bozena lozowicka*, ewa rutkowska, izabela hrynko ... · supplement: determination of pesticides in...
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Open Chem., 2015; 13: S40–S51
Research Article Open Access
Bozena Lozowicka*, Ewa Rutkowska, Izabela Hrynko
Supplement: Simultaneous determination of 223 pesticides in tobacco by GC with simultaneous electron capture and nitrogen-phosphorous detection and mass spectrometric confirmation
*Corresponding author: Bozena Lozowicka: Plant Protection Institute - National Research Institute, Regional Experimental Station, Laboratory of Pesticide Residues, Chelmonskiego 22, Postal code: 15-195 Bialystok, Poland, E-mail: [email protected] Ewa Rutkowska, Izabela Hrynko: Plant Protection Institute - National Research Institute, Regional Experimental Station, Laboratory of Pesticide Residues, Chelmonskiego 22, Postal code: 15-195 Bialystok, Poland
© 2015 Bozena Lozowicka, Ewa Rutkowska, Izabela Hrynko, licensee De Gruyter Open.This work is licensed under the Creative Commons Attribution-NonCommercial-NoDerivs 3.0 License.
Suppementary Table 1: Validation parameters and matrix effect of LSE method in tobacco studied by GC-µECD/NPD. Negative values of matrix effects mean suppression of the signal and positives values enhancement.
Active substance (Pesticide type)
Substance group EC NP Spiking level (mg/kg)
Mean recovery ± RSD(%)
Matrix effect (%)
LOQ(mg/kg)
LOD (mg/kg)
LSE
1. Napropamide (H) Alkanamide + 0.05 97 ± 4 1 0.01 0.003
2. Cyflufenamid (F) Amide + 0.01 78 ± 9 30 0.01 0.003
3. Amitraz (I) Amidine + 0.01 n.d. -32 0.01 0.003
4. Cyprodinil (F) Anilinopyrimidine + 0.01 82 ± 7 11 0.009 0.003
5. Mepanipirym (F) + 0.01 65 ± 5 7 0.01 0.003
6. Pyrimethanil (F) + 0.01 85 ± 10 5 0.01 0.003
7. Chlorantraniliprole1 (I) Anthranilic diamide ++ + 0.01 86 ± 15 -98 0.01 0.003
8. Fenoxaprop-p-ethyl (H) Aryloxyphenoxypropionate + ++ 0.05 92 ± 3 38 0.03 0.009
9. Fluazifop-p-butyl1 (H) + 0.01 87 ± 6 42 0.03 0.009
10. Propaquizafop (H) ++ + 0.05 69 ± 13 -71 0.03 0.009
11. Quizalofop-p-ethyl (H) ++ + 0.01 68 ± 6 2 0.01 0.003
12. Fluopicolide (F) Benzamide + 0.01 83 ± 13 13 0.01 0.003
13. Propyzamide (H) ++ + 0.01 97 ± 7 36 0.01 0.003
14. Bromopropylate (A) Benzilate + 0.01 96 ± 13 65 0.01 0.003
15. Fuberidazole (F) Benzimidazole + 0.01 n.d. 1 - -
16. Thiabendazole (I) + 0.01 n.d. 23 - -
17. Dichlobenil (H) Benzonitrile ++ + 0.01 45 ± 5 8 0.01 0.003
18. Metrafenone (F) Benzophenone + 0.01 44 ± 4 16 0.01 0.003
Supplement: Determination of pesticides in tobacco and nitrogen-phosphorous detection by MS S41
