Multiresidue analysis of four pesticide residues in water dropwort (Oenanthe javanica) via pressurized liquid extraction, supercritical fluid extraction, and liquid-liquid extraction and gas chromatographic determination

The primary objective of this study was to simultaneously analyze the residues of the most commonly used pesticides, chlorpyrifos-methyl, endosulfan, EPN, and iprodione in the water dropwort, via accelerated solvent extraction (ASE), supercritical fluid extraction (SFE), and conventional solvent extraction (LLE) techniques. Residue levels were determined using GC with electron-capture detection (GC-ECD). The confirmation of pesticide identity was performed by GC-MS in a selected ion-monitoring (SIM) mode. In none of the ASE and SFE techniques were the extraction conditions optimized. Rather, the experimental variables were predicated on the author's experience. The ECD response for all pesticides was linear in the studied range of concentrations of 0.005-5.0 ppm, with correlation coefficients in excess of 0.9991. At each of the two studied fortification levels, the pesticides yielded recoveries in excess of 72% with RSDs between 1 and 19%. The LODs were achieved at a range of levels from 0.001 to 0.063 ppm, depending on the pesticide utilized. The LOQs, which ranged from 0.003 to 0.188 ppm, were lower than the maximum residue limits (MRLs) authorized by the Korean Food and Drug Administration (KFDA). All of the methods were applied successfully to the determination of pesticide residues in the real samples. It could, therefore, be concluded that any of the techniques utilized in this investigation might prove successful, given that the applied extraction conditions are wisely chosen.     

Comparison of different extraction methods for the simultaneous determination of pesticide residues in kiwi fruit using gas chromatography-mass spectrometry

The methods of simultaneous extraction of iprodione, chlorpyrifos-methyl, EPN and endosulfan (with its metabolites) from kiwi fruit using accelerated solvent extraction (ASE), supercritical fluid extraction (SFE), and liquid-liquid extraction (LLE) were tested and compared in terms of their of limits of detection and quantification, as well as the highest pesticide recoveries with the lowest residues in the final extracts. The analysis was performed using gas chromatography-mass spectrometry in the selected ion monitoring mode. The proposed methods featured good sensitivity, pesticide quantification limits were low enough, and the precision (expressed as relative standard deviations) ranged from 0.56 to 7.17%. The recoveries obtained from ASE, SFE and LLE were 77.5-120, 71.9-109.1 and 75.6-127.1%, respectively. The proposed methods were successfully applied for the monitoring of the selected pesticide residues in kiwi fruit samples collected from Jollanamdo area, Republic of Korea. Iprodione was detected at a level lower than the maximum residue limit (MRL) established by the Korea Food and Drug Administration (5 ppm), while EPN was detected at a level higher than the Korea Food and Drug Administration MRL (0.1 ppm) in the real samples. The proposed sample preparations led to a higher preconcentration of the pesticide fraction, and allowed the sensitive and selective determination of pesticides with varied physicochemical properties in kiwi fruit. Copyright (c) 2008 John Wiley & Sons, Ltd.     

基于多壁碳纳米管改进QuEChERS法结合气相色谱-串联质谱检测茶叶中10种拟除虫菊酯类农药残留

利用多壁碳纳米管(MWCNTs)QuEChERS法提取茶叶中拟除虫菊酯类残留农药,采用气相色谱-串联质谱(GC-MS/MS)分析测定,建立了一种灵敏度高、可靠性强的茶叶中农药残留检测方法。比较了单壁碳纳米管(SWCNTs)、MWCNTS、氨基化多壁碳纳米管和石墨烯4种碳纳米材料和其不同用量下的净化效果;采用正交试验设计对前处理最佳实验条件进行筛选,并对实验影响因素进行方差分析。结果表明:提取溶剂、碳纳米材料种类对10种拟除虫菊酯类农药回收率的影响具有极显著统计学差异(p<0.001),提取时间对回收率的影响有统计学差异(p<0.05),碳纳米材料用量对回收率影响不显著(p>0.05);最佳样品前处理条件为以乙腈为提取溶剂,超声提取35 min,净化剂为60 mg MWCNTs、200 mg PSA和200 mg C18。方法学考察表明,10种拟除虫菊酯类农药在0.01~2 mg/L范围内线性良好;检出限(LOD)为0.001~0.01 mg/kg,定量限(LOQ)为0.005~0.04 mg/kg;绿茶样品空白基质加标试验中,10种农药的回收率为91.4%~109.7%,相对标准偏差为0.12%~9.80%(n=6)。对花茶、绿茶、红茶3种茶叶基质进行基质效应(ME)评价,结果发现净化剂中加入MWCNTs在绿茶和红茶基质中能有效降低ME。利用该方法检测了市售120份茶叶中拟除虫菊酯类农药的残留,多个样品中检出目标物,但均未超标。该方法检测灵敏度高,可靠性好,具有良好的回收率和稳定性,能满足茶叶中农药残留快速定量分析的要求。     

