and 0.0203 ppm.     

Effect of pesticide residues on the aromatic composition of red wines.

The influence of pesticide residues on the aromatic composition (major and minor volatiles) of red wines made from Vitis vinifera (Monastrell var.) was studied by comparing the concentration of aromas in wines made from grapes subjected (or not) to phytosanitary treatment with chlorpyrifos, fenarimol, mancozeb, metalaxyl, penconazole, and vinclozolin, according to the agricultural practice of the area. The analytical determination of the major volatiles was made by gas chromatography using a flame ionization detector, while the minor volatiles were determined by adsorption-thermal desorption gas chromatography using a mass selective detector. There were significant differences between the ethyl acetate, methanol, isobutanol, and diethylacetal levels of the control wine and that containing chlorpyrifos residues, although only the ethyl acetate exceeded the olfactory threshold. With regard to the minor volatiles, significant differences were detected in the concentrations of some esters, aldehydes, and acids. However, only isoamyl acetate exceeded the olfactory threshold in wines containing residues of chlorpyrifos, fenarimol, and vinclozolin.     

Separation of pesticide residues from lipids prior to gas-liquid chromatographic analysis.

Lipids are separated from dieldrin, endrin, and p,p'-DDE residues by saponification in ethanolic sodium hydroxide, acidification with dilute sulfuric acid, and adsorption chromatography on deactivated alumina, using petroleum ether as the eluant. Dieldrin, endrin, and p,p'-DDE are efficiently recovered (95-102%), and p,p'-DDT is converted to p,p'-DDE, which is then recovered with high yield (90-96%). Extremely low lipid carryover (less than 0.3-0.5%) is observed for 0.5-1.0 g samples of chicken fat.     

用于农药残留快速检测的压电免疫生物传感器的研究

该文建立了一种压电免疫生物传感器结合流动注射的方法检测样品中的农药残留.为了有效地捕获有机磷农药抗原,比较了三种在石英晶体金电极表面上固定有机磷单克隆抗体的方法.在0.005～10μg/mL范围内,有机磷浓度与晶体频率的变化之间呈较好的相关关系.回归方程:y=5.9111Ln(x) 51.979,决定系数为:0.93.该传感器的最低检测限为2.16×103μg/mL,选择性好,可以重复使用.     

Determination of chlorinated pesticide residues in foods. II. Simultaneous analysis of chlorinated pesticide and phthalate ester residues by using AgNO3-coated Florisil column chromatography for cleanup of various samples.

A simplified method suitable for simultaneous analysis of chlorinated pesticide and phthalate ester residues in various foods was developed. Chemical residues were quantitatively extracted from fatty and vegetable samples with acetonitrile as follows: Chemical standard in 0.5 mL ethanol solution was added to 10 g homogenized sample. After 3 hr, pork and beef were extracted 3 times with 20 mL portions of acetonitrile. The acetonitrile layers were diluted with water and extracted with n-hexane. Rice samples were combined with 10 mL water, 5 mL acetonitrile and 1 mL ethanol and extracted 3 times with 20 mL portions of n-hexane. The n-hexane concentrate from each sample was submitted to AgNO3-coated Florisil column chromatography. The AgNO3 coating adequately adsorbed interfering coextractives. Extracts of fish and vegetable samples were separated into 2 fractions by the above column chromatography. Supplemental cleanup procedures were also developed to accurately determine phthalate esters eluted in the second fraction. Satisfactory gas chromatograms were obtained for most samples.     

Pesticide residues in Lake Albufera, Valencia, Spain

Analysis of water samples from the lake in Albufera, Valencia, indicates that the pesticides molinate, benthiocarb, and fenitrothion do not reach levels that are lethal to fish.     

