Formulas for calculation of extraction volumes for commonly used pesticide residue extraction procedures

Formulas are presented for the calculation of extraction volume for pesticide residue procedures that use a single extraction with acetone, acetonitrile, or methanol, with or without prior dilution of these solvents with water. These formulas account for the volume change on mixing and for the volume contribution from the soluble sugars sucrose, glucose, and fructose. Results using these formulas are in agreement with the observed volumes of such mixtures within 0.3% throughout the following ranges, expressed as percent water in the mixtures: 15-38% for acetone, 4.8-59% for acetonitrile, and 9.3-33% for methanol.     

Evaluation of extraction procedures on determination of critical soil and foliar levels of boron and zinc in coffee plants

Abstract

Six‐month‐old coffee plants were grown in the greenhouse in pots containing a Dark Red Latosol (Orthox), to study the effect of boron (B) and zinc (Zn) on growth and leaf content of these micronutrients. Boron was added at levels of 0, 1, 3, and 5 mg kg^‐1, whereas Zn was added in proportions of 0, 5, 10, and 20 mg kg^‐1. Boron application affected total dry matter, height and diameter of stem, length and number of plagiotropic branches, number of leaves, ratio between total leaf area and number of leaves (ULA), ratio between total leaf area and total dry matter (LAR), leaf moisture, and index of potential yield (IPY). The IPY, defined as the ratio of dry matter of developed flowering buds plus flowers to the dry matter of underdeveloped flower buds and flowers, proved to be the an excellent parameter to assess B levels. Leaf B, well correlated with IPY, varied from 50 to 60 mg kg^‐1. Available B in soils, in nig kg^‐1, ranged from (with the critical levels between parentheses): 0.2 to 0.3 (0.2), as determined in a saturation paste, 0.6 to 1.0 (0.9), as determined in a hot water extract, 0.9 to 1.3 (1.2), with monocalcium phosphate in acetic acid, 1.1 to 1.4 (1.3), by Mehlich 1 method, 2.1 to 2.4 (2.4), by 0.05N HC1, 2.2 to 2.4 (2.4), by 0.1N HCl. Zinc additions caused a decrease in growth when B supply was limiting. On the other hand, B had no effect on dry matter yield when Zn was not added. Adequate Zn soil levels in mg kg^‐1 were 4.4, as determined by 0.05N HCl extraction, 4.2, by 0.1N HC1, 3.9, by Mehlich 1, 2.7, by EDTA extraction, and 2.1, in DTPA extracts. Leaf Zn, not affected by Zn additions, was between 12–14 mg kg^‐1.     

Comparison of two extraction procedures for recovering nitrite from cured meat products

A study was undertaken to determine the extent of loss of nitrite during the analytical workup of cured meats for nitrite analysis. Two extraction techniques were compared: (A) a relatively long (2 hr) and hot (80 degrees C) procedure carried out at the natural pH of the sample, and (B) the method of Sen and Donaldson that specifies an alkaline solution and much milder conditions (20 min at 50 degrees C at pH 8) for extraction. The data obtained suggest that considerable losses of nitrite can occur with the former procedure, especially in acidic samples. The overall percentage recoveries of added nitrite by the 2 methods ranged between 20 and 112, and 80 and 114, respectively. Average percentage recoveries for the acidic (pH less than 5) samples only were 47.2 for Method A as compared with 100.2 for Method B.     

Evaluation of supercritical fluid extraction/aminopropyl solid-phase "in-line" cleanup for analysis of pesticide residues in rice

Supercritical fluid extraction (SFE) and the use of aminopropyl solid-phase material for "in-line" cleanup was evaluated for residue analysis of 22 GC-amenable pesticides in wild- and white-rice samples with a fat content of 1.9 and 0.4%, respectively. After optimizing the extraction conditions on glass beads as inert material and evaluating the fat amount extracted from rice by SFE, the use of Florisil, Celite, Extrelut, Hydromatrix, and an aminopropyl material as fat-retention materials for SFE "in-line" cleanup was assessed, aminopropyl being the most suitable material for this cleanup of fat. Pesticide mean recoveries obtained from rice samples, at fortification levels around 0.5 mg/kg, by means of the SFE/in-line cleanup method finally proposed (15-mL CO2 volume, 50 degrees C temperature, 200 atm pressure, 200 muL of methanol static modifier, and a 1-cm layer of aminopropyl at the bottom of the extraction vessel), ranged between 74 and 98%, except for captafol and dimethoate for which mean recoveries lower than 21% were determined.     

