Simultaneous Determination Of Pesticide Residues Research Articles

Determination of pesticide residues and heavy metals in Adhatoda Vasaka Linn.

Heavy metals and pesticide residue analysis plays an important role in the quality control of medicinal plants like Vasaka (Adhatoda vasica). Hence a study was conducted to determine heavy metals and pesticide residues in this medicinal herb, which is a highly useful commodity in the health system. The reliable, rapid and nontoxic sample preparation method like QuEChERS and analytical methods like GC-MS were proposed for the simultaneous determination of pesticide residues and Heavy metal detection was carried out by ICP-MS. In this study, the presence of organophosphorus and organochlorine pesticides like alachlor, heptachlor, heptachlor epoxide, aldrin, dieldrin, endrin, etc was checked but not detected. Heavy metals like Arsenic (As), Cadmium (Cd), Mercury (Hg) and Lead (Pb) are traced in samples about 2.3005 ppb, 0.799 ppb, 2.290 ppb and 10.204 ppb respectively in the present study.

Chemometric Optimization of SPE for the Determination of Multiclass Pesticides in Portable Water Samples by UHPLC-MS/MS

This study aimed on the development of a SPE-UHPLC-MS/MS method for the simultaneous determination of pesticide residues in drinking water samples. A chemometric approach was applied to optimize the efficiency of the SPE pretreatment procedure. This study involved (i) the application of a Full Factorial Design for the screening of the significant factors, (ii) the application of a Central Composite Design for the determination of the optimal conditions and (iii) the evaluation and validation of the significance of the statistically proposed models. Oasis HLB cartridges were used for the extraction. The optimum sample volume was 300 mL and the elution solvent 3 mL of the mixture of methanol:ethylacetate 70:30 v/v. The method was validated according to the international guidelines. Recoveries were ranged from 63 to 116% and the detection limits were between 0.1 and 1.5 pg mL− 1. The validated method could be used in routine analysis for pesticides screening.

Simultaneous Determination of Pesticide Residues in Brown Rice Using GC-MS/MS and LC-MS/MS

This study developed a method that simultaneously detected 283 pesticide residues in brown rice using GC-MS/MS and LC-MS/MS. In this method, we examined the desirable amount of sodium chloride required for salting out and the SPE cartridge required for clean-up. Pesticide residues from the sample were extracted with acetonitrile using a homogenizer and mixed with salts including anhydrous magnesium, two types of citrate, and sodium chloride. The sample solution of the acetonitrile layer was cleaned up using the GCB/NH2 (200 mg/200 mg, 6 mL) SPE cartridge. The determination method was validated using two concentrations (0.01 and 0.1 μg/g) of 283 pesticides based on the validation guideline of the Ministry of Health, Labor and Welfare in Japan. Of the 283 pesticides, 250 were detected satisfactorily. In addition, 59 brown rice samples sold in Tokyo were surveyed using the same method. Out of 44 samples, 12 pesticide residues below MRLs were detected. Therefore, this developed method is useful for the simultaneous determination of pesticide residues in brown rice.

Simultaneous Determination of Pesticide Residues and Mycotoxins in Storage Pu-erh Tea Using Ultra-High-Performance Liquid Chromatography Coupled with Tandem Mass Spectrometry.

Mycotoxins and pesticides are the most concerning chemical contaminants that can affect the quality of Pu-erh tea during its production and storage. This study presents a method that can simultaneously determine 31 pesticide residues and six mycotoxins in Pu-erh tea within 11 min using ultra-high-performance liquid chromatography coupled with tandem mass spectrometry (UPLC-MS/MS) after QuEChERS extraction. The lower limit of quantification (LOQ) for all analytes ranged between 0.06 and 50 ppb. Recoveries for each pesticide and mycotoxin ranged between 62.0 and 130.3%, with intra- and inter-day precisions lower than 15%. Good linear relationships were obtained, with correlation coefficients of r2 > 0.991 for all analytes. The established method was applied to 31 Pu-erh tea samples, including raw and ripened Pu-erh tea with different storage times. As a result, pesticide residues were not detected in any of the collected samples, and the mycotoxins detected in the samples were well below the official maximum residue limits (MRLs). Notably, the levels of aflatoxin B1 (AFB1), aflatoxin G1 (AFG1) and aflatoxin G2 (AFG2) were lower than 1 ppb in the samples stored for more than 30 years.

