Thermal desorption sampling-gas chromatography-tandem mass spectrometry with a carbonyl-iron powder composite silica monolithic column for enrichment and determination of pyrethroid pesticide residues in tea samples

doi:10.3724/SP.J.1123.2019.12019

Abstract

Abstract:

Long-term exposure to pyrethroid insecticides is detrimental to the nervous system, reproductive system, and immune system in humans. Therefore, enrichment detection of pyrethroid pesticides is imperative. In this study, a novel carbonyl-iron powder composite silica monolithic column was first prepared for the enrichment of pyrethroid pesticide residues in tea samples. Then, the target analytes were thermally desorbed and online-injected into a gas chromatography-tandem mass spectrometry (GC-MS/MS) system. In the present method, hydroxy-terminated polydimethylsiloxane (PDMS) was covalently bonded to the surface of the SiO₂ network and subsequently bonded with the carbonyl-iron powder. After the target analytes were adsorbed and concentrated in the PDMS spots, high-frequency induction heating was used for GC-MS/MS sampling. Under the optimal conditions, the detection limits of the pyrethroid pesticide residues were 3.8 to 7.5 μg/kg, and the relative standard deviation was 3.2% to 6.8% (n=6). The extraction recovery ranged from 97.7% to 110.5%, and the correlation coefficient was ≥ 0.9960. In addition, the enrichment factor could reach 1000 times. PDMS materials show excellent adsorption properties for non-polar solutes. In our experiment, carbonyl iron powder-bonded monolithic columns were prepared on the basis of stir bar sorptive extraction (SBSE). Carbonyl iron powder magnetic particles were evenly implanted into the inorganic-organic hybrid cassia material for realizing rapid and uniform desorption upon electromagnetic induction heating. Under the premise of perfectly integrating the technical advantages of SBSE and solid-phase microextraction (SPME), the electromagnetic induction characteristics of carbonyl iron powder can be exploited for thermal desorption and directly combined with GC-MS to facilitate online analysis and solvent-free elution. Compared with the conventional SPME method, the proposed method has the advantages of high enrichment factor, large adsorption capacity of the column, reusability, high degree of automation, and good universality. This method has high significance for sample preparation and for the extraction of pesticide residues in complex matrices.

Key words: monolithic column, gas chromatography-tandem mass spectrometry (GC-MS/MS), pyrethroid pesticides, tea, thermal desorption

WU Yonghui, DENG Yun, LÜ Yaning, GAN Wu'er. Thermal desorption sampling-gas chromatography-tandem mass spectrometry with a carbonyl-iron powder composite silica monolithic column for enrichment and determination of pyrethroid pesticide residues in tea samples[J]. Chinese Journal of Chromatography, 2020, 38(8): 961-967.

Figures/Tables 11

Fig. 1 Schematic of extraction/desorption system HFPS: high-frequency induction heating power source; MC: monolithic column.

Table 1 Ion channel data for five targeted pyrethroid pesticides

Component	Ion channel 1 (m/z)	Ion channel 2 (m/z)	Ion channel 3 (m/z)	Ion channel 4 (m/z)
Permethrin	183.10＞153.10	183.10＞158.10	183.10＞165.1	0.00＞0.00
Cyfluthrin	163.10＞127.10	163.10＞91.00	226.10＞206.1	0.00＞0.00
Cypermethrin	163.10＞127.10	163.10＞91.00	181.10＞152.1	0.00＞0.00
Alphacypermethrin	163.10＞127.10	163.10＞91.00	181.10＞152.1	0.00＞0.00
Deltamethrin	180.90＞151.90	252.90＞93.00	252.90＞171.90	0.00＞0.00

Fig. 2 Schematic diagram of the preparation process of monolithic column material

Fig. 3 Scan electron microscope(SEM) images of materials with magnetic particles a. CIP; b. reduced iron powder.

Fig. 4 SEM images of materials under different water contents a. 0.6 mL; b. 0.7 mL; c. 0.8 mL.

Fig. 5 Infrared spectra of PDMS, TEOS and CIP/SiO2/PDMS

Fig. 6 TGA curve of the CIP/SiO2/PDMS material

Fig. 7 Enrichment efficiency of five pyrethroid pesticide targets with different column flow rates

Fig. 8 Curve of temperature-time of the monolithic column under different power

Table 2 Linear relationships, RSDs of peak areas, detection limits and recoveries of five pesticides

Pesticide	Linear equation	r	RSD/% (n=6)	LOD/(μg/kg)	Recovery/%
Y: peak area; X: mass concentration, mg/L.
Deltamethrin	Y=980776X-40711.4	0.9979	4.7	7.5	98.2-110.5
Permethrin	Y=3604110X+419440.7	0.9966	3.2	3.8	98.6-108.2
Cyfluthrin	Y=2494180X+82573.8	0.9960	4.8	5.8	99.3-103.3
Cypermethrin	Y=2098440X+53478.4	0.9984	6.8	7.5	97.7-102.7
Alphacypermethrin	Y=1858200X+227007	0.9980	6.2	5.0	98.9-104.1

Fig. 9 Comparison of (a) conventional method and (b) this method

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