Analyse LC de multi-résidus de pesticides dans la farine de riz brun en 7.5 minutes
Application phare : Mélange de résidus de pesticides extrait de la farine de riz brun par extraction et purification QuEChERS
- Analyse de 7.5 minutes avec un cycle analytique total de moins de 10 minutes.
- Plus de 90% des 200 résidus analysés donnent des rendements compris entre 70 et 120 %.
- Méthode compatible avec les systèmes HPLC et UHPLC.
L’analyse multi-résidus de pesticides n’est pas chose aisée, et elle est rendue encore plus difficile par les matrices d’échantillons complexes et l’instrumentation LC-MS/MS couramment utilisées pour cette analyse. La LC-MS/MS peut fournir une sensibilité remarquable et elle peut même permettre des coélutions chromatographiques tout en pouvant quantifier les analytes d’intérêt. Mais trop de coélutions peuvent surcharger le spectromètre de masse et une bonne méthode chromatographique est donc essentielle. La méthode chromatographique optimisée décrite ici permet l’analyse de centaines de composés en moins de 7.5 minutes, garantissant un "screening" rapide et précis des échantillons et une productivité accrue du laboratoire.
Comme détaillé ci-dessous, un échantillon de farine de riz brun a été dopé avec tous les composés inclus dans le Kit LC multi-résidus de pesticides Restek, extrait à l’aide de sels d’extraction QuEChERS Q-sep, purifié par dSPE, et analysé sur une colonne Raptor ARC-18 2.7 µm. L’efficacité inhérente à une colonne faite de particules superficiellement poreuses de 2.7 µm offre des pics fins, ce qui permet d’analyser plus de composés dans une unité de temps donnée. La sélectivité de la phase stationnaire de la colonne Raptor ARC-18 garantit que les composés éluent sur toute la durée de l’analyse, ce qui évite de surcharger le chromatogramme à certains endroits et permet au spectromètre de masse de suivre plus efficacement les ions d’intérêt. Notez qu’il est important de réduire au minimum le volume interne du système donc utiliser des colonnes LC "narrow-bore" et éviter des longueurs de tubulures excessives aideront à obtenir des pics plus fins et une chromatographie plus rapide et plus efficace. Cette analyse multi-résidus de pesticides dans la farine de riz brun utilisent des phases mobiles simples et compatibles avec une analyse MS, et un débit maintenant la contre-pression dans la plage de travail des instruments HPLC conventionnels. Même dans une matrice aussi complexe, tous ces avantages permettent d’analyser plus de 200 pesticides et standards internes en quelques minutes.
| Peaks | tR (min) | Precursor Ion | Product Ion 1 | Product Ion 2 | |
|---|---|---|---|---|---|
| 1. | Cyromazine | 0.747 | 167.1 | 68.1 | 43.1 |
| 2. | Methamidophos | 1.318 | 142.0 | 94.0 | 125.1 |