Current Role of Mass Spectrometry in the Determination of Pesticide Residues in Food

The extensive use of pesticides represents a risk to human health. Consequently, legal frameworks have been established to ensure food safety, including control programs for pesticide residues. In this context, the performance of analytical methods acquires special relevance. Such methods are expected to be able to determine the largest number of compounds at trace concentration levels in complex food matrices, which represents a great analytical challenge. Technical advances in mass spectrometry (MS) have led to the development of more efficient analytical methods for the determination of pesticides. This review provides an overview of current analytical strategies applied in pesticide analysis, with a special focus on MS methods. Current targeted MS methods allow the simultaneous determination of hundreds of pesticides, whereas non-targeted MS methods are now applicable to the identification of pesticide metabolites and transformation products. New trends in pesticide analysis are also presented, including approaches for the simultaneous determination of pesticide residues and other food contaminants (i.e., mega-methods), or the recent application of techniques such as ion mobility–mass spectrometry (IM–MS) for this purpose.

Development of a Microwave-Assisted Extraction Protocol for the Simultaneous Determination of Mycotoxins and Pesticide Residues in Apples by LC-MS/MS

The possible presence of contaminants, pesticide residues and mycotoxins, in agricultural commodities is a critical issue for food safety, causing great concern. In this work, a simple and rapid analytical method employing liquid chromatography–tandem mass spectrometry (LC-MS/MS) was developed for the simultaneous determination of pesticide residues and mycotoxins in apples. Microwave-assisted extraction (MAE) was used for sample preparation. The MAE protocol was optimized after evaluating the effects of the following extraction parameters: (a) extraction solvent, (b) acidic environment, (c) temperature, and (d) extraction time. The multiresidue MAE-LC-MS/MS method was validated for linearity, accuracy (bias and precision), limits of detection (LODs), limits of quantification (LOQs), and matrix effect. The validation of the method was carried out according to the SANTE/12682/2019 document. The method demonstrated good linearity with R2 ≥ 0.99, acceptable accuracy in the recovery rate range 70–116%, acceptable interassay precision with RSD% ≤ 20, and low LODs and LOQs in the ranges 0.005–0.015 μg/g and 0.01–0.03 μg/g, respectively. Matrix effects were observed only for the 25% of the analytes. The performance of the MAE-LC-MS/MS method was compared to that of the QuEChERS sample preparation method, and the MAE-LC-MS/MS method proved to be rapid and effective.

Validation of short run time GC-EI (+) MS/MS method for pesticide residues determination in dry Hibiscus syriacus L. via application of d-MRM and end-point backflush quantification techniques

ABSTRACT In this paper, the short injection method using GC-EI (+) MS/MS with end-point back-flush and dynamic-multi-reaction mechanism technique was validated for simultaneous determination of pesticide residues in dry Hibiscus syriacus L. applying QuEChERS extraction covering 176 GC-amenable pesticide residues. The GC optimum temperature program achieved a short run time and it was 20 minutes. The linearity of method was evaluated using matrix matched calibration standards at five concentration levels and the results showed that the coefficient of determination (r2) of each analyte was more than 0.990. The LODs was considered to be the lowest concentration that could be detected under optimal experimental conditions and it was 2 μg/kg (S/N = 3) and the LOQs was 10 μg/kg (S/N = 10). Acceptable recoveries of all the selected pesticides at three fortification levels were in the range from 60% to 102% with relative standard deviations ≤20% (n = 6) and matrix effect ranged from −31% to 6%‎. The method expanded measurement uncertainty was estimated as 40% (coverage factor k = 2, confidence level 95%). The validation results prove that it fit the intended use in accordance with the EC guidelines (SANTE/12682/2019) and could successfully expand the detection efficiency of pesticide residues in dry Hibiscus syriacus L. and other dry commodities.