Active substance (Pesticide type)
Substance group EC NP Spiking level (mg/kg)
Mean recovery ± RSD(%)
Matrix effect (%)
LOQ(mg/kg)
LOD (mg/kg)
LSE
19. Teflubenzuron (I) Benzoylurea + 0.05 69 ± 9 171 0.02 0.006
20. Tetradifon (I) Bridged diphenyl + 0.01 83 ± 5 8 0.01 0.003
21. Carbaryl1 (I) Carbamate + 0.01 102 ± 7 248 0.02 0.006
22. Carbofuran1 (I) + 0.01 75 ± 5 207 0.02 0.006
23. Carbosulfan (I) + 0.01 n.d. -60 - -
24. Chlorpropham (H) + 0.05 84 ± 10 -52 0.01 0.003
25. Fenoxycarb (I) + 0.01 58 ± 9 105 0.01 0.003
26. Iprowalikarb (F) + 0.05 84 ± 6 80 0.01 0.003
27. Isoprocarb (I) + 0.01 69 ± 6 -77 0.01 0.003
28. Pirimicarb1.2 (I) + 0.01 78 ± 3 -1 0.01 0.003
29. Pirimicarb desmethyl (I) + 0.01 80 ± 7 8 0.01 0.003
30. Propham (H) + 0.05 77 ± 7 16 0.02 0.006
31. Propoxur1 (I) + 0.01 91 ± 10 -8 0.02 0.006
32. Boscalid (F) Carboxamide ++ + 0.01 72 ± 6 0.3 0.01 0.003
33. Diflufenican (DFF) (H) + 0.01 89 ± 10 75 0.01 0.003
34. Hexythiazox (A) ++ + 0.05 89 ± 8 -50 0.04 0.012
35. Acetochlor (H) Chloroacetamide ++ + 0.01 80 ± 10 1 0.01 0.003
36. Dimethenamid (H) ++ + 0.05 80 ± 11 87 0.02 0.006
37. Metazachlor (H) ++ + 0.01 97 ± 15 11 0.01 0.003
38. Metolachlor (H) ++ + 0.05 79 ± 6 5 0.02 0.006
39. Propachlor (H) ++ + 0.05 82 ± 10 21 0.02 0.006
40. Chlorothalonil1 (F) Chlorine-substituted aromatics
+ 0.01 91 ± 11 70 0.01 0.003
41. Dicloran1 (F) + 0.01 77 ± 3 -0.2 0.01 0.003
42. HCB (Hexachlorobenzene)1 (F)
+ 0.01 69 ± 3 -10 0.005 0.001
43. Quintozene (PCNB) (F) + 0.01 99 ± 6 3 0.01 0.003
44. Tecnazene (TCNB) (F) + 0.01 67 ± 6 4 0.009 0.003
45. Tolclofos methyl (F) + ++ 0.01 84 ± 5 21 0.01 0.003
46. Cymoxanil1 (F) Cyanoacetamide oxime + 0.05 49 ± 7 33 0.04 0.012
47. Iprodione1 (F) Dicarboximide + 0.05 92 ± 7 1870 0.02 0.006
48. Procymidone (F) ++ + 0.01 85 ± 8 12 0.01 0.003
49. Pendimethalin1 (H) Dinitroaniline ++ + 0.01 89 ± 14 8 0.01 0.003
50. Trifluralin1 (H) ++ + 0.01 97 ± 6 2 0.01 0.003
51. Nitrofen1 (H) Diphenyl ether + 0.01 78 ± 8 -17 0.009 0.003
52. Oxyflurofen (H) + 0.01 89 ± 8 22 0.009 0.003
53. Fenhexamid (F) Hydroxyanilide + 0.05 78 ± 12 -103 0.02 0.006
54. Fenamidon (F) Imidazole ++ + 0.01 103 ± 8 7 0.01 0.003
55. Imazalil (F) ++ + 0.01 41 ± 10 72 0.02 0.006
56. Prochloraz (F) ++ + 0.01 88 ± 9 -40 0.01 0.003
57. Triflumizole (F) ++ + 0.01 85 ± 11 27 0.02 0.006
58. Isoxaflutole (H) Isoxazole ++ + 0.05 74 ± 5 61 0.02 0.006
ContinuedSuppementary Table 1: Validation parameters and matrix effect of LSE method in tobacco studied by GC-µECD/NPD. Negative values of matrix effects mean suppression of the signal and positives values enhancement.
