Evaluation of pressurized liquid extraction for determination of organophosphorus and pyrethroid pesticides in soybean

The purpose of this study was to develop an analytical method for the determination of organophosphorus and pyrethroid pesticides in soybean by pressurized liquid extraction (PLE). Two organic solvents, acetone and acetonitrile, were evaluated as extraction solvents. In both cases, the amount of extract was enhanced with increasing extraction temperature. The extracts obtained using acetonitrile were measured by gas chromatography/mass spectrometry after a cleanup process based on the analytical method for the Japanese Positive List System for Agricultural Chemicals Remaining in Foods. The effect of extraction temperature (range: 40– 130°C) on extraction efficiency was evaluated by a recovery study using 21 organophosphorus pesticides and 10 pyrethroid pesticides as target analytes and acetonitrile as the solvent. The results indicated that at 130°C, some organophosphorus pesticides might be degraded, whereas extraction temperatures between 70°C and 100°C were optimal. Next, a prepared sample containing fenitrothion and permethrin was analyzed. Although the sample was not soaked in water prior to analysis, PLE provided analytical results comparable to those obtained by solvent extraction with homogenization. Therefore, PLE is considered a simple and alternative technique for the extraction of organophosphorus and pyrethroid pesticides in soybean.     

Validation of a QuEChERS-based gas chromatographic method for analysis of pesticide residues in Cassia angustifolia (senna)

A simple multi-residue method based on modified QuEChERS (Quick, Easy, Cheap, Effective, Rugged and Safe) approach was established for the determination of 17 organochlorine (OC), 15 organophosphorous (OP) and 7 synthetic pyrethroid (SP) pesticides in an economically important medicinal plant of India, Senna (Cassia angustifolia), by gas chromatography coupled to electron capture and flame thermionic detectors (GC/ECD/FTD) and confirmation of residues was done on gas chromatograph coupled with mass spectrometry (GC-MS). The developed method was validated by testing the following parameters: linearity, limit of detection (LOD), limit of quantification (LOQ), matrix effect, accuracy–precision and measurement uncertainty; the validation study clearly demonstrated the suitability of the method for its intended application. All pesticides showed good linearity in the range 0.01–1.0 μg mL^?1 for OCs and OPs and 0.05–2.5 μg mL^?1 for SPs with correlation coefficients higher than 0.98. The method gave good recoveries for most of the pesticides (70–120%) with intra-day and inter-day precision < 20% in most of the cases. The limits of detection varied from 0.003 to 0.03 mg kg^?1, and the LOQs were determined as 0.01-0.049 mg kg^?1. The expanded uncertainties were <30%, which was distinctively less than a maximum default value of ±50%. The proposed method was successfully applied to determine pesticide residues in 12 commercial market samples obtained from different locations in India.     

Validation of QuEChERS method for the determination of some pesticide residues in two apple varieties

This study was undertaken to validate the “quick, easy, cheap, effective, rugged and safe” (QuEChERS) method using Golden Delicious and Starking Delicious apple matrices spiked at 0.1 maximum residue limit (MRL), 1.0 MRL and 10 MRL levels of the four pesticides (chlorpyrifos, dimethoate, indoxacarb and imidacloprid). For the extraction and cleanup, original QuEChERS method was followed, then the samples were subjected to liquid chromatography-triple quadrupole mass spectrometry (LC-MS/MS) for chromatographic analyses. According to t test, matrix effect was not significant for chlorpyrifos in both sample matrices, but it was significant for dimethoate, indoxacarb and imidacloprid in both sample matrices. Thus, matrix-matched calibration (MC) was used to compensate matrix effect and quantifications were carried out by using MC. The overall recovery of the method was 90.15% with a relative standard deviation of 13.27% (n = 330). Estimated method detection limit of analytes blew the MRLs. Some other parameters of the method validation, such as recovery, precision, accuracy and linearity were found to be within the required ranges.     

