Multiresidue Pesticide Analysis of Dried Botanical Dietary Supplements Using an Automated Dispersive SPE Cleanup for QuEChERS and High-Performance Liquid Chromatography-Tandem Mass Spectrometry

Institute for Food Safety and Health, Moffett Campus, Illinois Institute of Technology , 6502 South Archer Road, Bedford Park, Illinois 60501-1957, United States.
Journal of Agricultural and Food Chemistry (Impact Factor: 2.91). 08/2012; 60(40). DOI: 10.1021/jf301723g
Source: PubMed


An automated dispersive solid phase extraction (dSPE) cleanup procedure as part of the Quick, Easy, Cheap, Effective, Rugged, and Safe (QuEChERS) method, coupled with liquid chromatography-tandem mass spectrometry using electrospray ionization in positive mode, was used for the simultaneous analysis of 236 pesticides in three dried powdered botanical dietary supplements (ginseng, saw palmetto, and gingko biloba). The procedure involved extraction of the dried powdered botanical samples with salt-out acetonitrile/water extraction using anhydrous magnesium sulfate and sodium chloride, followed by an automated dSPE cleanup using a mixture of octadodecyl- (C(18)) and primary-secondary amine (PSA)-linked silica sorbents and anhydrous MgSO(4) and online LC-MS/MS analysis. Dynamic multiple-reaction monitoring (DMRM) based on the collection of two precursor-to-product ion transitions with their retention time windows was used for all of the targeted pesticides and the internal standard. Matrix-matched calibration standards were used for quantitation, and standard calibration curves showed linearity (r(2) > 0.99) across a concentration range of 0.2-400 ng/mL for the majority of the 236 pesticides evaluated in the three botanical matrices. Mean recoveries (average %RSD, n = 4) were 91 (6), 93 (4), 96 (3), and 99 (3)% for ginseng, 101 (9), 98 (6), 99 (4), and 102 (3)% for gingko biloba, and 100 (9), 98 (6), 96 (4), and 96 (3)% for saw palmetto at fortification concentrations of 25, 100, 250, and 500 μg/kg, respectively. The geometric mean matrix-dependent instrument detection limits were 0.17, 0.09, and 0.14 μg/kg on the basis of the studies of 236 pesticides tested in ginseng roots, gingko biloba leaves, and saw palmetto berries, respectively. The method was used to analyze incurred ginseng samples that contained thermally labile pesticides with a concentration range of 2-200 μg/kg, indicating different classes of pesticides are being applied to these botanicals other than the traditional pesticides that are commonly used and analyzed by gas chromatography techniques. The method demonstrates the use of an automated cleanup procedure and the LC-MS/MS detection of multiple pesticide residues in dried, powdered botanical dietary supplements.

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    • "It forms part of the QuEChERS (quick, easy, cheap, effective , rugged and safe) procedure, the other part of which involves salting-out extraction. QuEChERS is commonly used for the extraction of pesticides in fruits and vegetables [21] [22]. DSPE alone, as an independent sample preparation method, has been widely applied for the enrichment of analytes in aqueous samples [23] [24]. "
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    ABSTRACT: Layered double oxide hollow spheres (LDO-HSs) were synthesized and employed as a dissolvable sorbent in dispersive solid-phase extraction (DSPE) to extract eleven United States Environmental Protection Agency's priority phenols from aqueous samples. With their higher specific surface area, LDO-HSs showed much higher extraction efficiency than normal layered double hydroxides and layered double oxides. The entire extraction process was accomplished in a syringe. After DSPE, the sorbent with the analytes was isolated conveniently by directly expelling the spent sample solution out of the syringe. The analyte-enriched sorbent was then subsequently dissolved by withdrawing an acidic solution into the syringe. The final extract was analyzed by high-performance liquid chromatography with ultraviolet detection. The results showed that this method provided low limits of detection for the phenols (0.005-0.153μg/L), good linearity (r(2)≥0.9956) and relative standard deviations of ≤6.7%. The optimized method was applied to water samples from 3 rivers. This simple extraction procedure was demonstrated to be a fast, efficient and convenient DSPE approach. Copyright © 2014 Elsevier B.V. All rights reserved.
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    ABSTRACT: This study was conducted to monitor residual pesticides in ginseng and balloon flower roots and to assess their risk to human health. All of 112 samples consisted of ginseng and balloon roots were purchased from traditional domestic markets and supermarkets in nine provinces of Korea in 2012. Multi-residue analysis of 122 pesticides was conducted and the analysis was performed by gas chromatography-electron capture detector, gas chromatography- nitrogen/phosphorus detector, and high-performance liquid chromatography. Seven pesticides were detected in 12 root samples and the detection rate was 10.7%. The detected twelve root samples were 10 ginseng root samples and 2 balloon root samples. Pesticides detected in root samples were procymidone, kresoxim-methyl, endosulfan, cypermethrin, tralomethrin, tetraconazole and chlorfluazuron. Among them, two pesticides as tetraconazole in a balloon flower root and cypermethrin in a ginseng root exceeded the recommended maximum residue limit set by Korea Food and Drug Administration. Five pesticides detected from 10 root samples were identified as unregistered pesticides in Korea. In order to do risk assessment with Korean medicinal plant consumption, estimated daily intake of residual pesticides were determined and compared to acceptable daily intake, referring to %ADI values. The range of %ADI values was from 0.006% to 0.333%. Taken together, it demonstrates the pesticides found in the two root samples were below the safety margin, indicating no effect on human health.
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