Method for the analysis of triadimefon and ethofumesate from dislodgeable foliar residues on turfgrass by solid-phase extraction and in-vial elution.

Triadimefon, a fungicide, and ethofumesate, an herbicide, are commonly applied to turfgrass in the Pacific Northwest, resulting in foliar residues. A simple and rapid method was developed to determine triadimefon and ethofumesate concentrations from dislodgeable foliar residues on turfgrass. Turfgrass samples were washed, and wash water containing surfactant (a 0.126% solution) was collected for residue analysis. This analytical method utilizes a 25 mm C(8) Empore disk and in-vial elution to quantitatively determine triadimefon and ethofumesate in 170 mL aqueous samples. The analytes were eluted by placing the disk in a 2 mL autosampler vial with 980 microL of ethyl acetate and 20 microL of 2-chlorolepidine, the internal standard, for analysis by GC/MS. The method quantitation limits are 0.29 microg/L for ethofumesate and 0.59 microg/L for triadimefon. The method detection limits are 0.047 microg/L and 0.29 microg/L for ethofumesate and triadimefon, respectively. Concentrations of triadimefon and ethofumesate from dislodgeable foliar residues from a field study are reported.     

Evaluation of the studies on decline of pesticide residues

A specifically designed field trial was carried out in an apple orchard by applying Reldan 50 EC (active ingredient, chlorpyrifos-methyl) according to registered uses in Hungary to study the variability of results derived from supervised field trials. Two types of composite samples (A, size 24; and C, size 12) were taken at days 0, 3, 7, 10, and 14 after application to study the uncertainty of estimated residue values derived from supervised trials. In the case of type A the sampling officer selected the fruits from the specified quadrant of the tree, whereas for type C the fruits were taken from the vicinity of the marked position at consecutive sampling times. An evaluation model applying various formulas for the linearization of the decline curves of pesticide residues was applied, which enabled using the statistics of linear regression for calculating the best fit and confidence intervals for the experimental data. The results indicated that the uncertainty of sampling contributed approximately 84-90% of the combined uncertainty of the results (24-30%). In the decline studies performed simultaneously on the same field, the estimated time required to decrease the initial concentration to half ranged from 0.64 to 4.7 days. Despite the fact that the sample size of type C is half that of type A, both sampling methods provided similar results.     

Gas chromatographic determination of electron capture sensitive volatile industrial chemical residues in foods, using AOAC pesticide multiresidue extraction and cleanup procedures

Electron capture (EC) gas chromatographic (GC) parameters have been developed for determining some of the more volatile industrial chemicals that can be determined by the AOAC multiresidue method for organochlorine and organophosphorus pesticides with modified GC operating conditions. Retention times relative to pentachlorobenzene are reported for 143 industrial chemicals, pesticides, and related compounds on OV-101 GC columns at 130 degrees C. Also reported for most of the compounds are recoveries from fortified samples carried through the AOAC extraction and cleanup procedures for fatty and/or nonfatty foods, Florisil elution characteristics, and GC relative retention times on mixed OV-101 + OV-210 columns at 130 degrees C. Our laboratory has used the modified EC/GC parameters with the AOAC multiresidue extraction/cleanup procedures to determine many volatile halogenated industrial chemical contaminants in foods, chiefly in samples of fresh-water fish. Other modifications of the AOAC method are described to improve the tentative identification and quantitative measurement of these volatile residues.     

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.     

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.     

Determination of organochlorine and organophosphorus pesticide residues in eggs using a solid phase extraction cleanup

A multiresidue solid phase extraction (SPE) method for the isolation and subsequent gas chromatographic determination of nonpolar organochlorine and polar organophosphorus pesticide residues in eggs is described. The method uses an acetonitrile extraction followed by an SPE cleanup using graphitized carbon black and aminopropyl SPE columns. Organophosphorus pesticides are determined by gas chromatography with flame photometric detection. After further cleanup of the extract using Florisil SPE columns, organochlorine pesticides are determined by gas chromatography with electron capture detection. Studies were performed using eggs containing both fortified and incurred pesticide residues. The average recoveries were 86-108% for 8 fortified organochlorine pesticide residues and 61-149% for 28 fortified organophosphorus pesticide residues.     

