High Sensitivity and Rugged Pesticide Residue Analysis in Food Samples by GC/MS Triple Quadrupole

EPRW June 2010

Dr. Finbarr ORegan Pesticide Control Service, Department of Agriculture, Fisheries and Food, Backweston Campus, Youngs Cross, Celbridge, Co. Kildare

Overview
Extraction Methods Compound optimisation Retention Time Locking Limits of Detection Linearity

Agilent 7000A Triple Quadrupole GC/MS

Fruit and veg. Extraction

Mini-Luke extraction Acetone , DCM, Petroleum Ether Sodium Sulphate GPC Clean-up (also run without GPC) Samples made up and run in Ethyl Acetate
methods for pesticide residues in foodstuffs" 6th Ed. Ministry of Health Welfare and Sport - The Netherlands

Based on standard multi-residue method published as "Analytical

Fat matrix Extraction

Acetone , Acetonitrile Celite clean-up GPC Clean-up Samples made up and run in Ethyl Acetate
Based on standard multi-residue method published as "Manual of Pesticide Analysis - Vol 1" DFG - Deutsche Forschungsgemeinschaft

Milk and Egg extraction

QuEChERS extraction Acetonitrile Sodium Acetate/Acetic Acid Buffer, Magnesium Sulphate and Sodium Chloride Samples made up and run in Ethyl Acetate
Based on standard multi-residue method published as J. AOAC Int. 88 615-

629 - Steven J. Lehotay, Katerina Mastrovska & Alam R. Lightfield

Optimisation

GC-QqQ Method Overview

200 compounds in two runs Retention Time Locking
Locked to pp-dde

Limits of Detection
10ppb for 178 compounds 20 - 50ppb for remaining 22 compounds

Linearity
R2 = 0.999 (captan and captafol can be problematic)

Internal Standard TPP

Quantitation Method

Calibration

Qualifier

Malathion LCL (10ppb)

Malathion Positive

Chlorpyriphos LCL (10ppb)

Chlorpyrifos Positive

EUPT FV11 Cauliflower Matrix z-scores

Mini Luke No GPC

EU Median

Mini Luke GC-MSD

No GPC GC-QqQ

azinphos-methyl 0.316 0.409 Boscalid buprofezin 0.347 0.495 0.477 0.681

0.355 0.414 0.638

-0.44 -0.65 -1.01

0.61 0.78 0.27

cadusofos
carbofuran

0.598 0.639
0.231 0.218

0.611
0.283

-0.09
-0.73

0.18
-0.92

EUPT FV11 Cauliflower Matrix z-scores

Mini Luke No GPC Mini Luke EU Median GC-MSD No GPC GC-QqQ

deltamethrin diazinon

0.144 0.162 1.120 1.550

0.157 1.250

-0.33 -0.42

0.13 0.96

isofenphos-methyl 0.411 0.570 l-cyhalothrin

metaxyl

0.540 0.266
0.450

-0.96 -0.80
0.61

0.22 -0.21
0.09

0.213 0.252
0.519 0.460

EUPT FV11 Cauliflower Matrix z-scores

Mini Luke No GPC Mini Luke EU Median GC-MSD No GPC GC-QqQ

methamidophos methidathion

0.416 0.446

0.387 0.528

0.405 0.472

0.11 -0.22

-0.18 0.47

monocrotophos sum parathionmethyl

phosalone

0.516
0.358 0.285

0.420
0.226 0.412

0.438
0.320 0.368

0.71
0.48 -0.90

-0.16
-1.18 0.48

EUPT FV11 Cauliflower Matrix z-scores

Mini Luke procymidone triazophos 0.676 0.450

No GPC 0.811 0.631

EU Median 0.780 0.538

Mini Luke -0.53 -0.65

No GPC 0.16 0.69

Thank you for your attention questions?