Vol. 44, No. 6 GC/MS/MS. Determination of Low-level Pesticide Residues in Agricultural Products by Ion-trap GC/MS/MS

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1 310 Vol. 44, No. 6 GC/MS/MS , Determination of Low-level Pesticide Residues in Agricultural Products by Ion-trap GC/MS/MS Tomoko ICDJ: 1,,Saori S6H6@> 1,Seiji U8=>@6L6 1,Yoshichika H>G6=6G6 1, Yukihiro S=>DB> 1 and Yasuhide TDCD<6> 2 ( 1 Kobe Quarantine Station, Center for Inspection of Imported Foods and Infectious Diseases: 1 1, Toyahama-cho, Hyogo-ku, Kobe , Japan; 2 National Institute of Health Sciences, Osaka Branch: , Hoenzaka, Chuo-ku, Osaka , Japan; Corresponding author) The objective of this study was to elucidate the utility of ion-trap GC/MS/MS for the analysis of pesticides in extracted matrices from various agricultural products. Identification and quantitative analysis of pesticides in matrices were performed by quadrupole GC/MS and ion-trap GC/ MS/MS. Chlorpyrifos was added to the matrix of spinach, soybean in the pod or corn, and aldrin, dieldrin, endrin, a-bhc, b-bhc, g-bhc, d-bhc, p,p -DDD p,p -DDE, o,p -DDT and p,p -DDT were added to each matrix of green tea, black tea or oolong tea. Although most of the pesticides in the matrix could not be determined by quadrupole GC/MS-Scan analysis at 0.1 mg/ml, every pesticide was identified from the mass spectrum using ion-trap GC/MS/MS at the same concentration. The quantitation limit of every pesticide in each matrix by ion-trap GC/MS/MS analysis was higher than that by GC/MS-SIM analysis. The calibration curves obtained by GC/MS/MS were linear in the range of mg/ml of each pesticide. The recoveries of each pesticide from four kinds of samples spiked at the levels of 0.01 ppm to 0.02 ppm in extracts were with SD values in the range from 1.2 to This study revealed that ion-trap GC/MS/MS was useful for the identification and quantitative analysis of low-level pesticides residues in matrices of agricultural products. (Received July 18, 2003) Key words: GC/MS/MS ion-trap GC/MS/MS; matrix; agricultural product; pesticide residue; identification; quantitative analysis GC GC GC/MS Selected Ion Monitoring (SIM) 1) 4) SIM GC/MS SIM 5)

2 December 2003 GC/MS/MS 311 GC/MS/MS 6) GC/MS/MS (Tandem-in-space) 7) 12) (Tandem-in-time) 13), 14) GC/MS GC/MS/MS GC/MS GC/MS GC/MS/MS 1. a-bhc, b-bhc, g-bhc, d-bhc, p,p -DDD, p,p -DDE, o,p -DDT, p,p -DDT, 2. a-bhc, b-bhc, g-bhc, d-bhc, p,p -DDD, p,p -DDE, o,p -DDT, p,p -DDT, Riedel-de-Ha\n 1,000 mg/ ml a-bhc, b-bhc, g-bhc, d-bhc, p,p -DDD, p,p -DDE, o,p -DDT, p,p -DDT, 0.01, 0.025, 0.05, mg/ml 0.02, 0.05, 0.1, mg/ml 3. GC/MS Agilent Technologies HP6890 HP5973 GC/MS/MS Thermoquest Trace GC2000 PolarisQ GC/MS J&W Scientific DB-5 MS 30 m 0.25 mm i.d., 0.25 mm 80 (2 min) 10 /min 250 (10 min); 250 ; 280 ; 70 ev; 6.82 psi 2 ml 4.2 GC/MS/MS Restek Rtx-5 MS 30 m 0.25 mm i.d., 0.25 mm 85 (2 min) 4 /min 250 (5 min); 250 ; 280 ; 270 ; 0.8 ml/min 1 ml Table 1. GC/MS/MS Conditions for Determination of 12 Kinds of Pesticides Pesticide Precursor ion (m/z) Product ion (m/z) Excitation voltage (V) Maximum excitation energy (V) Chlorpyrifos a-bhc b-bhc g-bhc d-bhc Aldrin Dieldrin Endrin p,p -DDD o,p -DDT p,p -DDT p,p -DDE