Application of the QuEChERS method for the determination of organochlorine pesticide residues in Brazilian fruit pulps by GC-ECD

The Quick, Easy, Cheap, Effective, Rugged, and Safe (QuEChERS) method was applied to the extraction of 14 organochlorine pesticides (OCPs) residues from commercial fruit pulps available in supermarkets in Fortaleza, Northeastern Brazil. The analyses were carried out by gas chromatography (GC), coupled to an electron-capture detector (ECD), and were confirmed by GC-tandem mass spectrometry (MS). The parameters of the analytical method, such as accuracy, precision, linear range, limits of detection and quantification, were determined for each pesticide. The results showed good linearity (R² ≥ 0.9916) and the overall average recoveries were considered satisfactory obtaining values between 69 and 110%, RSD of 2–15 %, except for hexachlorobenzene (HCB) in açai, acerola and guava pulp samples. The OCPs were detected in guava (α–HCH; lindane) and soursop (α, β–HCH isomers) samples. The QuEChERS method and GC–ECD were successfully used to analyze OCPs in commercially available Brazilian fruit pulps and can be applied in routine analytical laboratories.     

Solid-phase extraction for multi-residue analysis of pesticides in honey

A fast and simple multi-residue method for the analysis of 15 organophosphorus (OP), 17 organochlorine (OC), 8 pyrethroids (PYR), 12 N-methyl-carbamate (NMC) pesticide residues and bromopropylate in honey is presented. Ready–to–use EXtrelut®NT 20 column, eluted with dichloromethane, was used to extract the pesticide residues from the aqueous-acetone honey sample, obtaining a clean extract directly analyzable. Determination was carried out by gas chromatography (GC) coupled with flame photometric detector (FPD) for OP compounds and by GC coupled with mass spectrometry detector (MSD) for OC and PYR pesticides and bromopropylate. The NMC pesticides were analysed by liquid chromatography-double derivatization coupled with spectrofluorimetric detector (LC/DD/Fl). This method allows the determination of the 53 pesticide residues at low concentrations (0.0005–0.074 mg/kg) and can be used to assess the compliance with the Maximum Residues Levels (MRLs) set by the European Union. The performance of the method was evaluated and specificity, linearity, recovery, repeatability, reproducibility, limit of quantification (LOQ) and limit of detection (LOD) were determined. A good linearity (r²? 0.99) was found in the range 0.0005–0.074 mg/kg for the majority of the compounds studied. Most of the pesticides had recoveries in the range 70–103 % and values of relative standard deviation (RSD) < 20 for repeatability and reproducibility, showing good accuracy and precision of the method. Aldicarb partially degraded in aldicarb sulphoxide during the analytical procedure, giving anomalous values. The LOQ for all pesticides investigated was from 0.0005 to 0.025 mg/kg while the LOD ranged from 0.0002 to 0.008 mg/kg.     

Simple analytical method for determination of pesticide residues in human serum by liquid chromatography tandem mass spectrometry

The aim of this study was to develop an analytical method for the determination of residues of organophosphorus and carbamate pesticides which are widely used in Tunisia. This method involves a liquid-liquid extraction procedure followed by liquid chromatography tandem mass spectrometry (LC/MS/MS) for the identification and quantification of compounds. Ionization of molecules was performed by the electrospray mode. Multiple reactions monitoring (MRM) was the acquisition mode used for the monitoring of two MS/MS transitions for each compound. The average recoveries obtained, at three different fortification levels, ranged between 65% and 106% for most of the pesticides studied, except for methamidophos (lower than 25%).The linearity of the method was in the range of 5 to 50 μ g/L with a correlation coefficient from 0.995 to 0.999, depending on the analyte. The estimated limit of detection and limit of quantification were 2 μ g/L and 5 μ g/L, respectively. The precision of the analytical procedure was satisfactory and the coefficients of variation, evaluated at three concentration levels were lower than 15% for most pesticides studied. The application of the method was investigated in a population of agricultural workers chronically exposed to various pesticides some of which, such as carbofuran, carbendazim, methomyl and pirimicarb, were detected in some serum samples.     