Assessment of pesticide residues in honey samples from portugal and Spain

Fifty samples of honey collected from local markets of Portugal and Spain during year 2002 were analyzed for 42 organochlorine, carbamate, and organophosphorus pesticide residues. An analytical procedure based on solid-phase extraction with octadecyl sorbent followed by gas chromatography-mass spectrometry (GC-MS), for organochlorines, and by liquid chromatography-atmospheric pressure chemical ionization-mass spectrometry (LC-APCI-MS), for organophosphorus and carbamates, has been developed. Recoveries of spiked samples ranged from 73 to 98%, except for dimethoate (40%), with relative standard deviations from 3 to16% in terms of repeatability, and from 6 to 19% in terms of reproducibility. Limits of quantification were from 0.003 to 0.1 mg kg(-)(1). Most of the pesticides found in honey were organochlorines. Among them, gamma-HCH was the most frequently detected in 50% of the samples, followed by HCB in 32% of the samples and the other isomers of HCH (alpha-HCH and beta-HCH) in 28 and 26% of the samples, respectively. Residues of DDT and their metabolites were detected in 20% of the samples. Of the studied carbamates, both methiocarb and carbofuran were detected in 10% of the samples, pirimicarb in 4% and carbaryl in 2%. The only organophosphorus pesticides found were heptenophos in 16%, methidathion in 4%, and parathion methyl in 2% of honey samples. Results indicate that Portuguese honeys were more contaminated than Spanish ones. However, honey consumers of both countries should not be concerned about the amounts of pesticide residues found in honeys available on the market.     

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.     

提取、纯化沉积物中有机磷农药和菊酯类农药的两种程序的比较

Two procedures were compared for extraction and clean-up of 20 organophosphorus and 19 pyrethroid pesticides in sediment to identify the more effective procedure for groups of pesticides or individual compounds. In Procedure Ⅰ, methanol/water and n-hexane were used for extraction, and 1:10 (v/v) dichloromethane in n-hexane and acetone were used as eluents for eluting the analyte through the cartridge, with one evaporating steps on a rotary evaporator and two eluting steps on the cartridge, n-hexane/acetone (2:1, v/v) was used for extraction and elution in Procedure Ⅱ with one evaporating step on a rotary evaporator and one eluting step on the cartridge. All extractions were performed under an ultrasonic bath and gas chromatography and mass spectrometry were utilized for measurements. Procedure Ⅱ was developed as a rapid, timesaving, less costly and safer substitute for Procedure Ⅰ which was an old method. Procedure Ⅱ was more effective for almost all the organophosphorus pesticides tested and 11 of the 19 pyrethroid pesticides, while Procedure I was more appropriate for analysis of 5 pyrethroid pesticides. However, recoveries of most pyrethroid pesticides were fairly low. Thus, further studies should focus on adjustment and formulation of solvents for more efficient extraction and clean-up of pyrethroid pesticides from sediment samples.     

Evaluation of an automated gel permeation cleanup and evaporation systems for determining pesticide residues in fatty samples

The AutoVap 600 system, used in conjunction with an automated gel permeation chromatography (GPC) instrument, automatically collects and evaporates the effluent from the GPC column, dissolves the residue in a fixed volume of desired solvent, and quantitatively transfers it to a sealed vial. This system was evaluated and found to automate efficiently the cleanup of butterfat for pesticide residue analysis. Quantitative recoveries were obtained for each of 4 pesticides fortified in butterfat and cleaned up through the system and for 12 pesticide standards in the absence of sample matrix collected through the system. After loading, the system operates unattended and will automatically prepare up to 23 individual fat samples for determination by gas chromatography without additional cleanup.     

Multiresidue method for the analysis of pesticide residues in fruits and vegetables by accelerated solvent extraction and capillary gas chromatography

An analytical procedure using accelerated solvent extraction and capillary gas chromatography with electron capture and flame photometric detections was developed to simultaneously determine residues of different pesticides in fruits and vegetables. Single laboratory validation of the method was carried out for 28 compounds selected from eight pesticide classes, in blank and fortified samples of fresh pear, cantaloupe, white potato, and cabbage. The method had to meet specific established validation criteria for regulatory purposes applicable to our laboratory. At each of the two fortification levels studied, 24 of the 28 pesticides gave recoveries of more than 70% with a coefficient of variation of less than 10%. With respect to existing procedures, the method showed acceptable limits of detection (from 0.0019 to 0.14 microg/g depending on the pesticide and matrix) while minimizing environmental concerns, time, and labor.     