Disposable Pipette Extraction (DPX) Coupled with Liquid Chromatography–Tandem Mass Spectrometry for the Simultaneous Determination of Pesticide Residues in Wine Samples

A novel multiresidue analytical method based on disposable pipette extraction (DPX) to determine the trace level of 28 pesticides in wine samples using liquid chromatography–tandem mass spectrometry (LC–MS/MS) has been developed. The DPX method is used for both extraction and purification. After the optimization, targets were eluted with 1% HCl in acetonitrile and the eluent was placed into LC analysis. The developed method exhibited good linearity (R2 > 0.99) for all 28 pesticides. Satisfactory recovery of 28 pesticides was observed ranging from 71 to 109%, with the intraday relative standard deviations (RSDs) and inter-day RSDs of 1–11% and 3–18%, respectively. Limits of detection (LODs) and limits of quantification (LOQs) were found to range from 1.5 to 3 μg/L and 5 to 10 μg/L, respectively. DPX was more suitable as compared with quick, easy, cheap, effective, rugged, and safe (QuEChERS) and solid-phase extraction (SPE) methods. The DPX method was applied to 47 commercial wine samples collected from China, and pesticide residues (0.02–0.09 mg/L) were found. In general, the developed method was highly reliable, selective, and sensitive for analyzing 28 pesticide residues in wine samples and would be applicable to other beverages.

Au-Decorated Dragonfly Wing Bioscaffold Arrays as Flexible Surface-Enhanced Raman Scattering (SERS) Substrate for Simultaneous Determination of Pesticide Residues.

Rapid sampling and multicomponent analysis are vital in pesticide residue detection. In this work, we proposed a SERS platform to detect three kinds of pesticides on apple peels simultaneously by a straightforward “press and peel off” method. The flexible Au/dragonfly wing (Au/DW) substrate was obtained from sputtering Au nanoislands on DW bioscaffold arrays by a simple direct current (DC) magnetron sputtering system. The high-performance substrate exhibited a low limit of detection (LOD) to 4-aminothiophenol (4-ATP) (10−9 M), outstanding reproducibility (less than 12.15%), good stability and suitability in multifold pesticide residues detection. Considering its excellent sample collection efficiency, the Au/DW substrate was employed to solve critical pesticide residue problems for detection of acephate (APT), cypermethrin (CPT), tsumacide (MTMC) and their multiple components on apple peels. The results show that the LOD was 10−3 ng/cm2 for APT obtained on the apple surface with a calculation equation of y = 0.26x + 6.68 and a determination coefficient (R2) of 0.970. Additionally, the LOD values for CPT and MTMC were 10−3 ng/cm2 and 10−4 ng/cm2, respectively. The finding in this work may provide a promising biomimetic SERS platform for on-spot detection of other organic pollutants in the food industry and inenvironmental protection.

Studying the Effect of Household-Type Treatment and Processing on the Residues of Ethion and Profenofos Pesticides and on the Contents of Capsaicinoids in Green Chili Pepper Using GC-MS/MS and HPLC