流动注射免疫分析及其在环境中农药残留分析研究综述

介绍了流动注射免疫分析、顺序流动注射免疫分析方法及其流动注射脂质体、荧光、化学发光、电化学等检测技术分析环境中的农药残留     

Analysis of pesticide residues using the Quick Easy Cheap Effective Rugged and Safe (QuEChERS) pesticide multiresidue method in traditional Chinese medicine by gas chromatography with electron capture detection

The Quick Easy Cheap Effective Rugged and Safe multiresidue method (QuEChERS) has been validated for the extraction of 15 organochlorine pesticides (OCPs) in completely different matrices of traditional Chinese medicine (TCM). The method employed a rapid, simple and cost-effective procedure. The spiking levels for the recovery experiments were 0.1, 0.5 and 2.0 mg kg⁻¹. Mean recoveries mostly ranged between 76.0% and 114.0% (96.0% on average), and relative standard deviations (RSD) were generally below 10% (4.72% on average). Based on these results, the methodology has been proven to be highly efficient and robust and thus suitable for monitoring the MRL compliance of a wide range of commodity. The contamination status of 15 OCPs on 80 different TCMs marketed in China, and a total of 400 samples were also performed using a previously validated method. 15 OCPs were benzene hexachloride (BHC, including α-BHC, β-BHC, γ-BHC, δ-BHC), hexachlorobenzene, heptachlor, heptachlor epoxide, aldrin, p, p′-DDE, p, p′-DDD, o, p′-DDT, p, p′-DDT, mirex, endrin, dieldrin. This study indicates that the proposed method is useful for analyzing OCPs in TCM.     

A multi-residue method for the analysis of organophosphorus residues in cooked and polished rice using accelerated solvent extraction and dispersive-solid phase extraction (D-SPE) technique and uncertainty measurement

Quick, simple and efficient multi-residue analytical methods were developed and validated for the determination of organophosphorous insecticides from polished and cooked rice. Polished rice was extracted using a simple, automated technique namely accelerated solvent extraction (ASE) using dichloromethane as the extraction solvent. Cooked rice was extracted with acetone and cleaned up using dispersive-solid phase extraction (D-SPE) technique. The single step extraction method adopted for polished rice using accelerated solvent extractor provided satisfactory recovery for eight organophosphorus pesticides (OPPs) which ranged from 85.5–116.7%; 90.0–110.3% and 93.5–118.8% at 1, 5 and 10 limit of quantification (LOQ) levels, respectively. The recovery of cooked rice was in the range of 74–124%; from 75–100% and from 73–87% for 1, 5 and 10 level of fortification, respectively. The total uncertainty was evaluated, taking four main independent sources viz., weighing, purity of the standard, GC calibration curve and repeatability under consideration. The expanded uncertainty was found to be in the range of 5–20%.     

Development of an efficient extraction method for oxytetracycline in animal manure for high performance liquid chromatography analysis

Oxytetracycline (2-(amino-hydroxy-methylidene)-4-dimethylamino-5,6,10,11,12a-pentahydroxy-6-methyl-4,4a,5,5a-tetrahydrotetracene-1,3,12-trione) is a major member of the tetracycline antibiotics family of which are widely administered to animals in concentrated animal feeding operations for purposes of therapeutical treatment and health protection. With the disposal of animal manure as fertilizer into agricultural land, tetracyclines enter the environment. However, tetracyclines chelate with multivalent cations and proteins, resulting in low extraction efficiencies from animal manure for tetracycline residue analysis. In this study an efficient extraction method for oxytetracycline from steer manure using methanol/water solution amended with chelating organic acid was developed for the analysis of high performance liquid chromatography. The effect of species and amount of amendment acids, shaking time, methanol/water ratio, manure weight, and repeated times of extraction was investigated. It was optimized to amend 2.5 g citric acid and 1.1 g oxalic acid with 10.0 g manure sample in a 50-ml centrifuge tube and extract with 15 ml methanol/water (9:1 in volume) by vigorously shaking for 30 min in a reciprocating shaker. After centrifugation at 11,000 rpm, supernatant is collected. Sample was extracted for a total of 3 times. The developed extraction method was further applied to extract oxytetracycline from fresh and aged cow manure, swine and poultry manure, and soil. Satisfactory recoveries ranging from (84.1 ± 2.4) % to (102.0 ± 3.1) % were obtained, demonstrating that the optimized extraction method is robust for oxytetracycline from different manure sample matrixes.     