Response surface optimization for determination of pesticide multiresidues by matrix solid-phase dispersion and gas chromatography

An optimized multiresidue analysis method based on matrix solid-phase dispersion (MSPD) and gas chromatography (GC) is proposed for the determination of organochlorines and pyrethroids in the tea samples. Response surface methodology (RSM) was used to optimize the extraction conditions of MSPD, such as the sorbent type, eluent composition, dichloromethane concentration and eluting volume. Desirability function approach was employed to optimize the pesticide recoveries and matrix cleanup. Compromising the recoveries and cleanup degree, MSPD was carried out with Florisil as the sorbent and n-hexane-dichloromethane (1:1, v/v) as the eluent. The pesticide recoveries in tea samples were better than 80% spiked in the concentration range of 0.01-0.05mg/kg and the relative standard deviations were lower than 7%. The quantification limits of the pesticides were in the range of 0.002-0.06mg/kg, which were lower than the maximum residue limits of the pesticides in tea samples established by the European Union.     

Determination of multiresidue pesticides in green tea by using a modified QuEChERS extraction and ion-trap gas chromatography/mass spectrometry

The pesticide residues in exported and imported tea products must not exceed the maximum residue limits (MRLs) regulated by the import countries. Tea is a complex matrix that obfuscates the determination of pesticide residues. Many available methods for multiresidue pesticide analysis of tea are time-consuming and require many cleanup steps. The objective of this study was to develop a simple multiresidue method by using a modified quick, easy, cheap, effective, rugged, and safe (QuEChERS) extraction and ion-trap GC/MS/MS, which can identify, confirm, and quantify pesticides in complex matrixes. A tea product was homogenized with water, and the pesticides were extracted with acetonitrile containing 1% acetic acid. The extract was subjected to centrifugation, initial cleanup with dispersive SPE (dSPE), solvent exchange, and final cleanup with dSPE. Diethyl-d10-parathion and triphenyl phosphate were used as the internal standard and surrogate, respectively. The final extract was injected into an ITQ 700 gas chromatograph/mass spectrometer. Quantitation of individual pesticides was based on matrix-matched calibration curves with a correlation coefficient of > 0.9930 for the 22 pesticides selected for the study. The recoveries of the 22 pesticides ranged from 78 to 115%, except those for diazinon (130%) and malathion (122%), with an average RSD of 8.7%. The LOD values of all of the pesticides, except for terbufos, were below the MRLs set by the European Union and Japan.     

Comparison of pressurized liquid extraction and microwave assisted extraction for the determination of organochlorine pesticides in vegetables

A method to determine organochlorine pesticides in horticultural samples (lettuce, tomato, spinach, potato, turnip leaf and green bean) using pressurized liquid extraction (PLE) is described and compared with microwave assisted extraction (MAE). Significant parameters affecting PLE procedure such as temperature, static extraction time and extraction solvent were optimised and discussed. Clean-up of extracts was performed by solid phase extraction (SPE) using a carbon cartridge as adsorbent. Pesticides were determined by gas chromatography and electron capture detection (GC-ECD). Analytical recoveries obtained were ca. 100% and the relative standard deviations were lower than 15% for most of the studied pesticides with the proposed methods in each analysed matrix.     

Comparison of solvent extraction and solid-phase extraction for the determination of organochlorine pesticide residues in water.