S42 Bozena Lozowicka, Ewa Rutkowska, Izabela Hrynko
Active substance (Pesticide type)
Substance group EC NP Spiking level (mg/kg)
Mean recovery ± RSD(%)
Matrix effect (%)
LOQ(mg/kg)
LOD (mg/kg)
LSE
59. Clomazone1.2 (H) Isoxazolidinone + 0.01 88 ± 10 5 0.01 0.003
60. Dimethomorph1 (F) Morpholine + 0.05 86 ± 3 -87 0.03 0.009
61. Fenpropimorph (F) + 0.05 43 ± 7 5 0.02 0.006
62. Acetamiprid1 (I) Neonicotinoid + 0.01 124 ± 4 20 0.01 0.003
63. Thiacloprid (I) ++ + 0.01 n.d. 16 - -
64. Thiametoxam1 (I) ++ + 0.01 52 ± 14 16 0.02 0.006
65. Aldrine1 (I) Organochlorine + 0.01 77 ± 12 -17 0.005 0.001
66. Alpha endosulfan1 (I) + 0.01 76 ± 3 -91 0.008 0.002
67. Alpha HCH1 (I) + 0.01 72 ± 8 -13 0.005 0.001
68. Beta endosulfan1 (I) + 0.01 84 ± 5 -2 0.008 0.002
69. Beta HCH1 (I) + 0.01 75 ± 4 -30 0.005 0.001
70. Dicofol (A) + 0.01 75 ± 4 9 0.01 0.003
71. Dieldrin1 (I) + 0.01 100 ± 7 -24 0.005 0.001
72. Sulfate endosulfan1 (I) Organochlorine + 0.01 78 ± 6 29 0.008 0.002
73. Endrin1 (I) + 0.01 94 ± 3 3364 0.005 0.001
74. Heptachlor1 (I) + 0.01 69 ± 7 -20 0.005 0.001
75. Heptachlor epoxide1 (I) + 0.01 77 ± 5 -27 0.005 0.001
76. Methoxychlor (DMDT)1 (I) + 0.01 92 ± 8 2162 0.01 0.003
77. o.p’-DDT1 (I) + 0.01 89 ± 6 -19 0.005 0.001
78. p.p’-DDD1 (I) + 0.01 85 ± 11 -19 0.005 0.001
79. p.p’-DDE1 (I) + 0.01 97 ± 5 -29 0.005 0.001
80. p.p’-DDT1 (I) + 0.01 97 ± 2 3186 0.005 0.001
81. Azinphos ethyl1 (I) Organophosphate + ++ 0.01 84 ± 6 3 0.01 0.003
82. Azinphos methyl1 (I) + ++ 0.01 95 ± 4 54 0.01 0.003
83. Chlorfenvinphos1 (I) + ++ 0.01 83 ± 7 0.1 0.008 0.002
84. Bromofos ethyl1 (I) + ++ 0.01 76 ± 4 5 0.009 0.003
85. Bromofos methyl (I) + ++ 0.01 76 ± 3 2 0.009 0.003
86. Cadusafos (I) + 0.01 67 ± 3 28 0.008 0.002
87. Chlorpyrifos1 (I) ++ + 0.01 81 ± 5 8 0.006 0.002
88. Chlorpyrifos methyl1 (I) ++ + 0.01 81 ± 8 8 0.006 0.002
89. Coumphos (I) + ++ 0.05 84 ± 6 86 0.03 0.009
90. Diazinon1 (I) + 0.01 83 ± 3 45 0.01 0.003
91. Dichlorvos1 (I) ++ + 0.01 76 ± 16 61 0.01 0.003
92. Dicrotophos (I) + 0.01 48 ± 5 211 0.01 0.003
93. Dimethoate1 (I) + ++ 0.01 88 ± 3 38 0.01 0.003
94. EPN (I) + ++ 0.01 73 ± 8 5 0.009 0.003
95. Ethion (I) + ++ 0.01 96 ± 7 59 0.01 0.003
96. Ethoprophos1 (I) + 0.01 83 ± 4 32 0.01 0.003
97. Fenchlorfos1 (I) + ++ 0.01 81 ± 9 3 0.01 0.003
98. Fenitrothion1 (I) + ++ 0.01 77 ± 6 5 0.01 0.003
ContinuedSuppementary Table 1: Validation parameters and matrix effect of LSE method in tobacco studied by GC-µECD/NPD. Negative values of matrix effects mean suppression of the signal and positives values enhancement.
