Development of automated online gel permeation chromatography–gas chromatograph mass spectrometry for measuring multiresidual pesticides in agricultural products

Abstract

An automated online gel permeation chromatography-gas chromatograph mass spectrometer (GPC-GC/MS) was developed for the rapid determination of residual pesticides in agricultural products. Pesticides were extracted from homogenized food samples with acetonitrile and decontaminated via the matrix solid-phase dispersion (MSPD) technique, using a primary secondary amine as sorbent prior to GPC-GC/MS analysis. A slightly modified preparation method and automated GPC step proved useful in minimizing matrix interference. To evaluate the performance of the system, 97 target pesticides were spiked at a concentration of 0.1 mg/kg into a range of food types, including potato, cabbage, carrot, apple, orange, cucumber, and rice. A low flow rate of 0.1 mL/min in GPC resulted in a 40-fold reduction in solvent consumption compared with conventional GPC column applications. The combination of MSPD technique and GPC-GC/MS for the analysis of the 97 pesticides can be accomplished within 90 min. Most pesticides were recovered in the range of 70-120%, with relative standard deviation generally less than 10%. The results demonstrate that the method can be successfully applied with acceptable recoveries to a broad range of target pesticides within a diverse range of food types.

Current mass spectrometry strategies for the analysis of pesticides and their metabolites in food and water matrices

“…Finally, on-line automated SPE extraction procedures hyphenated to LC-MS (Marín et al, 2006;Perreau et al, 2007;Pirard et al, 2007) or GG-MS (Planas et al, 2006) systems have been tested, aiming to minimize the time and cost of the sample preparation step. In some cases of fatty samples, gel-permeation chromatography (GPC) and/or GPC followed by SPE (Ballesteros, Sánchez, & H s e l p m a s r e t a W s e d i c i t s e p 0 0 3 -1 Greulich, & Alder, 2008 171 pesticides Fruits, vegetables, Botitsi et al, 2007 136 pesticides Fruit and Mol et al, 2007 187 pesticides Fruit and (Continued) Díez et al, 2006;Fernández Moreno et al, 2006;Garrido Frenich et al, 2006;Guardia-Rubio et al, 2006Pang et al, 2006a;Zhang et al, 2006;Huang et al, 2007;Liu et al, 2007;Van der Lee et al, 2008) or counter-current chromatography (CCC) (Goto et al, 2006a) are required for better clean up. Dispersive SPE (DSPE) or matrix-solid-phase dispersion (MSPD) involves treatment of the sample with a sorbent material either directly or after SE (Banerjee et al, 2007;Mol et al, 2007;Plaza Bolaños, Garrido Frenich, & Martínez Vidal, 2007;Kruves et al, 2008;Ramos et al, 2008;Patil et al, 2009;Radišic' et al, 2009).…”

Determination of estrogens and bisphenol A in bovine milk by automated on-line C30 solid-phase extraction coupled with high-performance liquid chromatography–mass spectrometry

“…In order to improve the performance of on-line SPE, dispersive SPE with primary secondary amine (PSA) was employed for the further cleanup. This method was introduce by Anastassiades et al [30] and has gained wide acceptance for the determination of various analytes in recent years [31][32][33]. In the proposed method, PSA was used to adsorb and eliminate the impurities which were polar with -OH and -COOH in samples.…”

Determination of triazine herbicides in fruits and vegetables using dispersive solid‐phase extraction coupled with LC–MS

“…When the samples contain less water, modifications must be made. Some researchers added water to the extraction [22], or reduced the sample amount [26]. In the present study, we reduced the amount of MgSO 4 , and finally obtained acceptable results.…”

“…However, the application of QuEChERS in pesticide extraction is limited to hydrophobic compounds. For example, our previous study reported that highly water-soluble pesticides showed low recoveries (a 70%), for they would probably move into the water layer during the extraction step [22]. Up to now, to the best of the authors' knowledge, there has been no report on the extraction of triazines, which are a type of highly hydrophilic pesticides, from real samples using QuEChERS.…”

“…Therefore, it has attracted much attention in several fields. In 2005, Min Liu et al determined carbamate and organophosphorus pesticides in fruits and vegetables simultaneously using dispersive-SPE sample cleanup [21], and Li-Bin Liu et al developed a multiple pesticides residue method based on QuEChERS for 97 pesticides [22]. Other examples were the determination of sulfonamides in chicken muscle [23], pharmaceuticals in whole blood [24], and antibiotics in bovine kidney tissue [25], etc.…”