Solid-phase extraction (SPE) of organochlorine pesticide residues from environmental water samples was evaluated using octadecyl (C18)-bonded porous silica. The efficiency of SPE of these pesticide residues from reagent water samples at 1-5 micrograms dm-3 levels was compared with those obtained by solvent extraction with hexane and Freon TF (trichlorotrifluoroethane). Average recoveries exceeding 80% for these organochlorine pesticides were obtained via the SPE method using small cartridges containing 100 mg of 40 microns C18-bonded porous silica. The average recovery by solvent extraction with hexane and Freon TF exceeded 90% in both instances. It was concluded that the recoveries and precision for the SPE of organochlorine pesticides were poorer than those for the solvent extraction method. Organochlorine pesticide residue levels in environmental water samples from two major rivers flowing through predominantly rice-growing areas were monitored by gas chromatography using the solvent extraction method with hexane. Exceptionally high levels of organochlorine pesticide residues such as BHC, DDT, heptachlor, endosulfan and dieldrin were found in these water samples.     

Development of methods for determination of the residues of 15 pesticides in medicinal herbs Isatis indigotica Fort. by capillary gas chromatography with electron capture or flame photometric detection

Two multiresidue methods were developed for the determination of 15 pesticides (organochlorines, organphosphorus compounds, pyrethroids, and fungicides) in medicinal herbs Isatis indigotica Fort. and its formulations. The analytical procedure is based on ultrasonic assisted extraction and liquid-liquid extraction (LLE). After solvents were added, the raw material or granule sample was sonicated in an ultrasonic water bath and then centrifuged, filtered, and cleaned up by LLE. The infusion sample was extracted with petroleum ether by LLE. The pesticide residues were determined by capillary gas chromatography with electron-capture or flame photometric detection. Recoveries with the method at concentrations between 0.4 microg/kg and 10 mg/kg ranged from 70.2 to 119.5% for raw material, 73.2 to 105.1% for granule formulation, and 72.8 to 113.3% for infusion formulation. The relative standard deviation values were <20% for all of the pesticides studied. The pesticide detection limits were within the ranges 0.3-0.5 microg/L for endosulfan, 3-7.5 microg/L for pyrethroids, 0.7-32.5 microg/L for organophosphorus pesticides, and 0.1-0.6 microg/L for the other pesticides. The proposed methods are simple and rapid and provide simultaneous determination of pesticide residues in Isatis indigotica Fort. with acceptable recoveries and repeatability and an adequate limit of determination.     

Use of pressurized liquid extraction for the simultaneous analysis of 28 polar and 94 non-polar pesticides in agricultural soils by GC/QqQ-MS/MS and UPLC/QqQ-MS/MS

Due to the wide range of pesticides that can be used in agriculture, the development of fast multiresidue methods that simultaneously determine polar and non-polar pesticides is greatly demanded. This study shows the development and validation of a multiresidue method for the analysis of 98 non-polar pesticides and 28 polar pesticides in soil. A simultaneous extraction step by pressurized liquid extraction was utilized. The optimum results were obtained using ethyl acetate-methanol (3:1, v/v) with 2 min of preheat time and 85 degrees C as the extraction temperature. The final determination of non-polar pesticides was performed by GC, whereas polar pesticides were determined by ultra-performance liquid chromatography (UPLC). Both GC and UPLC were coupled to triple-quadrupole analyzers operating in tandem MS. The optimized extraction procedure was validated. The average extraction recoveries were in the range 72-108% (10 microg/kg) and 71-106% (50 microg/kg), with RSD values < or = 26%. The matrix effect was also evaluated, and matrix-matched standard calibration was finally applied for quantification. The suitability of the method was also checked by the analysis of a certified reference material. Furthermore, 26 real soil samples were analyzed by the proposed methods in order to assess their applicability. Several pesticides (e.g., bifenthrin, triadimefon, or endosulfan) were found in the samples.     

Analysis of pesticides in fruits by pressurized liquid extraction and liquid chromatography-ion trap-triple stage mass spectrometry

A multi-residue method using pressurized liquid extraction (PLE) and liquid chromatography-quadrupole ion trap-triple stage mass spectrometry (LC-IT-MS(3)) has been developed for determining trace levels of pesticides in fruits. The selected pesticides can be distinguished in: benzimidazoles and azoles, organophosphorus, carbamates, neonicotinoids, and acaricides. PLE has been optimized to extract these pesticide residues from oranges and peaches by studying the effect of experimental variables on PLE efficiency. Samples were extracted at high temperature and pressure (75 degrees C and 1500psi) using ethyl acetate as extraction solvent and acidic alumina as drying agent. The recoveries obtained by PLE ranged from 58% to 97% and the relative standard deviation (RSDs) from 5% to 19%. The limits of quantification (LOQs) of the compounds were from 0.025 to 0.25mgkg(-1), which are well-below the maximum residue limits (MRLs) established by the European Union (EU) and the Spanish legislations.     

