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Determination of 69 Pesticide Residues in Cowpea Products by Gas

Chromatography-Tandem Mass Spectrometry and Liquid
Chromatography-Tandem Mass Spectrometry
Combined with QuEChERS

ZENG Ting, LIU Jiaxin, PENG Rulin, ZHUO Chengbang, TANG Su, ZHU Yutian *
(Shenzhen Academy of Metrology and Quality Inspection, Shenzhen 518100, China)

Abstract: Cowpea is prone to pesticide residues due to its growth habits and unique planting environment, while pesticides
are also introduced when producing and processing sour and dry bean products, further increasing the potential food safety risks
of cowpea products. However, research on pesticide residue detection methods of cowpea products lacked, so the title method
was proposed. After crushing the sour and dry bean samples, 10 g of sour bean sample was taken (5 g of dry bean sample was
taken, and 5 mL of water was added), and 10 mL of acetonitrile was taken. The mixture was extracted by vortex for 2 min, and
1 ceramic average proton and a QuEChERS extraction salt package containing 4 g of magnesium sulfate, 1 g of sodium chloride,
1 g of sodium citrate, and 0.5 g of disodium hydrogen citrate were added. The mixture was extracted by vortex for 2 min, and
centrifuged for 2 min. The supernatant was placed into a QuEChERS purification tube containing 900 mg of anhydrous magnesium
sulfate, 150 mg of PSA, and 15 mg of GCB, and the tube was vortexed for 1 min, and centrifuged for 2 min. An aliquot (1 mL) of
the supernatant was passed through a 0.22 μm organic filter membrane, and the filtrate was analyzed by LC-MS/MS. An aliquot
(1 mL) of the supernatant was taken, and blown to near dryness by nitrogen at 40 ℃. After 1 mL of acetone was added, the mixture
was vortexed for 30 s, and passed through a 0.22 μm organic filter membrane, and the filtrate was analyzed by GC-MS/MS.
In GC-MS/MS analysis, the 41 pesticides were separated on Thermo TG-5SILMS chromatographic column under temperature
programmed conditions, ionized by EI source, detected by MRM mode, and quantified by matrix matching method. In LC-MS/
MS analysis, the 28 pesticides were separated by gradient elution on ACQUITY UPLC BEH C column with mixed solutions
18
composed of 5 mol · L ammonium acetate solution containing 0.01% (volume fraction, the same below) formic acid and methanol
−1
+
solution containing 0.01% formic acid at different volume ratios, ionized by ESI mode, detected by MRM mode, and quantified by
matrix matching method. It was shown that linear relationships between values of the mass concentration and peak area of pesticides
−1
−1
were kept in the ranges of 0.010-0.400 mg · L for GC-MS/MS and 0.005-0.150 mg · L for LC-MS/MS, with correlation
coefficients greater than 0.998 0, and lower limits of determination (10S/N) of 0.01 mg · kg . Test for recovery was made according
−1
to standard addition method, giving recoveries in the range of 70.6%-117%, and RSDs (n=6) of the determined values ranged
from 0.45% to 7.0%. The proposed method was applied to the analysis of 26 batches of sour samples and 22 batches of dry bean
samples, the detection rate of the positive samples was up to 81.2%, and the number of pesticides detected was up to 57 kinds.
Keywords: QuEChERS; gas chromatography-tandem mass spectrometry; liquid chromatography-tandem mass spectrometry;
pesticide; sour bean; dry bean
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