| 3. | Formetanate | 1.681 | 222.1 | 165.0 | 46.1 |
| 4. | Carbofuran | 1.682 | 222.2 | 165.0 | 123.1 |
| 5. | Methabenzthiazuron | 1.686 | 222.0 | 165.0 | 150.0 |
| 6. | Acephate | 1.690 | 184.0 | 143.0 | 49.0 |
| 7. | Pymetrozine | 1.708 | 218.1 | 105.0 | 78.0 |
| 8. | Aminocarb | 1.716 | 209.1 | 137.1 | 152.1 |
| 9. | Propamocarb | 1.735 | 189.1 | 102.0 | 144.1 |
| 10. | Omethoate | 1.905 | 214.0 | 125.0 | 183.0 |
| 11. | Dinotefuran | 1.972 | 203.1 | 129.1 | 87.1 |
| 12. | Aldicarb sulfoxide | 2.010 | 207.1 | 89.0 | 132.1 |
| 13. | Butoxycarboxim | 2.022 | 223.0 | 106.0 | 166.0 |
| 14. | Nitenpyram | 2.049 | 271.0 | 225.0 | 56.0 |
| 15. | Aldicarb sulfone | 2.062 | 240.2 | 148.0 | 86.0 |
| 16. | Carbendazim | 2.090 | 192.0 | 160.0 | 131.9 |
| 17. | Oxamyl | 2.154 | 237.1 | 72.0 | 90.0 |
| 18. | Flonicamid | 2.234 | 230.1 | 203.0 | 148.0 |
| 19. | Methomyl | 2.259 | 163.1 | 88.0 | 106.1 |
| 20. | Thiabendazole | 2.284 | 201.8 | 92.2 | 104.0 |
| 21. | Thiamethoxam | 2.289 | 292.1 | 211.1 | 181.1 |
| 22. | Fuberidazole | 2.368 | 185.0 | 157.1 | 103.0 |
| 23. | Monocrotophos | 2.375 | 224.1 | 127.0 | 193.1 |
| 24. | Mexacarbate | 2.393 | 223.2 | 166.1 | 151.1 |
| 25. | Dioxacarb | 2.397 | 224.1 | 167.0 | 77.1 |
| 26. | Dicrotophos | 2.526 | 238.1 | 112.1 | 72.0 |
| 27. | Imidacloprid | 2.536 | 256.1 | 175.0 | 209.0 |
| 28. | Clothianidin | 2.545 | 250.0 | 169.0 | 113.0 |
| 29. | Dimethoate-d6 (IS) | 2.652 | 236.2 | 205.2 | 131.2 |
| 30. | Fenuron | 2.662 | 165.0 | 72.1 | 46.1 |
| 31. | Trichlorfon | 2.667 | 257.0 | 108.9 | 220.8 |
| 32. | Dimethoate | 2.668 | 230.0 | 199.0 | 125.0 |
| 33. | 3-Hydroxycarbofuran | 2.679 | 238.1 | 181.0 | 163.0 |
| 34. | Vamidothion | 2.695 | 288.0 | 146.0 | 118.0 |
| 35. | Mevinphos | 2.715 | 225.1 | 127.0 | 127.0 |
| 36. | Acetamiprid | 2.724 | 223.0 | 126.0 | 56.1 |
| 37. | Propoxur | 2.777 | 210.0 | 111.0 | 168.0 |
| 38. | Ethirimol | 2.780 | 210.2 | 140.2 | 98.2 |
| 39. | Cymoxanil | 2.805 | 199.1 | 128.2 | 111.2 |
| 40. | Thiacloprid | 2.865 | 253.0 | 126.0 | 99.0 |
| 41. | Pirimicarb | 2.896 | 239.2 | 72.0 | 182.1 |
| 42. | Aldicarb | 3.022 | 208.2 | 116.2 | 89.2 |
| 43. | Tricyclazole | 3.066 | 190.0 | 163.0 | 136.0 |
| 44. | Oxadixyl | 3.076 | 279.1 | 219.1 | 132.1 |
| 45. | Carbetamide | 3.085 | 237.1 | 192.0 | 118.1 |
| 46. | Simetryn | 3.122 | 214.1 | 68.0 | 96.0 |
| 47. | Thiophanate-methyl | 3.146 | 343.0 | 151.0 | 311.1 |
| 48. | Thidiazuron | 3.150 | 221.1 | 102.1 | 127.9 |
| 49. | Bendiocarb | 3.212 | 224.1 | 167.1 | 109.0 |
| 50. | Imazalil | 3.225 | 297.1 | 159.0 | 41.1 |
| 51. | Prometon | 3.227 | 226.1 | 142.1 | 184.0 |
| 52. | Metribuzin | 3.230 | 215.1 | 187.1 | 131.0 |
| 53. | Secbumeton | 3.232 | 226.2 | 170.2 | 100.2 |