Multiresidue analysis of pesticides in vegetables and fruits using two-layered column with graphitized carbon and water absorbent polymer

A high-throughput multiresidue analysis of pesticides in non-fatty vegetables and fruits was developed. The method consisted of a single extraction and a single clean-up procedure. Food samples were extracted with ethyl acetate and the mixture of extract and food dregs were poured directly into the clean-up column. The clean-up column consisted of two layers of water-absorbent polymer (upper) and graphitized carbon (lower), which were packed in a reservoir (75 ml ) of a cartridge column. The polymer removed water in the extract while the carbon performed clean-up. In a recovery test, 110 pesticides were spiked and average recoveries were more than 95% from spinach and orange. Most pesticides were recovered in the range 70-115% with RSD usually < 10% for five experiments. The residue analyses were performed by the extraction of 12 pesticides from 13 samples. The two methods resulted in similar residue levels except chlorothalonil in celery, for which the result was lower with the proposed method. The results confirmed that the proposed method could be applied to monitoring of pesticide residue in foods.     

Supercritical fluid extraction for pesticide multiresidue analysis in honey: determination by gas chromatography with electron-capture and mass spectrometry detection

An analytical procedure using supercritical fluid extraction (SFE) and capillary gas chromatography with electron-capture detection was developed to determine simultaneously residues of different pesticides (organochlorine, organophosphorus, organonitrogen and pyrethroid) in honey samples. Fortification experiments were conducted to test conventional extraction (liquid-liquid) and optimize the extraction procedure in SFE by varying the CO2-modifier, temperature, extraction time and pressure. Best efficiency was achieved at 400 bar using acetonitrile as modifier at 90 degrees C. For the clean-up step, Florisil cartridges were used for both methods LLE and SFE. Recoveries for majority of pesticides from fortified samples of honey at fortification level of 0.01-0.10 mg/kg ranged 75-94% from both methods. Limits of detection found were less than 0.01 mg/kg for ECD and confirmation of pesticide identity was performed by gas chromatography-mass spectrometry in selected-ion monitoring mode. The multiresidue methods in real honey samples were applied and the results of developed methods were compared.     

低温冷冻及分散固相萃取净化-超高效液相色谱-串联质谱法测定植物油中104种农药残留

建立了适用于植物油中104种农药残留的检测方法。通过液液萃取(LLE)提取目标化合物,再借助离心、冷冻和分散固相萃取(D-SPE)净化手段,依托超高效液相色谱-串联质谱测定。以回收率和共提取物为衡量指标,着重优化了6种提取方式、不同冷冻时间及PSA(primary secondary amine)、GCB(graphite carbon black)和C18这3种不同固相萃取填料不同组合的效果。在0.01、0.02和0.05 mg/kg水平的平均添加回收率为55%~121%, RSD为0.47%~19.2%, 80%的目标物的定量限可达到1 μg/kg,低于我国相关标准限量,能够满足多种农药残留同时分析的要求。该方法步骤简便、可靠、稳定,可应用于进口植物油中多种农药残留的快速检测与确证的日常检测工作中,具有一定的推广价值。     

A rapid multiresidue method for determination of pesticides in fruits and vegetables by using acetonitrile extraction/partitioning and solid-phase extraction column cleanup

A modification of a rapid and inexpensive multiresidue method for determination of pesticides in fruits and vegetables (QuEChERS method) is presented. Samples were extracted by shaking with acetic acid-acetonitrile (1 + 99). Water was removed by liquid-liquid partitioning with magnesium sulfate and sodium acetate. The extract was subjected to a single solid-phase extraction (SPE) column cleanup, which produced a cleaner extract than did the dispersive SPE cleanup used in the original QuEChERS method. Recovery data were obtained for 316 pesticide residues, at levels ranging from 20 ppb to 1.0 ppm. Data were provided by 3 different laboratories. The modified QuEChERS method resulted in a 65% reduction in solvent usage, when compared with the traditional multiresidue methods previously used in our laboratories.     