The first aim of this study was to create, test, and apply a quick, easy, cheap, effective, rugged, and safe (QuEChERS) method, based on acetonitrile extraction, for simultaneous determination of pesticide residues in green chili pepper (fresh and dried forms). There is a group of 86 repeatedly detected pesticides in the agricultural food commodity in Al-Qassim region, Saudi Arabia. The suggested method is utilizing GC-MS/MS for simultaneous determination of those 86 pesticides. The limit of quantitation (LOQ) for each pesticide was set as the lowest fortification level that achieved acceptable recoveries in the range 70–120% with precision (RSD ≤ 20%). The results indicated that two organophosphorus pesticides, ethion and profenofos, in the analyzed chili pepper samples have significantly exceeded the European maximum residual limit (MRL) for pesticides. The second purpose of the study was to evaluate the effect of some different household-type treatment and processing procedures on the detected pesticide residues and on capsaicinoids (particularly, capsaicin and dihydrocapsaicin) which are responsible for the pungency of chili pepper, using GC-MS/MS and HPLC. Some recommendations were concluded for the best practices.

Simultaneous determination of pesticide residues and antioxidants in blended oil using a liquid-liquid extraction combined with dispersive solid phase extraction method.

This article developed a method to detect two antioxidants (butylated hydroxyl anisole (BHA), butylated hydroxyl toluene (BHT)) and twelve pesticides (dichlorvos, pirimicarb, prothiofos, fenitrothion, ethoprophos, malathion, beta-Cypermethrin, profenofos, diazinon, propoxur, procymidon, captan) in blended oil samples after their extraction simultaneously. The establishment of the method was based on two-step process of screening and optimization experiment design. With a Plackett-Burman (PB) design, significant parameters were found by screening experiment and single factor experiment accompanied by a central composite design (CCD) experiment were used to make important parameters optimal. The coefficients of determination (r2) was between 0.9931 and 0.9996 while the limits of quantification (LOQs) and limits of detection (LODs) were found in scope of 0.002-0.04mg·kg-1 and 0.0006-0.0012mg·kg-1. Recovery values of analytes were above 74%, at the same time the relative standard deviations (RSDs) under 10% at the concentrations ranging from 0.05mg·kg-1 to 0.20mg·kg-1. To sum up, this method with shorter time and fewer consumption of reagents could be employed in various occasions to detect antioxidants and pesticides.

LC-MS/MSを用いた茶中の残留農薬一斉分析法 : 厚生労働省通知一斉試験法の改良

LC-MS/MSを用いた茶中の残留農薬一斉分析法 : 厚生労働省通知一斉試験法の改良

Validation Study on a Rapid Method for Simultaneous Determination of Pesticide Residues in Vegetables and Fruits by LC-MS/MS.

A validation study was carried out on a rapid method for the simultaneous determination of pesticide residues in vegetables and fruits by LC-MS/MS. Preparation of the test solution was performed by a solid-phase extraction technique with QuEChERS (STQ method). Pesticide residues were extracted with acetonitrile using a homogenizer, followed by salting-out and dehydration at the same time. The acetonitrile layer was purified with C18 and PSA mini-columns. The method was assessed for 130 pesticide residues in 14 kinds of vegetables and fruits at the concentration level of 0.01 μg/g according to the method validation guideline of the Ministry of Health, Labour and Welfare of Japan. As a result 75 to 120 pesticide residues were determined satisfactorily in the tested samples. Thus, this method could be useful for a rapid and simultaneous determination of multi-class pesticide residues in various vegetables and fruits.

Method Validation for Simultaneous Determination of Pesticide Residues in Post-Mortem Samples by High Performance Liquid Chromatography-Ultraviolet Method

Method Validation for Simultaneous Determination of Pesticide Residues in Post-Mortem Samples by High Performance Liquid Chromatography-Ultraviolet Method

Analysis of pesticide residues in tea using accelerated solvent extraction with in-cell cleanup and gas chromatography tandem mass spectrometry

A fast, simple and easily automated method was developed for the simultaneous determination of pesticide residues in tea using accelerated solvent extraction (ASE) with in-cell cleanup and gas chromatography-tandem mass spectrometry (GC-MS/MS).

