LC-MS Application Data Sheet No.

039
Analysis of Residual Pesticides in Farm Products using LC-MS
Residual Pesticides in farm products are strictly regulated
by the Food Sanitation Law. At present standards have
been set for 217 types of pesticides for approximately 130
types of farm products. Of these, pesticides that are subject
to thermal decomposition or highly volatile are analyzed
using LC. However, the high percentage of interfering
substances included in extracts from food products require
highly selective detectors. This is why LC-MS has been
attracting attention in this field.
Introduced here is an example of an LC-MS
simultaneous analysis of 20 components of residual
pesticides on a farm product. Fig.1 shows the mass
chromatogram in the scan mode. Highly sensitive analysis
is possible with the conditions set during auto-tuning,
eliminating the need of conditional optimization for each
pesticide. In addition, the multi-sequence mode enables
accurate qualification and quantitation of each component
by performing mass chromatography at the proper mass
number for each pesticide, whether it includes positive or
negative ions.

1
4
6
2 5 11
3
7 9
8 10
12
14
13
16 17
15 18 19
20
Fig. 1 Mass chromatograms of pesticides in foods
ESI-Positive mode
1. thiabendazole MW 201
2. methabenzthiazuron MW 221
3. furametpyr MW 333
4. imazalil MW 296
5. etobenzanid MW 339
6. dymron MW 268
7. tebufenozide MW 352
8. pyrazoxyfen MW 402
9. triflumizole MW 345
10. pencycuron MW 328
11. buprofezin MW 305
12. fenpyroximate MW 421
ESI-Negative mode
13. imibenconazole-debenzyl MW 270
14. inabenfide MW 338
15. myclobutanil MW 288
16. iprodione metabolite MW 329
17. diflubenzuron MW 310
18. hexaflumuron MW 460
19. flufenoxuron MW 488
20. chlorfluazuron MW 539
2.6 6.O 7.6 1O.O 12.6 16.O 17.6 2O.O m1n
26Oo8
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176Oo8
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2`486.9O|8.OO)
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2`8O8.9O|4.OO)
2`827.9O|4O.OO)
2`847.O6|8O.OO)
2`887.OO|4.OO)
2`268.9O|4.OO)
1`422.OO|11.86)
1`8O6.96|1.OO)
1`828.9O|2.46)
1`846.9O|2.69)
1`4O2.9O|1O.68)
1`868.O6|2.19)
1`268.96|1.OO)
1`889.9O|1.28)
1`296.86|1.OO)
1`888.96|7.24)
1`221.9O|2.44)
1`2O1.86|1.OO)
The SIM chromatograms and calibration curves (n=5) of
pencycuron and hexaflumuron are shown in Figs. 2 and 3
respectively. Tables 1 and 2 show the reproducibility for
these two components. As shown in this example,
components with similar of the same retention times, and
different measurement modes (positive and negative ions)
can be quantified at the same time.
Y = |6666.86188)X |4O84.O6828) r2=O.99982
Fig. 2 SIM chromatogram (12.5pg) and calibration curve (12.5-500pg) of pencycuron
Y = |1766.68898)X |192.42889) r2=O.99998
Fig. 3 SIM chromatogram (25pg) and calibration curve (25-1250pg) of hexaflumuron
Table 1 Reproducibility of pencycuron







Table 2 Reproducibility of hexaflumuron
1 2 8 4 6
11168 8984 9869 9766 9OO7 9768.8O 888.O74O1 9.O6 \
1869O 19229 2O478 1868O 17762 18946.8O 1OO1.644 6.29 \
42881 48726 4OOO1 4484O 48646 48O18.8O 1826.96O9 4.24 \
81842 8928O 9O686 8668O 91164 87868.4O 88O8.8O29 4.88 \
174911 1776OO 18OOO1 174126 172789 176886.2O 2894.6718 1.66 \
126Op 487OOO 487627 489882 484111 46O184 44176O.8O 1O6O2.686 2.88 \
* This data has been acquired with the cooperation of Dr. Kimihiko Yoshii and Dr. Yasuhide Tonogai from the Osaka branch
of the National Institute of Health Sciences. We hereby express our appreciation for their cooperation.
Table 3 Analytical conditions for LC-MS
Column : Shimadzu Shim-pack VP-ODS (2.0 mmI.D. x 150 mm)
Mobile phase A : water Mobile phase B : acetonitrile
Gradient program : 20%B - 60%B(0.03min) - 80%B(20min) - 100%B(20.01-30min) - 20%B(30.01-40min)
Flow rate : 0.2 mL/min
Injection volume : 5 uL Column temperature : 40 degree C
Probe voltage : +4.5 kV (ESI-Positive mode), -3.0 kV (ESI-Negative mode)
CDL temperature : 200 degree C Block Heater temperature : 200 degree C
Nebulizing gas flow : 4.5 L/min
CDL voltage : +0 V (ESI-Positive mode), +0 V (ESI-Negative mode)
Q-array DC voltage : scan mode Q-array RF : scan mode
Scan range : m/z 50 - 650 (1.5 sec/scan)
SHIMADZU CORPORATION International Marketing Division
3. Kanda-Nishikicho 1-chome, Chiyoda-ku, Tokyo 101-8448, Japan
Phone: 81 (3) 3219-5641 Fax. 81 (3) 3219-5710
Cable Add. SHIMADZU TOKYO
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Exact Mass: 328.13
Mol. Wt.: 328.84
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Exact Mass: 459.98
Mol. Wt.: 461.14