| 54. | Terbumeton | 3.235 | 226.1 | 114.1 | 170.1 |
| 55. | Sulfentrazone* | 3.263 | 387.0 | 309.0 | 201.0 |
| 56. | Pyracarbolid | 3.279 | 218.1 | 125.1 | 97.0 |
| 57. | Tebuthiuron | 3.310 | 229.1 | 172.1 | 116.0 |
| 58. | Carbaryl | 3.316 | 202.1 | 145.0 | 127.0 |
| 59. | Carboxin | 3.326 | 236.1 | 143.0 | 87.1 |
| 60. | Monolinuron | 3.373 | 215.1 | 126.0 | 148.0 |
| 61. | Fluometuron | 3.381 | 233.1 | 72.1 | 46.1 |
| 62. | Diuron | 3.382 | 233.1 | 72.1 | 46.0 |
| 63. | Ethiofencarb | 3.406 | 226.0 | 107.0 | 164.0 |
| 64. | Ametryn | 3.447 | 228.1 | 68.1 | 186.1 |
| 65. | Chlorotoluron | 3.450 | 213.0 | 72.1 | 46.1 |
| 66. | Metobromuron | 3.483 | 259.0 | 170.0 | 148.1 |
| 67. | Propham | 3.500 | 180.1 | 120.2 | 77.1 |
| 68. | Flutriafol | 3.508 | 302.0 | 70.1 | 123.0 |
| 69. | Methoprotryne | 3.532 | 272.1 | 170.0 | 198.1 |
| 70. | Forchlorfenuron | 3.536 | 248.1 | 129.0 | 93.0 |
| 71. | Isoprocarb | 3.537 | 194.1 | 95.1 | 137.1 |
| 72. | Fenpropimorph | 3.561 | 304.2 | 147.1 | 117.0 |
| 73. | Atrazine-d5 (SS) | 3.575 | 221.2 | 179.2 | 101.3 |
| 74. | Isocarbophos | 3.606 | 291.1 | 231.1 | 121.1 |
| 75. | Isoproturon | 3.612 | 207.1 | 72.1 | 46.1 |
| 76. | Desmedipham | 3.620 | 318.0 | 154.1 | 301.0 |
| 77. | Phenmedipham | 3.623 | 318.1 | 108.1 | 93.1 |
| 78. | Spiroxamine | 3.626 | 298.2 | 144.2 | 58.2 |
| 79. | Pyrimethanil | 3.659 | 200.0 | 107.0 | 82.0 |
| 80. | Metalaxyl | 3.691 | 280.1 | 220.1 | 192.1 |
| 81. | Chlorantraniliprole | 3.730 | 484.0 | 452.8 | 285.8 |
| 82. | Cycluron | 3.785 | 199.1 | 89.1 | 46.0 |
| 83. | Prometryn | 3.830 | 242.1 | 158.0 | 200.2 |
| 84. | Linuron-d6 (SS) | 3.843 | 255.1 | 160.1 | 185.2 |
| 85. | Linuron | 3.854 | 249.0 | 160.0 | 182.0 |
| 86. | Thiofanox | 3.876 | 242.1 | 57.2 | 184.0 |
| 87. | Fenobucarb | 3.894 | 208.0 | 95.1 | 152.1 |
| 88. | Azoxystrobin | 3.915 | 404.2 | 329.0 | 344.0 |
| 89. | Diethofencarb | 3.924 | 268.1 | 226.1 | 124.0 |
| 90. | Ethofumesate | 3.925 | 304.1 | 121.1 | 241.0 |
| 91. | Ethiprole | 3.932 | 397.0 | 350.9 | 255.0 |
| 92. | Fludioxonil* | 3.935 | 247.1 | 180.1 | 126.1 |
| 93. | Methiocarb | 3.958 | 226.1 | 169.1 | 121.1 |
| 94. | Siduron | 3.967 | 233.3 | 94.0 | 137.1 |
| 95. | Halofenozide | 3.974 | 331.1 | 104.9 | 275.0 |
| 96. | Fenamidone | 3.993 | 312.0 | 92.1 | 236.1 |
| 97. | Furalaxyl | 3.995 | 302.1 | 242.1 | 95.0 |
| 98. | Acibenzolar-S-methyl | 4.023 | 210.9 | 136.1 | 91.1 |
| 99. | Nuarimol | 4.030 | 315.1 | 252.0 | 207.0 |
| 100. | Dimethomorph | 4.044 | 388.2 | 300.9 | 165.1 |
| 101. | Boscalid | 4.050 | 343.0 | 306.8 | 140.0 |
| 102. | Mandipropamid | 4.067 | 412.1 | 328.1 | 125.0 |
| 103. | Flutolanil | 4.079 | 324.1 | 262.0 | 242.0 |
| Peaks | tR (min) | Precursor Ion | Product Ion 1 | Product Ion 2 | |