Application of isotope dilution gas chromatography-mass spectrometry in analysis of organochlorine pesticide residues in ginseng root

A highly accurate and precise method based on isotope dilution gas chromatography-mass spectrometry was developed for the determination of five matrix-bound organochlorine pesticides, namely, hexachlorobenzene and hexachlorocyclohexanes (alpha-, beta-, delta-, and gamma- isomers), in a reference sample of Panax gingseng. Identification of the analytes was confirmed under selective ion monitoring mode by the presence of two dominant ion fragments within the specific time windows (+/-1% of the relative retention time with respect to the calibration standards) and matching of relative ion intensities of the concerned ions in samples and calibration standards (within +/-5%). Quantification was based on the measurement of concentration ratios of the natural and isotopic analogues in the sample and calibration blends. To circumvent the tedious iterative process of exact isotope matching that is often used in isotope dilution mass spectrometry analysis, a single-point calibration procedure was adopted with the isotopic amount ratios in the sample and calibration blends close to unity (0.9-1.1). Under the described approach, intraday and interday repeatability of replicate analyses of organochlorine pesticides in the ginseng root sample were below 1.4%. The expanded relative uncertainty ranging from 4.0 to 6.5% at a coverage factor of 2 was significantly lower than those of conventional gas chromatographic methods using other calibration techniques (internal or external standards). A deviation of less than 2.0% from the certified values was achieved when applying the developed method to determine hexachlorobenzene, alpha-, and beta-hexachlorocyclohexane in a certified reference material (CRM), BCR-CRM 115. Because of the unavailability of relevant CRMs of herbal origins, the concerned ginseng root sample, after verification of the "true values" of the concerned organochlorine pesticides by the valid primary method, is suitable for serving as an in-house reference material for quality assurance and method validation purposes.     

Determination of neonicotinoid pesticide residues in vegetables and fruits with solid phase extraction and liquid chromatography mass spectrometry

A rapid and simple extraction method for the simultaneous analysis of five neonicotinoid insecticides has been developed. Twelve different fruit and vegetable matrixes were extracted with methanol and cleaned up using a graphitized carbon solid phase extraction cartridge loading with a 20% methanol solution. The concentrated eluate after methanol elution was then analyzed for pesticide residues by liquid chromatography/mass spectrometry in the APCI positive mode. The five pesticides including nitenpyram, thiamethoxam, imidacloprid, acetamiprid, and thiacloprid were recovered at 70-95% at spike levels of 0.1 and 1 mg/kg in bell pepper, cucumber, eggplant, grape, grapefruit, Japanese radish, peach, pear, potato, rice, and tomato. Relative standard deviations were less than 10% for all of the recovery tests. The proposed method is fast, easy to perform, and could be utilized for regular monitoring of pesticide residues.     

土壤中有机磷农药的提取纯化和气相色谱-氮磷检测器测定

The objectives of this study were to optimize instrumental parameters and conditions for analysis of selected organophosphorus pesticides (OPPs) by gas chromatography (GG) with nitrogen-phosphorus detection (NPD) (GG-NPD); to select an appropriate solvent system; to conduct a comparison of sonication and shaking extractions; and to select an appropriate procedure for extracting organophosphorus pesticides from soils. Procedure Ⅰ consisted of n-hexane or petroleum ether together with acetone used as solvents, while Procedure II contained several solvents including acetone,methanol, dichloromethane, and n-hexane or petroleum ether. Experimental results indicated that a mixture of petroleum ether/acetone (2:1, v/v) could be used in place of n-hexane/acetone (2:1, v/v) as it was a less expensive solvent system.In addition, shaking under a water bath at 20℃ was more effective than sonication. Also, Procedure Ⅰ was more effective,safer, and more timesaving than Procedure Ⅱ. Procedure Ⅰ was applied to three soil types of different organic matter content, with recoveries of the OPPs from the yellow-brown soils, which had a higher organic matter content, being lower than those from the yellow and red soils.