3 312 Table ) BHC 16) a-bhc, b-bhc, g-bhc, d-bhc, p, p -DDD, p, p -DDE, o, p -DDT p,p -DDT 0.01 mg/ml 0.02 mg/ml 1. GC/MS/MS GC/MS GC/MS/MS 11 GC/MS GC/MS/MS 1.1 GC/MS/MS GC/MS GC/MS/MS GC/ MS 0.01, 0.05, 0.1, 1.0, mg/ml Table 2. Detection Limits of MS for 12 Kinds of Pesticides in Matrix of Spinach or Green Tea by GC/MS/MS-Scan and GC/MS-Scan Analysis Matrix Pesticide added Detection limit of each pesticide in matrix ( mg/ml) GC/MS/MS-Scan GC/MS-Scan Spinach Chlorpyrifos Green tea Vol. 44, No. 6 a-bhc b-bhc g-bhc d-bhc Aldrin Dieldrin Endrin p,p -DDD o,p -DDT p,p -DDT p,p -DDE Matrices were extracted from spinach and green tea by the standard method. Chlorpyrifos was added to the matrix of spinach (4 g/ml), and the concentration was adjusted to 0.01, 0.04, 0.2, 0.4 and 2.0 mg/ml. Aldrin, dieldrin, endrin, a-bhc, b-bhc, g-bhc, d-bhc, p,p -DDD, o,p -DDT, p,p -DDT and p,p -DDE were added to the matrix of green tea (2 g/ml), and the concentration was adjusted to 0.1, 0.2, 1.0, 2.0 and 5.0 mg/ml in each case. Each pesticide in the matrix was measured by GC/MS/MS-Scan and GC/MS-Scan analysis. Fig. 1. Mass chromatograms of chlorpyrifos and 11 kinds of organochlorine pesticide standards by GC/MS/MS and GC/ MS-(SIM) The concentration of each pesticide was 0.01 mg/ml, with the exception of endrin (0.02 mg/ml).

4 December 2003 GC/MS/MS 313 Fig. 2. E#ect of components of vegetable extracts on the determination of chlorpyrifos by GC/MS/MS and GC/MS-SIM Chlorpyrifos standard solution (0.1 mg/ml, 0.1 ml) was spiked into 0.9 ml of extract from spinach, soybeans in the pod and corn. Fig. 3. E#ect of components of green tea extract on the determination of 11 kinds of oganochlorine pesticides by GC/ MS/MS and GC/MS-SIM a-bhc, b-bhc, g-bhc, d-bhc, aldrin, dieldrin, endrin, o,p -DDT, p,p -DDT, p,p -DDD and p,p -DDE standard solution (0.1 mg/ml with the exception of endrin: 0.2 mg/ml, 0.1 ml) was spiked into 0.9 ml of green tea extract.

5 GC/MS/MS GC/MS Table 2 GC/MS p,p - DDE 0.1 mg/ml, 0.2 mg/ml, 2.0 mg/ml, o,p -DDT 5.0 mg/ml 1.0 mg/ml GC/MS/MS 1/10 1/500 GC/MS/MS GC/MS 1.2 GC/MS/MS GC/MS SIM GC/MS (SIM) GC/MS/MS Fig. 1 Fig. 2 GC/MS (SIM) GC/MS/MS GC/MS Fig. 3 SIM p,p -DDE a-bhc, b-bhc, g-bhc, d-bhc, p,p -DDD, p,p -DDT o,p -DDT GC/MS/MS Vol. 44, No. 6 GC/MS (SIM) GC/MS/MS GC/MS(SIM) GC/MS/ MS 2. GC/MS/MS GC/MS/MS ppm a-bhc, b-bhc, g-bhc, d-bhc, p,p -DDD, p,p -DDT, o,p -DDT p,p -DDE 0.01 mg/ml ppm 0.02 mg/ml 0.01 ppm GC/MS/MS Table 3. Recovery of 12 Kinds of Pesticides from Sample Extract by GC/MS/MS Pesticide Recovery ( ) Spinach Soybeans in the pod Corn Chlorpyrifos Black tea Oolong tea Green tea a-bhc b-bhc g-bhc d-bhc Aldrin Dieldrin Endrin p,p -DDD o,p -DDT p,p -DDT p,p -DDE Chlorpyrifos standard solution (0.1 mg/ml, 0.1 ml) was spiked with 0.9 ml of extract from spinach, soybeans in the pod and corn. a-bhc, b-bhc, g-bhc, d-bhc, aldrin, dieldrin, o,p -DDT, p,p -DDT, p,p -DDD or p,p -DDE standard solution (0.1 mg/ml with the exception of endrin: 0.2 mg/ml, 0.1 ml) was spiked into 0.9 ml of tea extract. Data are the mean S.D. of three samples.

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