|---|---|---|---|---|---|
| 104. | Promecarb | 4.104 | 208.1 | 109.0 | 151.0 |
| 105. | Paclobutrazol | 4.119 | 294.0 | 70.1 | 125.0 |
| 106. | Triadimenol | 4.119 | 296.1 | 70.1 | 43.1 |
| 107. | Mepronil | 4.161 | 270.1 | 91.1 | 119.0 |
| 108. | Cyproconazole | 4.175 | 292.2 | 70.1 | 125.0 |
| 109. | Myclobutanil | 4.195 | 289.2 | 70.1 | 125.1 |
| 110. | Chloroxuron | 4.225 | 291.1 | 72.1 | 46.1 |
| 111. | Bupirimate | 4.226 | 317.2 | 166.0 | 237.1 |
| 112. | Methoxyfenozide | 4.230 | 369.2 | 149.0 | 313.1 |
| 113. | Triadimefon | 4.287 | 294.0 | 69.0 | 197.0 |
| 114. | Bifenazate | 4.290 | 301.1 | 198.0 | 170.1 |
| 115. | Cyprodinil | 4.313 | 226.1 | 93.0 | 77.0 |
| 116. | Mefenacet | 4.325 | 299.1 | 148.1 | 120.1 |
| 117. | Mepanipyrim | 4.334 | 224.1 | 77.1 | 106.1 |
| 118. | Fluquinconazole | 4.346 | 376.0 | 348.9 | 307.0 |
| 119. | Fenhexamid | 4.383 | 302.1 | 97.1 | 55.1 |
| 120. | Fluoxastrobin | 4.385 | 459.2 | 427.0 | 188.1 |
| 121. | Tetraconazole | 4.387 | 372.0 | 159.0 | 70.0 |
| 122. | Bromuconazole isomer 1 | 4.392 | 376.0 | 159.0 | 159.0 |
| 123. | Butafenacil | 4.411 | 492.1 | 330.9 | 179.9 |
| 124. | Iprovalicarb | 4.412 | 321.2 | 119.0 | 91.1 |
| 125. | Flufenacet | 4.427 | 364.1 | 152.0 | 194.1 |
| 126. | Triticonazole | 4.429 | 318.0 | 70.0 | 125.0 |
| 127. | Cyazofamid | 4.441 | 325.1 | 108.0 | 44.0 |
| 128. | Diflubenzuron | 4.464 | 311.0 | 158.0 | 141.0 |
| 129. | Spirotetramat | 4.478 | 374.1 | 330.1 | 302.0 |
| 130. | Fenarimol | 4.510 | 331.0 | 267.9 | 189.1 |
| 131. | Fenbuconazole | 4.516 | 337.0 | 125.0 | 70.1 |
| 132. | Epoxiconazole | 4.529 | 330.0 | 121.1 | 101.0 |
| 133. | Etaconazole | 4.552 | 328.1 | 159.0 | 55.0 |
| 134. | Fipronil* | 4.571 | 436.9 | 332.0 | 252.0 |
| 135. | Neburon | 4.635 | 275.0 | 57.1 | 88.1 |
| 136. | Flusilazole | 4.646 | 316.1 | 247.1 | 165.1 |
| 137. | Fenoxycarb | 4.653 | 302.2 | 88.1 | 116.1 |
| 138. | Picoxystrobin | 4.674 | 368.0 | 145.0 | 205.0 |
| 139. | Rotenone | 4.683 | 395.1 | 213.1 | 192.1 |
| 140. | Tebufenozide | 4.719 | 353.2 | 133.1 | 105.0 |
| 141. | Dimoxystrobin | 4.738 | 327.1 | 205.1 | 116.1 |
| 142. | Bromuconazole isomer 2 | 4.740 | 378.0 | 159.0 | 159.0 |
| 143. | Flubendiamide | 4.745 | 700.0 | 408.0 | 274.0 |
| 144. | Diclobutrazol | 4.764 | 328.0 | 70.1 | 159.0 |
| 145. | Carfentrazone ethyl | 4.773 | 429.1 | 412.1 | 346.1 |
| 146. | Kresoxim-methyl | 4.795 | 314.0 | 267.1 | 116.0 |
| 147. | Tebuconazole | 4.827 | 308.0 | 70.1 | 124.9 |
| 148. | Spinosad A | 4.840 | 732.5 | 142.1 | 98.1 |
| 149. | Penconazole | 4.853 | 284.1 | 70.1 | 159.0 |
| 150. | Prothioconazole | 4.857 | 344.0 | 189.0 | 154.0 |
| 151. | Zoxamide | 4.893 | 336.1 | 187.0 | 159.0 |
| 152. | Famoxadone | 4.933 | 392.2 | 331.1 | 238.0 |