Determination of Pesticide Residues in Teas via QuEChERS Combined with Dispersive Liquid–Liquid Microextraction Followed by Gas Chromatography–Tandem Mass Spectrometry

In this study, an effective gas chromatography–tandem mass spectrometry method was developed to determine 47 pesticide residues in tea. Sample preparation involved a quick, easy, cheap, effective, rugged, and safe (QuEChERS) procedure, wherein the sample is extracted by acetonitrile and cleaned up with multiwalled carbon nanotubes and primary secondary amine adsorbents; dispersive liquid–liquid microextraction (DLLME) was subsequently performed using carbon tetrachloride as extractive solvent and the extract obtained by QuEChERS as dispersive solvent. Factors influencing DLLME efficiency, including type and volume of extractive solvent, volume of dispersive solvent, and extraction time were evaluated. For validation purposes, recovery studies were performed using matrix blanks fortified with pesticides at three concentrations, namely, 10, 50, and 100 μg kg^?1. Most of the analytes were recovered at an acceptable range of 70?120% and RSDs ≤ 20% were acquired for green tea, oolong tea, black tea, and puer tea. Limits of quantification of pesticides obtained for these teas were sufficiently low, and most pesticides levels were lower than 10 μg kg^?1, which satisfies the requirements for maximum residue levels (MRLs) as prescribed by the European Community. Twenty-four commercially available tea samples were analyzed using this optimized method. Results revealed that the contents of chlorpyrifos and alpha-HCH from different green tea samples exceed the MRLs, and chlorpyrifos, bifenthrin, lambda-cyhalothrin, and cypermethrin are among the most frequently detected pesticides in teas.     

快速滤过型净化结合气相色谱-串联质谱法同时检测茶叶中10种拟除虫菊酯农药残留

建立了快速滤过型净化（m-PFC）结合气相色谱-串联质谱（GC-MS/MS）测定茶叶中10种拟除虫菊酯类农药残留的方法。比较了采用不同提取溶剂（乙腈、丙酮和乙酸乙酯）和不同提取方式（不加水浸泡和加水浸泡）时10种农药的提取效率；比较了2种QuEChERS净化管和m-PFC柱对茶叶提取液的净化效果和农药残留的回收率。结果表明，茶叶样品不加水浸泡，用乙腈提取效果最好；m-PFC柱对茶叶提取液净化效果良好，而且能保证较高的农药回收率。10种拟除虫菊酯农药在相应的范围内有良好的线性关系，相关系数（R²）大于0.9980；10种农药在4个水平添加下的回收率为87.5%~111.3%，RSD为2.1%~8.9%。方法的检出限为0.001~0.015 mg/kg，定量限为0.003~0.05 mg/kg。利用该方法检测市售50例茶叶样品中10种拟除虫菊酯农药的残留，检出率为48%，但农药残留量均在国家标准限量值以下。与传统QuEChERS法和固相萃取法相比，该方法具有操作简单、准确度和精密度良好等优点，为多种拟除虫菊酯类农药在茶叶中的残留测定提供了快速检测的新方法。     

Pressurized liquid extraction and microwave-assisted extraction in the determination of organochlorine pesticides in fish muscle samples

This paper describes a comparative study of 2 extraction methods, pressurized liquid extraction (PLE) and microwave-assisted extraction (MAE), for the determination of organochlorine pesticides (OCPs) in fish muscle samples. In both cases, samples were extracted with hexane-acetone (50 + 50), and the extracts were purified by solid-phase extraction using a carbon cartridge as the adsorbent. Pesticides were eluted with hexane-ethyl acetate (80 + 20) and determined by gas chromatography with electron-capture detection. Both methods demonstrated good linearity over the range studied (0.005-0.100 microg/mL). Detection limits ranged from 0.029 to 0.295 mg/kg for PLE and from 0.003 to 0.054 mg/kg for MAE. For most of the pesticides, analytical recoveries with both methods were between 80 and 120%, and the relative standard deviations were < 10%. The proposed methods were shown to be powerful techniques for the extraction of OCPs from fish muscle samples. Although good recovery rates were obtained with both extraction methods, MAE provided advantages with regard to sample handling, cost, analysis time, and solvent consumption. Acceptable validation parameters were obtained although MAE was shown to be more sensitive than PLE.     

