Wheat
Olive Oil
Lemon Cucumber
New Validation Concept Two matrices (x2) Two replicates and one blank (x2+1) Two concentration Levels 0.01 and 0.1 mg/kg (x2) 10 samples per matrix Five matrices groups (x5) 50 samples in total for the validation in one laboratory Eight laboratories (x8) 400 samples for the complete validation
Parameter sr (repeatability s.d. matrix comprehensive) sR(reproducibility s.d. matrix comprehensive) Rec (recovery) Example 8.0 % 20.0 % 94.0 %
Grape Seed
Rape Seed
Pumpkin Seed
The uncertainties of the validation parameters were calculated using algorithms specifically provided by InterVal (following CD 2002/657/EC) and published in [3]. Rec [%] 99.1 100.1 89.6 72.8 81.7 90.0 87.8 64.6 95.7 82.3 94.8 93.1 89.2 72.5 92.0 53.8 95.3 92.6 44.9 88.0 94.5 92.0 95.8 75.1 73.5 65.9 97.8 89.4 98.0 96.2 91.1 77.9 91.3 86.6 80.6 81.8 91.3 74.4 53.6 26.0 21.6 94.9 75.0 80.0 93.7 78.1 100.6 90.9 97.2 85.7 sr [%] 11.9 10.6 14.0 12.2 13.8 9.18 11.0 11.1 11.5 13.4 8.9 11.9 11.7 15.7 11.3 14.6 9.2 12.8 19.3 11.8 10.7 14.2 10.8 13.7 18.5 19.6 12.4 11.8 10.3 12.4 9.6 11.4 10.9 13.5 12.0 9.3 9.4 10.5 15.3 > 20 > 20 11.6 10.5 10.5 10.8 13.7 14.0 10.5 11.5 10.4 MU [%] 26.2 23.7 30.9 34.6 30.4 46.7 24.9 26.9 25.5 29.5 20.8 26.5 26.2 35.4 25.1 34.8 21.3 28.1 46.9 26.3 25.5 30.5 24.0 30.8 39.8 46.1 27.1 27.6 23.2 27.0 21.8 26.3 24.5 29.7 27.2 22.1 21.9 25.0 36.0 > 50 > 50 25.6 24.8 24.5 24.5 30.8 30.0 23.7 25.4 23.9
Weight 2.0 g sample in a 50-mL centrifugal tube (with screw cap) Spike samples with pesticide mix and blanks with acetonitrile (ACN) Add 10 mL ACN Shake 15 min with shaker (first extraction)
Analyte Aldicarb Azoxystrobin Boscalide Carbendazim Chlorpyrifos-methyl Clofentezine Cyproconazole Cyprodinil Desmethylpirimicarb Difenoconazole Dimethomorph Epoxiconazole Ethoprophos Etofenprox Fenamidone Fenazaquin Fenbuconazole Fenoxycarb Fenpropimorph Fluquinconazole Flusilazole Flutriafole Fosthiazate Hexaconazole Hexythiazox Imazalil Indoxacarb Linuron Malathion Metalaxyl Myclobutanil Pendimethalin Phosalone Pirimiphos-methyl Prochloraz
Rank 195 333 374 324 209 167 308 415 212 358 229 366 296 171 163 178 270 201 200 282 430 304 218 299 175 359 266 319 191 266 414 181 173 199 277 274 176 174 210 210 174 260 191 315 256 196 256 255 165
RL [mg/kg] 0.02 0.02 0.02 0.02 0.02 0.025 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.04 0.02 0.02 0.02 0.02 0.02 0.02 0.05 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02 0.02
Centrifuge for 5 min at 3000 g Transfer 6 ml of the extract in a 12-mL centrifugal tube (with screw cap) Add 60 L of Internal Standard (e.g. TRIS) For Blanks 60 L ACN mix it Transfer extract in a centrifugal tube containing 150 mg PSA and 150 mg ODS C18 (shake briefly) Shake for 30 sec Centrifuge for 5 min at 3000 g Transfer 4 mL of extract in 12-mL centrifugal tube (with screw cap) add 40 L of 5% formic acid in ACN (10 L/mL extract) Fill in vials and spike extracts according to spiking scheme HPLC-MS/MS
The
Propiconazole Pyraclostrobin Pyriproxifen Quinoxyfen SpinosynA SpinosynD Tebufenozid Tebufenpyrad Terbuthylazin Tetraconazole Thiabendazole Thiamethoxam Triadimefon Trifloxystrobin Triticonazole
References
[1] METHOD VALIDATION AND QUALITY CONTROL PROCEDURES FOR PESTICIDE RESIDUES ANALYSIS IN FOOD AND FEED - Document N SANCO/2009/10684 [2] Anastassiades, M., et. al. Fast and Easy Multiresidue Method Employing Acetonitrile Extraction/ Partitioning and Dispersive Solid-Phase Extraction" for the determination of pesticide Residues in Produce. Journal of AOAC International 2003, 86 (2), 412-431. [3] Jlicher, B., Gowik, P. and Uhlig, S. A top-down in-house validation-based approach for the investigation of the measurement uncertainty using fractional factorial experiments. Analyst 1999, 124, 537-545.
1 Federal
Office of Consumer Protection and Food Safety (BVL) National Reference Laboratories for Pesticide Residues (NRL) P.O. Box 11 02 60 10832 Berlin Germany e-mail: NRL-Pestizide@bvl.bund.de 2 quo data - quality management and statistics GmbH Kaitzer Str. 135 01187 Dresden Germany