| 153. | Diazinon-diethyl-d10 (IS) | 4.961 | 315.2 | 170.2 | 154.3 |
| 154. | Hydramethylnon | 4.979 | 495.2 | 323.2 | 45.2 |
| 155. | Triflumuron | 4.986 | 359.1 | 156.0 | 111.0 |
| 156. | Prochloraz | 4.986 | 376.0 | 308.0 | 70.1 |
| 157. | Hexaconazole | 4.993 | 314.1 | 70.0 | 158.8 |
| 158. | Benalaxyl | 5.021 | 326.2 | 148.0 | 208.1 |
| 159. | Metconazole | 5.033 | 320.1 | 70.1 | 125.0 |
| 160. | Propiconazole | 5.054 | 342.0 | 159.0 | 69.0 |
| 161. | Pyraclostrobin | 5.076 | 388.0 | 194.0 | 163.1 |
| 162. | Clofentezine | 5.080 | 303.0 | 138.0 | 102.0 |
| 163. | Bitertanol | 5.120 | 338.2 | 269.2 | 70.1 |
| 164. | Spinosad D | 5.142 | 746.5 | 142.0 | 98.0 |
| 165. | Benzoximate | 5.171 | 364.0 | 199.1 | 105.0 |
| 166. | Diniconazole | 5.184 | 326.1 | 70.0 | 158.9 |
| 167. | Thiobencarb | 5.197 | 258.0 | 125.0 | 89.1 |
| 168. | Pencycuron | 5.229 | 329.1 | 125.0 | 89.0 |
| 169. | Spinetoram | 5.234 | 748.5 | 142.1 | 98.2 |
| 170. | Hexaflumuron* | 5.351 | 459.0 | 439.0 | 175.0 |
| 171. | Triflumizole | 5.366 | 346.1 | 278.0 | 73.1 |
| 172. | Indoxacarb | 5.375 | 528.1 | 149.9 | 203.0 |
| 173. | Difenoconazole | 5.380 | 406.1 | 251.1 | 152.0 |
| 174. | Ipconazole | 5.426 | 334.2 | 70.0 | 124.9 |
| 175. | Trifloxystrobin | 5.426 | 409.0 | 186.0 | 206.0 |
| 176. | Novaluron* | 5.455 | 491.0 | 471.0 | 304.9 |
| 177. | Emamectin-benzoate B1b | 5.463 | 872.2 | 158.2 | 82.1 |
| 178. | Clethodim | 5.565 | 360.1 | 164.1 | 268.1 |
| 179. | Teflubenzuron | 5.614 | 380.9 | 140.9 | 158.0 |
| 180. | Alanycarb | 5.636 | 400.1 | 91.0 | 238.0 |
| 181. | Buprofezin | 5.642 | 306.2 | 106.1 | 86.0 |
| 182. | Emamectin-benzoate B1a | 5.644 | 886.5 | 158.0 | 82.1 |
| 183. | Benfuracarb | 5.695 | 411.2 | 194.9 | 251.9 |
| 184. | Fluazinam* | 5.726 | 463.0 | 415.9 | 397.9 |
| 185. | Metaflumizone* | 5.728 | 505.1 | 302.1 | 328.0 |
| 186. | Furathiocarb | 5.735 | 383.1 | 195.0 | 252.1 |
| 187. | Temephos | 5.757 | 467.1 | 125.0 | 418.9 |
| 188. | Lufenuron | 5.767 | 511.2 | 141.0 | 158.0 |
| 189. | Tebufenpyrad | 5.778 | 334.0 | 117.0 | 145.0 |
| 190. | Pyriproxyfen | 5.843 | 322.0 | 96.0 | 227.1 |
| 191. | Piperonyl butoxide | 5.864 | 356.2 | 177.0 | 119.1 |
| 192. | Hexythiazox | 5.924 | 353.2 | 228.0 | 168.1 |
| 193. | Quinoxyfen | 5.935 | 308.1 | 197.0 | 162.0 |
| 194. | Flufenoxuron | 5.984 | 489.1 | 158.0 | 141.0 |
| 195. | Propargite | 6.088 | 368.1 | 231.1 | 175.0 |
| 196. | Etoxazole | 6.099 | 360.2 | 141.0 | 57.1 |
| 197. | Spiromesifen | 6.129 | 371.3 | 273.2 | 255.2 |
| 198. | Chlorfluazuron | 6.165 | 539.8 | 382.9 | 158.0 |
| 199. | Spirodiclofen | 6.269 | 428.3 | 71.1 | 313.1 |
| 200. | (E)-Fenpyroximate | 6.283 | 422.1 | 366.1 | 138.1 |
| 201. | Pyridaben | 6.442 | 365.2 | 147.0 | 309.1 |
