Optimized residue analysis method for broflanilide and its metabolites in agricultural produce using the QuEChERS method and LC-MS/MS.

Since broflanilide is a newly developed pesticide, analytical methods are required to determine the corresponding pesticide residues in diverse crops and foods. In this study, a pesticide residue analysis method was optimized for the detection and quantification of broflanilide and its two metabolites, DM-8007 and S(PFH-OH)-8007, in brown rice, soybean, apple, green pepper, mandarin, and kimchi cabbage. Residue samples were extracted from the produce using QuEChERS acetate and citrate buffering methods and were purified by dispersive solid-phase extraction (d-SPE) using six different adsorbent compositions with varying amounts of primary secondary amine (PSA), C18, and graphitized carbon black. All the sample preparation methods gave low-to-medium matrix effects, as confirmed by liquid chromatography-tandem mass spectrometry using standard solutions and matrix-matched standards. In particular, the use of the citrate buffering method, in combination with purification by d-SPE using 25 mg of PSA and a mixture of other adsorbents, consistently gave low matrix effects that in the range from -18.3 to 18.8%. Pesticide recoveries within the valid recovery range 70-120% were obtained both with and without d-SPE purification using 25 mg of PSA and other adsorbents. Thus, the developed residue analysis method is viable for the determination of broflanilide and its metabolites in various crops.

Optimization of a Simplified and Effective Analytical Method of Pesticide Residues in Mealworms (Tenebrio molitor Larvae) Combined with GC-MS/MS and LC-MS/MS.

An effective analytical method was optimized for residues including chlorpyrifos-methyl, deltamethrin, fenoxanil, thiobencarb and fludioxonil in mealworms, the larval form of Tenebrio molitor. They are listed for pest control during wheat cultivation and can be found in wheat-bran feed for growing mealworms in South Korea. Analytes were extracted using acetonitrile and salt packet. Four clean-up methods ((1) MgSO4 + 25 mg PSA + 25 mg C18; (2) MgSO4 + 50 mg PSA + 50 mg C18; (3) EMR-lipidTM tube; and (4) 10 mL n-hexane) were investigated and the method (1) was selected due to its robustness. Low-temperature precipitation of fat and proteins improved the recoveries. Recoveries from the Method (1) were satisfying with 70-120% with <20% relative SD at a spiking level of 0.01 mg/kg. With the simultaneous sample preparation, fenoxanil, thiobencarb and fludioxonil were analyzed by liquid chromatography tandem mass spectrometry (LC-MS/MS) and chlorpyrifos-methyl and deltamethrin by gas chromatography tandem mass spectrometry (GC-MS/MS). Quantification limits for LC-MS/MS and GC-MS/MS were 0.5 and 2.5 µg/L, respectively. No pesticides of interest were detected in 30 real samples collected across the nation. However, the data can be provided for establishing maximum residue limits for the pesticides in mealworms in response to the positive list system.

Identification and characterization of matrix components in spinach during QuEChERS sample preparation for pesticide residue analysis by LC-ESI-MS/MS, GC-MS and UPLC-DAD.

In this article matrix components in spinach were investigated in detail. The samples were prepared using two QuEChERS (quick, easy, cheap, effective, rugged and safe) methods, AOAC and CEN. Liquid chromatography-electrospray ionization-tandem mass spectrometry (LC-ESI-MS/MS), gas chromatography-mass spectrometry (GC-MS) and ultra performance liquid chromatography-diode array detector (UPLC-DAD), were applied for component identification. The strategies of identification by LC-ESI-MS/MS include accurate mass spectra of the parent ion, comparison with previous literature data and investigation of the mass spectral decomposition pattern. Overall, fourteen components were identified by LC-ESI-MS/MS in each methods of AOAC and CEN, which were phytosteroids, flavonoids, fatty acids and fatty acid amides. Fifty components using AOAC method and fifty-seven components using CEN method were identified in GC-MS by comparing mass data with the National Institute of Standards and Technology (NIST, U.S.) database. The results indicate that the major components of the matrix are terpenoids, fatty acids and fatty acid esters. Moreover, three pigments (neoxanthin, violaxanthin and lutein) in the AOAC method and eight pigments (neoxanthin, violaxanthin, zeaxanthin, lutein, chlorophyll a, chlorophyll b, pheophytin a and beta-carotene) in the CEN method that gave a characteristics peak at 440 nm were identified by the UPLC-DAD. According to the sample preparation condition using different amounts of graphitized carbon black (GCB) in this study, the AOAC method had higher matrix component removal efficiency than the CEN method. A better understanding of matrix components would increase the current knowledge for improvement of existing QuEChERS methodology, as well as contribute to new method developments.

Compensation for matrix effects in GC analysis of pesticides by using cucumber extract.

Matrix effects (MEs) can adversely affect quantification in pesticide residue analysis using GC. Analyte protectants (APs) can effectively interact with and mask active sites in the GC system, and are added individually or in combination to sample extracts and calibration solutions to minimize errors related to MEs. Unfortunately, APs cannot sufficiently compensate for MEs in all cases. Plant extracts, containing a broad range of natural compounds with AP properties, can also be used for this purpose. In this study, the applicability of cucumber extract as a natural AP mixture was investigated both alone and in combination with traditional APs. Extracts of two selected difficult matrices (onion and garlic) were prepared according to the citrate-buffered QuEChERS (quick, easy, cheap, effective, rugged, and safe) procedure. ME values of 40 representative GC-amenable pesticides were compared when calibrating against standards in pure solvent and in cucumber extract, with and without the addition of APs. Using a GC system with a contaminated inlet liner, the use of a cucumber-based calibration solution decreased MEs remarkably. The combination of APs with cucumber raw extract further decreased MEs, resulting in more than 85% of the tested pesticides showing ≤ 10% ME in onion and ≤ 20% ME in garlic. These results demonstrate that the preparation of calibration standards based on cucumber extracts (with or without the addition of APs) is a very useful and practical approach to compensate for MEs in pesticide residue analysis using QuEChERS and GC-MS/MS. The use of various internal standards is furthermore critically discussed.