Supplement: Determination of pesticides in tobacco and nitrogen-phosphorous detection by MS S43
Active substance (Pesticide type)
Substance group EC NP Spiking level (mg/kg)
Mean recovery ± RSD(%)
Matrix effect (%)
LOQ(mg/kg)
LOD (mg/kg)
LSE
99. Fention1 (I) Organophosphate + 0.01 68 ± 8 21 0.01 0.003
100. Formothion1 (I) ++ + 0.01 88 ± 3 3 0.01 0.003
101. Fostiazate (I) + 0.01 63 ± 8 77 0.01 0.003
102. Heptenophos (I) Organophosphate + 0.01 85 ± 4 55 0.01 0.003
103. Isocarbophos (A) + 0.01 68 ± 9 89 0.01 0.003
104. Isofenphos (I) + 0.01 89 ± 10 57 0.01 0.003
105. Isofenfos methyl (I) + 0.01 86 ± 9 35 0.01 0.003
106. Malaoxon (I) + 0.01 84 ± 14 37 0.01 0.003
107. Malathion1 (I) + 0.01 93 ± 13 66 0.01 0.003
108. Mecarbam (I) ++ + 0.01 92 ± 8 10 0.01 0.003
109. Methacrifos (F) + ++ 0.01 67 ± 4 28 0.01 0.003
110. Methidathion1 (I) + ++ 0.01 85 ± 3 7 0.01 0.003
111. Mevinphos (I) + 0.01 80 ± 14 33 0.01 0.003
112. Paraoxon ethyl (I) + ++ 0.01 72 ± 11 -4 0.01 0.003
113. Paraoxon methyl (I) + ++ 0.01 72 ± 12 67 0.01 0.003
114. Parathion ethyl1 (I) + ++ 0.01 81 ± 4 6 0.01 0.003
115. Parathion methyl1 (I) + ++ 0.01 81 ± 5 2 0.01 0.003
116. Phentoate (I) + ++ 0.01 78 ± 9 2 0.01 0.003
117. Phorate1 (I) + 0.01 67 ± 10 46 0.01 0.003
118. Phosalone1 (I) + ++ 0.01 88 ± 6 16 0.01 0.003
119. Phosmet (I) + ++ 0.01 93 ± 4 98 0.01 0.003
120. Pirimiphos ethyl (I) + 0.01 83 ± 4 47 0.009 0.003
121. Pirimiphos methyl1 (I) + 0.01 86 ± 15 46 0.009 0.003
122. Profenofos1 (I) + ++ 0.01 91 ± 5 42 0.01 0.003
123. Quinalphos (I) + ++ 0.01 90 ± 10 31 0.008 0.002
124. Tetrachlorwinfos1 (I) ++ + 0.01 93 ± 7 94 0.01 0.003
125. Triazophos (I) + 0.01 94 ± 7 52 0.01 0.003
126. Indoxacarb1 (I) Oxadiazine + 0.01 82 ± 4 -79 0.01 0.003
127. Flutolanil (F) Oxathin ++ + 0.05 108 ± 9 154 0.03 0.009
128. Famoksadone1 (F) Oxazole ++ + 0.05 53 ± 5 79 0.01 0.003
129. Vinclozolin (F) + 0.01 86 ± 6 9 0.01 0.003
130. Chlozolinate (F) Oxazolidin + 0.01 74 ± 4 -7 0.01 0.003
131. Flufenacet (H) Oxyacetamide + 0.01 78 ± 9 1 0.01 0.003
132. Benalaxyl1 (F) Phenylamide + 0.01 83 ± 13 26 0.01 0.003
133. Metalaxyl1.2 (F) + 0.01 84 ± 5 127 0.01 0.003
134. Oksadixyl1 (F) + 0.01 68 ± 8 14 0.01 0.003
135. Fipronil (I) Phenylpyrazole + 0.01 93 ± 14 184 0.009 0.003
136. Fluazinam (F) Phenylpyridinamine + 0.01 107 ± 5 -21 0.01 0.003
137. Fludioxonil (F) Phenylpyrole + 0.01 76 ± 4 -24 0.01 0.003
138. Pencycuron (F) Phenylurea + 0.05 54 ± 5 -76 0.02 0.006
139. Isoprothiolane (F) Phosphorothiolate + 0.01 89 ± 7 51 0.01 0.003
140. Pyrazofos (I) + ++ 0.01 92 ± 10 38 0.01 0.003
ContinuedSuppementary Table 1: Validation parameters and matrix effect of LSE method in tobacco studied by GC-µECD/NPD. Negative values of matrix effects mean suppression of the signal and positives values enhancement.