| 202. | Eprinomectin | 6.466 | 914.6 | 186.1 | 154.1 |
| 203. | Abamectin B1a | 6.544 | 890.6 | 305.4 | 567.2 |
| 204. | Fenazaquin | 6.559 | 307.1 | 161.0 | 131.1 |
| 205. | Doramectin | 6.733 | 916.6 | 331.2 | 593.4 |
| 206. | Ivermectin | 6.893 | 892.6 | 551.4 | 569.4 |
*Detected in ESI- mode
| Column | Raptor ARC-18 (cat.# 9314A12) | ||||||||||||||||||||||||||||||||
|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|
| Dimensions: | 100 mm x 2.1 mm ID | ||||||||||||||||||||||||||||||||
| Particle Size: | 2.7 µm | ||||||||||||||||||||||||||||||||
| Pore Size: | 90 Å | ||||||||||||||||||||||||||||||||
| Guard Column: | Raptor ARC-18 EXP guard column cartridge 5 mm, 2.1 mm ID, 2.7 µm (cat.# 9314A0252) | ||||||||||||||||||||||||||||||||
| Temp.: | 50 °C | ||||||||||||||||||||||||||||||||
| Standard/Sample | LC multiresidue pesticide kit (cat.# 31971) | ||||||||||||||||||||||||||||||||
| Diluent: | Water:acetonitrile 9:1 | ||||||||||||||||||||||||||||||||
| Conc.: | 1 ng/mL see notes for details | ||||||||||||||||||||||||||||||||
| Inj. Vol.: | 5 µL | ||||||||||||||||||||||||||||||||
| Mobile Phase | |||||||||||||||||||||||||||||||||
| A: | 0.2% Formic acid, 2 mM ammonium formate in water | ||||||||||||||||||||||||||||||||
| B: | 0.2% Formic acid, 2 mM ammonium formate in methanol | ||||||||||||||||||||||||||||||||
|
| Detector | MS/MS |
|---|---|
| Ion Mode: | ESI+/ESI- |
| Mode: | Scheduled MRM |
| Instrument | UHPLC |
| Sample Preparation | Brown rice flour (10 g), purchased from a local market, was mixed with 10 mL water. After mixing for 10 min, the brown rice flour was fortified at 10 ng/g with all residues from the LC multiresidue pesticide kit (cat.# 31971), which had been previously combined into a single mixture that day. The fortified brown rice flour suspension was then mixed for 30 min to ensure uniform dispersion of the added pesticide residues in the brown rice flour suspension. Extraction was performed using 10 mL of acetonitrile and original unbuffered QuEChERS salts (cat.# 25848). After centrifugation, 1 mL supernatant was added to a 2 mL dSPE vial containing magnesium sulfate, PSA, and C18 (cat.# 26125) for cleanup. After centrifugation, 100 μL of the 10 ng/mL extract was diluted with 900 μL water and injected onto the UHPLC. |
| Notes | Although the ten LC multiresidue pesticides kit mixes are formulated to ensure maximum long-term stability and reliability as packaged, stability may become an issue when a large number of compounds with different chemical functionalities are combined together into a single mix. This should be taken into consideration for quantitative analysis. Want even better performance when analyzing metal-sensitive compounds? Check out Inert LC columns at www.restek.com/inert. |