Validation of QuEChERS method for the determination of 36 pesticide residues in fruits and vegetables from Ghana,using gas chromatography with electron capture and pulsed flame photometric detectors

In this study, “Quick, Easy, Cheap, Effective, Rugged and Safe” ‘QuEChERS’ method was modified for the determination of 36 pesticides fortified at (0.01–1.0) mg kg^?1 in three vegetables and a fruit (lettuce, carrot, tomatoes and pineapples respectively) from Ghana. The method involved extraction with acetonitrile, phase separation with primary secondary amine and magnesium sulfate; the final injection solution was reconstituted in ethyl acetate. Organochlorine and synthetic pyrethroids residues were detected with electron capture detector whereas organophosphorus, pulsed flame photometric detector was used. The recoveries at different concentration levels (0.01, 0.1 and 1.0 mg kg^?1) were in the range of 83% and 93% with relative standard deviation ranging from 2% to 10% (n = 5) and the coefficient of determination (R²) was greater than 0.99 for all the 36 pesticides. The method was successfully tested on 120 real samples from Accra markets and this proved to be useful for monitoring purposes particularly in laboratories that have no gas chromatography-mass spectrometry and liquid chromatography-mass spectrometry.     

Pilot scale application of a method for the analysis of perfluorinated compounds in surface soils

A growing number of studies now indicate that perfluorinated compounds (PFCs) are globally distributed in the environment. Their widespread distribution and presence in remote locations has led to questions about the importance of atmospheric and oceanic transport. Describing their distribution in surface soils is also an essential but neglected element in developing a comprehensive understanding of their occurrence in the environment. Soils are the critical link between global atmospheric and hydrologic processes where both local and distant contaminants can accumulate and be released into aquatic and terrestrial communities. Because PFC concentrations in soils will influence ground and surface water, wildlife, and crops, methods to accurately measure PFCs in soil are clearly needed. To help answer this need, we developed a method for the analysis of nine perfluorinated carboxylic acids and four perfluorinated sulfonic acids in soil. Samples from six nations (n = 10 per nation) were analyzed by LC-MS/MS to demonstrate the method performance parameters and to make preliminary observations about the occurrence of the PFCs in soils in different parts of the world. The resulting method shows acceptable performance characteristics for the target compounds in most soils while documenting the widespread occurrence of PFCs in surface soils.     

Evaluation and validation of two different chromatographic methods (HPLC and LC-MS/MS) for the determination and confirmation of ochratoxin A in pig tissues

This study was undertaken to compare two different analytical methods for the determination and confirmation of ochratoxin A (OTA) in blood serum, kidney and liver of pigs. Sample clean-up was based on liquid-liquid phase extraction. The detection of OTA was accomplished with high-performance liquid chromatography (HPLC) combined either with fluorescence detection (FL) or electro spray ionization (ESI+) tandem mass spectrometry (MS–MS). Comparative method evaluation was based on the investigation of 90 samples of blood serum, kidney and liver per animal originating from different regions of Serbia. The analytical results are discussed in view of the respective method validation data and the corresponding experimental protocols. In general, analytical data obtained with (LC–MS–MS) liquid chromatography electro spray tandem mass spectro metry detection offered comparable good results at the sub-ppb concentration level. The results indicate that the liquid chromatography electro spray tandem mass spectrometric (LC-MS/MS) method was more specific and sensitive for the analysis and confirmation of ochratoxin A in pig tissues then high pressure liquid chromatography (HPLC) method after methylation of OTA.     

Polycyclic aromatic hydrocarbons in crude oil-contaminated soil: A two-step method for the isolation and characterization of PAHs

A two-step analytical method is developed for the isolation and characterization of polycyclic aromatic hydrocarbons (PAHs) in crude oil contaminated soil. In the first step, those crude oil components were isolated which are easily mobilized with water from the contaminated soil (determination of groundwater pollution potential). In the second step, the fraction containing the remaining crude oil compounds was extracted using toluene. After the cleanup of the fractions, both fractions were analyzed using high-performance liquid chromatography (HPLC). The HPLC of the toluene extracted fraction shows that along with the sixteen priority pollutants from the US-EPA list, many other polycyclic aromatic hydrocarbons (PAHs) are present as well. It is evident from the chromatograms that a significant amount of PAHs are present as is also the case in the fractions eluted by water. The described method allows the determination of total organic pollutants from crude oil, some of them being potential groundwater contaminants. The major part of the total pollutants could not be mobilized by water and therefore remains in the soil, which was extracted in the second step.     

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.