QuEChERS 및 LC-MS/MS를 이용한 토양 중 124종 잔류농약다성분 분석법

토양환경 중 잔류농약 동시분석을 위해 124종의 농약을 대상으로 QuEChERS 전처리와 LC-MS-MS를 이용한 분석법을 개발하고자 하였다. QuEChERS 전처리 과정은 토양시료에 0.2N <TEX>$NH_4Cl$</TEX> 용액 침지하고 1% acetic acid 포함 acetonitrile 용매로 추출 후 <TEX>$MgSO_4$</TEX> 및 NaOAc로 salting out하고 PSA 50 mg, <TEX>$C_{18}$</TEX> 50 mg, <TEX>$MgSO_4$</TEX> 150 mg를 이용해 정제하였다. 분석법의 검증을 위해 양토 및 사양토 두 토양에서 0.005, 0.01, 0.02, 0.1 mg/kg 4수준으로 처리 후 회수율 실험을 실시하였다. 회수율 실험결과 Benfuracarb, Ethiofencarb, Pymetrozine, Pyrethrin 성분을 제외하고 나머지 성분들은 사양토와 양토 모두 70~120%의 적정 회수율을 나타내었으며, 상대표준편차도 20% 이내를 양호한 결과를 나타내었다. 따라서 QuEChERS 전처리 및 LC-MS를 이용한 분석법은 토양 중 잔류농약 다성분동시분석에 적용이 가능할 것으로 판단되었다. A QuEChERS (Quick, Easy, Cheap, Effective, Rugged and Safe) multiresidue method was developed for the simultaneous analysis of 124 pesticides in soil by LC-MS. The procedure involved liquid extraction of soil immersed with 0.2N <TEX>$NH_4Cl$</TEX> by acetonitrile with 1% acetic acid, followed by anhydrous <TEX>$MgSO_4$</TEX> and sodium acetate, and dispersive SPE cleanup with <TEX>$MgSO_4$</TEX>, primary secondary amine (PSA) and <TEX>$C_{18}$</TEX>. The extracts were analyzed with LC-MS/MS in ESI positive mode. Standard calibration curves were made by matrix matched standards and their correlation coefficients were higher than 0.99. Recovery studies for the validation were carried out using two type soils, loam and sandy loam, at four concentration levels (0.005, 0.01, 0.02, and 0.1 mg/kg). The recoveries of pesticides were in the range of 70-120% with < 20% RSD except 4 pesticides, Benfuracarb, Ethiofencarb, Pymetrozine, and Pyrethrin. This result indicated that the method using QuEChERS and LC-MS/MS could be applied for the simultaneous determination of pesticide residues in soils.

Determination of pesticides and related compounds in water by dispersive liquid–liquid microextraction and gas chromatography-triple quadrupole mass spectrometry

The declining quality of drinking water supplies due to industrial waste is the result of highly diverse industrial processes. In this context, the establishment of analytical methods focused on monitoring organic compounds related to environmental and health problems is very important. In this study, a quick and effective method based on dispersive liquid–liquid microextraction (DLLME) and gas chromatography coupled with triple quadrupole tandem mass spectrometry (GC-QqQ-MS/MS) was developed and validated for the simultaneous determination of pesticide residues and related compounds in water. The proposed DLLME method uses water sample aliquots of 5 mL, 2 mL of acetone as a dispersive solvent and 50 μL of carbon tetrachloride as an extraction solvent at low temperature. This method was successfully applied for the determination of pesticide residues and related compounds in water at quantification limits between 0.03 and 0.10 μg L−1. The method showed a linear range from 0.05 to 10.0 μg L−1 with r2 > 0.998. Recovery assays presented mean recoveries between 70 and 120% for most of the compounds with good precision, despite different chemical natures of the compounds analyzed.