Reduction of pesticide residues on produce by rinsing

In 1997 this laboratory initiated a research program with the objective of examining the effect that rinsing of produce with tap water would have on pesticide residues. Samples were obtained from local markets and/or grown at our experimental farm. Because approximately 35% of produce from retail sources contains pesticide residues, growing and treating produce at an experimental farm had the advantage that all such samples contain pesticide residues. Pesticides were applied under normal field conditions to a variety of food crops and the vegetation was allowed to undergo natural weathering prior to harvest. The resulting samples contained field-incurred or "field-fortified" residues. This experimental design was employed to mimic as closely as possible real world samples. Crops were treated, harvested, and divided into equal subsamples. One subsample was processed unwashed, whereas the other was rinsed under tap water. The extraction and analysis method used was a multi-residue method developed in our laboratory. Twelve pesticides were included in this study: the fungicides captan, chlorothalonil, iprodione, and vinclozolin; and the insecticides endosulfan, permethrin, methoxychlor, malathion, diazinon, chlorpyrifos, bifenthrin, and DDE (a soil metabolite of DDT). Statistical analysis of the data using the Wilcoxon signed-rank test showed that rinsing removed residues for nine of the twelve pesticides studied. Residues of vinclozolin, bifenthrin, and chlorpyrifos were not reduced. The rinsability of a pesticide is not correlated with its water solubility.     

Analysis of pesticide residues by chemical derivatization. II. N-methylcarbamates in natural water and soils.

A method for the quantitative determination of several N-methylcarbamates in natural waters and the applicability of the derivative to soil samples using a previously published extraction procedure are described. After extraction of the carbamates from the substrate, the carbamates are hydrolyzed in a 10% methanol-potassium hydroxide solution to form the phenolic hydrolysis products, which are isolated and derivatized with pentafluorobenzyl (PFB) bromide to produce the PFB ether derivatives. The PFB derivatives are cleaned up and fractionated on a silica gel microcolumn and determined by electron capture gas-liquid chromatography (GLC). Eight organophosphate pesticides and 2 phthalate acid esters that hydrolyze to phenols or phthalic acid were evaluated as potential interferences and were found not to interfere with any of the carbamates tested. Quantitative determinations of 0.1 mug carbofuran and 3-ketocarbofuran and 0.5 mug carbaryl, metmercapturon, and Mobam in a 1 L water sample are possible. Propoxur was not determined at levels less than 1 mug/L due to the short GLC retention time of the derivative and interferences from the reagents at the lower levels.     

基于荧光光谱的生菜农药残留检测

为了研究采用荧光光谱技术对生菜农药残留快速无损定性鉴别的可行性,该文通过采集180个生菜样品（3个浓度农药残留生菜,每个浓度农残生菜样本数为60,其中农药与水配比为1：500、1：1000、1：1200,即重度超标、轻微超标、标准农残）的荧光发射光谱,结合Savitzky-Golay（SG）、标准正态变量变换（standard normalized variable,SNV)、标准正态变量变换结合去趋势（standard normalized variable detrending,SNV detrending）、SG与SNV算法组合（SG-SNV）、SG与SNV detrending算法组合（SG-SNV detrending）对提取的荧光光谱进行预处理,基于全光谱、荧光特征峰值、小波特征建立支持向量机（Support Vector Machine, SVM）分类模型。其中,小波特征通过小波变换对原始光谱以及预处理后光谱进行特征选择获取,分别采用 db4、db6、sym5、sym7作为小波基函数。试验结果表明：基于小波特征、荧光特征峰值建立的 SVM 模型预测集识别率要高于基于全光谱建立的 SVM 模型。以 sym5作为小波基函数,基于 SG-SNV detrending预处理光谱选择的小波特征建立的SVM模型取得最优的预测集识别率93.33%,最佳小波分解层数为4。结果表明应用荧光光谱技术对生菜农药残留鉴别是可行的,为生菜农药残留快速、无损检测分析提供了参考。     

Investigation and simplification of the sweep co-distillation cleanup of pesticide residues in animal fats.

The sweep co-distillation technique of Storherr et al. was investigated and simplified. Six organochlorine pesticides in animal fats were cleaned up under various distillation conditions as follows: No solvent was used, or solvent injection rates were 1 mL/min or 2 mL/3 min. Distillation tubes of 6.7 and 9.0 mm id diameter were compared. Distillation temperatures were varied from 150 to 300 degrees C. The complex condenser of Storherr et al. was compared with a simpler pipet condenser. A U-tube condenser which allows direct introduction onto a Florisil column for secondary cleanup was evaluated. The following modifications to the sweep co-distillation technique resulted: no solvent introduction, distillation temperature 230 degrees C, nitrogen flow rate 600 mL/min, 6.7 mm id distillation tubes with simplified packing, and incorporation of the U-tube condenser. The new technique gave recoveries comparable to those of Storherr et al., but it is faster than most bisolvent partition methods and no large volumes of solvent are required.