S44 Bozena Lozowicka, Ewa Rutkowska, Izabela Hrynko
Active substance (Pesticide type)
Substance group EC NP Spiking level (mg/kg)
Mean recovery ± RSD(%)
Matrix effect (%)
LOQ(mg/kg)
LOD (mg/kg)
LSE
141. Captafol (F) Phthalimide + 0.01 107 ± 8 928 0.01 0.003
142. Captan1 (F) + 0.01 84 ± 4 1535 0.01 0.003
143. Folpet1 (F) + 0.01 43 ± 3 71 0.01 0.003
144. Tebufenpyrad (A) Pyrazole + 0.01 70 ± 14 -42 0.01 0.003
145. Acrinathrin (I) Pyrethroid + 0.01 100 ± 7 454 0.01 0.003
146. Bifenthrin1 (I) + 0.01 86 ± 4 27 0.01 0.003
147. Cyfluthrin1 (I) + 0.05 86 ± 8 36 0.02 0.006
148. Cypermethrin1.2 (I) + 0.05 79 ± 11 -69 0.01 0.003
149. Deltamethrin1 (I) + 0.05 97 ± 5 4 0.01 0.003
150. Esfenvalerate1 (I) + 0.01 76 ± 5 55 0.01 0.003
151. Fenpropathrin (I) + 0.01 84 ± 7 13 0.01 0.003
152. Fenvalerate1 (I) + 0.01 70 ± 3 -75 0.01 0.003
153. Gamma HCH (Lindane)1 (I) + 0.01 85 ± 11 -9 0.005 0.002
154. Lambda cyhalothrin1 (I) + 0.01 83 ± 5 10 0.01 0.003
155. Permethrin1 (I) + 0.05 99 ± 4 18 0.04 0.012
156. Pyrethrin1 (I) + 0.05 105 ± 4 35 0.04 0.012
157. Tau-Fluvalinate (I) + 0.01 75 ± 17 458 0.01 0.003
158. Tefluthrin1 (I) + 0.01 70 ± 1 21 0.009 0.003
159. Tetramethrin (I) + 0.05 101 ± 5 326 0.03 0.009
160. Zoxamide (F) + 0.01 84 ± 3 -79 0.009 0.003
161. Chloridazon (H) Pyridazinone ++ + 0.01 88 ± 4 -20 0.009 0.003
162. Flurtamone (H) + ++ 0.01 84 ± 5 -15 0.01 0.003
163. Pyridaben (A) ++ + 0.05 86 ± 10 28 0.02 0.006
164. Flonicamid (I) Pyridine ++ + 0.01 n.d. -1 - -
165. Fenarimol (F) Pyrimidine ++ + 0.01 78 ± 7 4 0.01 0.003
166. Bupirimate (F) Pyrimidinol ++ + 0.01 90 ± 4 6 0.01 0.003
167. Quinoxyfen (F) Quinoline ++ + 0.01 106 ± 4 61 0.009 0.003
168. Azoxystrobin (F) Strobilurin ++ + 0.01 69 ± 7 -76 0.01 0.003
169. Dimoksystrobina (F) ++ + 0.01 85 ± 5 44 0.01 0.003
170. Fluoxastrobin (F) ++ + 0.01 69 ± 14 229 0.01 0.003
171. Kresoxim methyl (F) ++ + 0.01 80 ± 9 14 0.01 0.003
172. Picoxystrobin (F) ++ + 0.05 76 ± 7 -3 0.04 0.012
173. Pyraklostrobina (F) ++ + 0.05 113 ± 4 46 0.05 0.015