Determination of pesticide residues and related compounds in water and industrial effluent by solid-phase extraction and gas chromatography coupled to triple quadrupole mass spectrometry

Pollution of drinking water supplies from industrial waste is a result of several industrial processes and disposal practices, and the establishment of analytical methods for monitoring organic compounds related to environmental and health problems is very important. In this work, a method using solid-phase extraction (SPE) and gas chromatography coupled to triple quadrupole tandem mass spectrometry (GC-QqQ-MS/MS) was developed and validated for the simultaneous determination of pesticide residues and related compounds in drinking and surface water as well as in industrial effluent. Optimization of the method was achieved by using a central composite design approach on parameters such as the sample pH and SPE eluent composition. A single SPE consisting of the loading on a polymeric sorbent of 100 mL of sample adjusted to pH 3 and elution with methanol/methylene chloride (10:90, v/v) permitted the obtaining of acceptable recoveries in most cases. The concentration factor associated with sensitivity of the chromatographic analysis permitted the achievement of the method limit of detection values between 0.01 and 0.25 μg L(-1). Recovery assays presented mean recoveries between 70 and 120% for most of the compounds with very good precision, despite the different chemical nature of the compounds analyzed. The selectivity of the method, evaluated through the relative intensity of quantification and qualification ions obtained by GC-QqQ-MS/MS, was considered adequate. The developed method was finally applied to the determination of target analytes in real samples. River water and treated industrial effluent samples presented residues of some compounds, but no detectable residues were found in the drinking water samples evaluated.

Application of QuEChERS Method for Simultaneous Determination of Pesticide Residues and PAHs in Fresh Herbs

The aim of this study was to evaluate the application of quick, easy, cheap, effective, rugged and safe method for simultaneous determination of polycyclic aromatic hydrocarbons and pesticide residues in fresh herbs. In the experiment two extraction solvents and standard types of sorbents were used. The extracts were analyzed using GC–SIM–MS. The results suggest that acetonitrile is more suitable extraction solvent giving more purified samples and better recovery values (71.6 %–116.9 %) with RSD lower than 15 % for most of the compounds. In real samples pesticides were identified in the samples of parsley, tarragon and lovage. In few samples the pesticide levels exceeded the MRL established by EU.

Critical assessment of extraction methods for the simultaneous determination of pesticide residues and mycotoxins in fruits, cereals, spices and oil seeds employing ultra-high performance liquid chromatography–tandem mass spectrometry

This study addresses a current trend in chemical food safety control represented by an effort to integrate analyses of various groups of food contaminants/toxicants into a single, high-throughput method. The choice of optimal sample preparation step is one of the key conditions to achieve good performance characteristics. In this context, we investigated the possibility to expand the scope of the three multi-analyte extraction procedures employed earlier in other studies for rapid isolation of either pesticides or mycotoxins from plant matrices. Following procedures were tested: A – aqueous acetonitrile extraction followed by partition (QuEChERS-like method), B – aqueous acetonitrile extraction, and C – pure acetonitrile extraction. On the list of target analytes, we had 288 pesticides (including ‘troublesome’ acidic, basic and base-sensitive compounds) together with 38 mycotoxins (including all EU regulated ones and many ‘emerging’ toxins on the European Food Safety Authority (EFSA) list). The matrices selected for the experiments, apple baby food, wheat flour, spices and sunflower seeds, represented various composition categories in terms of moisture, fat and extractable compounds (e.g. pigments and essential oils) content. In preliminary experiments, acceptable recoveries (70–120%) for most of analytes were obtained by the analysis of spiked matrices, regardless which extraction procedure was used. However, when analysing dry samples with incurred pesticide residues/mycotoxins, the method C did not enable efficient extraction of some common contaminants. Procedure A, thanks to a higher matrix equivalent compared to the method B and relatively less pronounced matrix effects, enabled lower quantification limits for all analyte/matrix combinations, with the exception of polar mycotoxins and/or pesticides. Higher recoveries for the latter group of analytes could be achieved by the method B; on the other hand, extraction efficiency of non-polar pesticides from fatty matrix was rather poor by this method.