Comprehensive multiresidue method for the simultaneous determination of 74 pesticides and metabolites in traditional Chinese herbal medicines by accelerated solvent extraction with high-performance liquid chromatography/tandem mass spectrometry

In this paper, a multiresidue method for the simultaneous target analysis of 74 pesticides and metabolites in traditional Chinese herbal medicines (TCHMs) was developed using accelerated solvent extraction (ASE) coupled with HPLC/MS/MS. Pesticide residues were extracted from the different samples using ASE, then purified by gel permeation chromatography and graphitized carbon black/primary, secondary amine SPE. Gradient elution was used in conjunction with positive mode electrospray ionization MS/MS to detect 74 pesticides and metabolites from Cortex Cinnamomi, Flos Carthami, Folium Ginkgo, Herba Pogostemonis, Radix Ginseng, and Semen Ginkgo using a single chromatographic run. The analytical performance was demonstrated by the analysis of extracts spiked at three concentration levels ranging from 0.005 to 0.125 mg/kg for each pesticide and metabolite. In general, recoveries ranging from 70 to 110%, with RSDs better than 15%, were obtained. The recovery and repeatability data were in good accordance with European Union guidelines for pesticide residue analysis. The LOD for most of the targeted pesticides and metabolites tested was below 0.01 mg/kg.     

Use of a Headspace Solid-Phase Microextraction-Based Methodology Followed by Gas Chromatography–Tandem Mass Spectrometry for Pesticide Multiresidue Determination in Teas

This study reports on the development of a fast and efficient method based on headspace solid-phase microextraction (HS-SPME) coupled to gas chromatography–tandem mass spectrometry (GC–MS/MS) for simultaneous analysis of 128 volatile or semi-volatile pesticide residues belonging to nine classes of pesticides. The important factors related to HS-SPME performance were optimized; these factors include fiber types, water volume, ion strength, extraction temperature, and extraction time. The best extraction conditions include a PDMS/DVB fiber, and analytes were extracted at 90 °C for 60 min from 1 g of tea added to 5 mL of 0.2 g mL^?1 NaCl solution. The methodology was validated using tea samples spiked with pesticides at three concentration levels (10, 50, and 100 μg kg^?1). In green tea, oolong tea, black tea, and puer tea, 82.8, 88.3, 79.7, and 84.3% of the targeted pesticides meet recoveries ranging from 70 to 120% with a relative standard deviation of?≤?20%, respectively, when spiked at a level of 10 μg kg^?1. Limits of quantification in this method for most of the pesticides were 1 or 5 μg kg^?1, which are far below their maximum residue limits prescribed by EU. The optimized method was employed to analyze 30 commercial samples obtained from local markets; 17 pesticide residues were detected at concentrations of 2–452 μg kg^?1. Chlorpyrifos was the most detected pesticide in 80% of the samples, and the highest concentration of dicofol (452 μg kg^?1) was found in a puer tea. This is the first time to find that the optimized extraction temperature for pesticide residues is 90 °C, which is much higher than other reported HS-SPME extraction conditions in tea samples. This developed method could be used to screen over one hundred volatile or semi-volatile pesticide residues which belong to multiple classes in tea samples, and it is an accurate and reliable technique.     

Analysis of insecticides in honey by liquid chromatography-ion trap-mass spectrometry: comparison of different extraction procedures

The feasibility of different extraction procedures was tested and compared for the determination of 12 organophosphorus and carbamates insecticides in honey samples. In this sense, once the samples were pre-treated - essentially dissolved in hot water by stirring - and before they could be analyzed by liquid chromatography-ion trap-second stage mass spectrometry (LC-MS(2)), four different approaches were studied for the extraction step: QuEChERS, solid-phase extraction (SPE), pressurized liquid extraction (PLE) and solid-phase microextraction (SPME). The main aim of this work was to maximise the sensitivity of pesticides and to minimise the presence of interfering compounds in the extract. All pesticides were linear in the range from CC(β) to 1000× CC(β) for the four extraction methods (three orders of magnitude). Detection capabilities (CC(β)) were 0.024-1.155 mg kg(-1) with QuEChERS, 0.010-0.646 mg kg(-1) with SPE, 0.007-0.595 mg kg(-1) with PLE, and 0.001-0.060 mg kg(-1) with SPME. All the target compounds could be recovered by any of the methods, at a CC(β) fortification level ranged from 28 to 90% for the SPME. In comparison, the PLE method was the most efficient extraction method with recoveries from 82 to 104%. It was followed by the QuEChERS method with recoveries between 78 and 101% and the SPE method with recoveries between 72 and 100%. The repeatability expressed as relative standard deviation (RSDs) was below 20% for all the pesticides by any of the tested extraction methods. Results obtained applying the four extraction techniques to real honey samples are analogous.