Liquid Chromatography-Tandem Mass Spectrometry for the Simultaneous Analysis of 353 Pesticides in the Edible Insect Tenebrio molitor Larvae (Mealworms)

Tenebrio molitor larvae (mealworm) is an edible insect and is considered a future food. Using liquid chromatography-tandem mass spectrometry (LC-MS/MS), a novel method for simultaneous analysis of 353 target analytes was developed and validated. Various sample preparation steps including “quick, easy, cheap, effective, rugged, and safe” (QuEChERS) extraction conditions, number of acetonitrile-hexane partitions, and dispersive-solid phase extraction (dSPE) sorbents were compared, and the optimal conditions were determined. In the established method, 5 g of homogenized mealworms was extracted with acetonitrile and treated with QuEChERS EN 15662 salts. The crude extract was subjected to three rounds of acetonitrile-hexane partitioning, and the acetonitrile layer was cleaned with C18 dSPE. The final solution was matrix-matched and injected into LC-MS/MS (2 μL). For target analytes, the limits of quantitation (LOQs) were ≤10 μg/kg, and the correlation coefficient (r2) of calibration was >0.990. In recovery tests, more than 90% of the pesticides showed an excellent recovery range (70–120%) with relative standard deviation (RSD) ≤20%. For more than 94% of pesticides, a negligible matrix effect (within ±20%) was observed. The analytical method was successfully applied and used for the detection of three urea pesticides in 4 of 11 mealworm samples.

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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

Molecules ◽

10.3390/molecules25153518 ◽

2020 ◽

Vol 25 (15) ◽

pp. 3518 ◽

Cited By ~ 1

Author(s):

Leesun Kim ◽

Sujin Baek ◽

Kyungae Son ◽

Eunsun Kim ◽

Hyun Ho Noh ◽

...

Keyword(s):

Mass Spectrometry ◽

Tandem Mass Spectrometry ◽

Analytical Method ◽

Tenebrio Molitor ◽

Tandem Mass ◽

Chromatography Tandem Mass Spectrometry ◽

Wheat Cultivation ◽

Maximum Residue Limits ◽

Liquid Chromatography Tandem Mass ◽

Tenebrio Molitor Larvae

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.

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Pitfalls Associated with the Use of Liquid Chromatography–Tandem Mass Spectrometry in the Clinical Laboratory

Clinical Chemistry ◽

10.1373/clinchem.2009.138602 ◽

2010 ◽

Vol 56 (8) ◽

pp. 1234-1244 ◽

Cited By ~ 210

Author(s):

Michael Vogeser ◽

Christoph Seger

Keyword(s):

Mass Spectrometry ◽

Liquid Chromatography ◽

Tandem Mass Spectrometry ◽

Matrix Effects ◽

Clinical Chemistry ◽

Tandem Mass ◽

Chromatography Tandem Mass Spectrometry ◽

Target Analytes ◽

Potential Sources ◽

Liquid Chromatography Tandem Mass

BACKGROUND Novel mass spectrometric techniques such as atmospheric pressure ionization and tandem mass spectrometry have substantially extended the spectrum of clinical chemistry methods during the past decade. In particular, liquid chromatography tandem–mass spectrometry (LC-MS/MS) has become a standard tool in research laboratories as well as in many clinical laboratories. Although LC-MS/MS has features that suggest it has a very high analytical accuracy, potential sources of inaccuracy have recently been identified. CONTENT The sources of inaccuracy in LC-MS/MS methods used in the routine quantification of small molecules are described and discussed. Inaccuracy of LC-MS/MS methods can be related to the process of ionization through the insource transformation of conjugate metabolites or target analytes and may also be attributable to ionization matrix effects that have a differential impact on target analytes and internal-standard compounds. Inaccuracy can also be associated with the process of ion selection, which mainly occurs when compounds from the sample matrix share mass transitions with a target analyte. In individual assays, most potential sources of inaccuracy can be controlled by sufficient LC separation–based sample workup before MS analysis. SUMMARY LC-MS/MS methods should undergo rigorous and systematic validation before introduction into patient care.

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Determination of steroid hormones in sediments based on quick, easy, cheap, effective, rugged, and safe (modified-QuEChERS) extraction followed by liquid chromatography-tandem mass spectrometry (LC-MS/MS)

Analytical Methods ◽

10.1039/c5ay01972a ◽

2015 ◽

Vol 7 (22) ◽

pp. 9577-9586 ◽

Cited By ~ 4

Author(s):

Julien Camilleri ◽

Emmanuelle Vulliet

Keyword(s):

Mass Spectrometry ◽

Liquid Chromatography ◽

Tandem Mass Spectrometry ◽

Steroid Hormones ◽

Tandem Mass ◽

Modified Quechers ◽

Chromatography Tandem Mass Spectrometry ◽

Target Analytes ◽

Liquid Chromatography Tandem Mass

The method enables the determination of the target analytes with limits of detection comprised between 0.03 and 0.2 ng g¬1and limits of quantification comprised between 0.1 and 0.6 ng g¬1.

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Effective and rugged analysis of glyphosate, glufosinate, and metabolites in Tenebrio molitor larva (mealworms) using liquid chromatography tandem mass spectrometry

Scientific Reports ◽

10.1038/s41598-021-96529-8 ◽

2021 ◽

Vol 11 (1) ◽

Author(s):

Leesun Kim ◽

Sujn Baek ◽

Kyungae Son ◽

Hee-Dong Lee ◽

Dal-Soon Choi ◽

...

Keyword(s):

Mass Spectrometry ◽

Liquid Chromatography ◽

Tandem Mass Spectrometry ◽

Tenebrio Molitor ◽

Tandem Mass ◽

Chromatography Tandem Mass Spectrometry ◽

Hydrophilic Lipophilic Balance ◽

Relative Standard ◽

Liquid Chromatography Tandem Mass ◽

Food And Feed

AbstractTenebrio molitor larva (mealworms) has recently attracted attention as a protein source for food and feed. The larva is generally fed with wheat bran, which can be possibly contaminated with glyphosate. To establish food safe standards, a rugged and effective analytical method for glyphosate, aminomethylphosphonic acid, glufosinate, and their metabolites including 3-methylphosphinico-propionic acid, and N-acetyl glufosinate, in mealworms was optimized using liquid chromatography tandem mass spectrometry. An anionic polar pesticide column was used due to its high suitability for glyphosate. Acidified water and acetonitrile were used to extract the target compounds without contribution from various fatty and pigment interferences derived from brownish insects. Seven different clean-up procedures ((1) 50 mg C18 (2) 20 mg C18/Z-sep (3) PRiME hydrophilic-lipophilic balance (HLB) cartridge (4) 75 mg Z-sep, (5) 75 mg Z-sep+, (6) EMR-lipid cartridge, and (7) 50 mg ENVI-Carb) were compared. Due to its simplicity and cost-effectiveness, PRiME HLB was selected for clean-up. The recoveries of the target compounds were ranged from 86 to 96% with < 20% relative standard deviations. Therefore, this simple and effective method can be applied for the two pesticides and their metabolites in other edible insects or high-fat matrices.

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