174. Trifloxystrobin (F) ++ + 0.01 91 ± 5 21 0.01 0.003
175. Propargite (A) Sulfite ester + 0.05 55 ± 19 325 0.05 0.015
176. Tritosulfuron (H) Sulfonylurea + 0.01 42 ± 15 95 0.01 0.003
177. Dichlofluanid (F) Sulphamide ++ + 0.01 63 ± 1 8 0.01 0.003
178. Tolylfluanid (F) ++ + 0.01 64 ± 3 21 0.01 0.003
179. Spirodiclofen (A) Tetronic acid + 0.01 83 ± 6 -44 0.01 0.003
ContinuedSuppementary Table 1: Validation parameters and matrix effect of LSE method in tobacco studied by GC-µECD/NPD. Negative values of matrix effects mean suppression of the signal and positives values enhancement.
Supplement: Determination of pesticides in tobacco and nitrogen-phosphorous detection by MS S45
Active substance (Pesticide type)
Substance group EC NP Spiking level (mg/kg)
Mean recovery ± RSD(%)
Matrix effect (%)
LOQ(mg/kg)
LOD (mg/kg)
LSE
180. Atrazine (H) Triazine + 0.01 67 ± 11 15 0.01 0.003
181. Cyanazine (H) + ++ 0.01 n.d. 21 - -
182. Cyprazine (H) + 0.01 57 ± 6 14 0.01 0.003
183. Procyazine (H) + ++ 0.01 60 ± 5 -51 0.01 0.003
184. Prometrine (H) + 0.01 75 ± 12 4 0.01 0.003
185. Propazine (H) + 0.01 62 ± 4 9 0.01 0.003
186. Simazine (H) + 0.01 71 ± 5 5 0.01 0.003
187. Terbuthylazine (H) + 0.01 75 ± 8 6 0.009 0.003
188. Terbutryn (H) + 0.01 56 ± 8 3 0.009 0.003
189. Metamitron (H) Triazinone + 0.01 108 ± 6 27 0.01 0.003
190. Metribuzin (H) ++ + 0.01 81 ± 7 3 0.009 0.003
191. Azaconazole (F) Triazole ++ + 0.01 83 ± 7 41 0.01 0.003
192. Bitertanol (F) + 0.05 67 ± 4 8 0.02 0.006
193. Bromuconazole (F) ++ + 0.01 95 ± 6 62 0.01 0.003
194. Cyproconazole (F) + 0.01 59 ± 5 -33 0.01 0.003
195. Difenoconazole (F) ++ + 0.05 59 ± 3 -19 0.01 0.003
196. Dinikonazol (F) ++ + 0.01 81 ± 8 32 0.009 0.003
197. Epoxiconazole (F) ++ + 0.01 92 ± 7 29 0.009 0.003
198. Etaconazole (F) ++ + 0.01 90 ± 9 -15 0.01 0.003
199. Fenbuconazole (F) + 0.01 70 ± 3 -10 0.01 0.003
200. Fluquinconazole (F) ++ + 0.01 79 ± 15 1 0.01 0.003
201. Flusilazole (F) + 0.01 92 ± 11 24 0.009 0.003
202. Flutriafol (F) + 0.05 85 ± 4 23 0.02 0.006
203. Hexaconazole (F) ++ + 0.01 105 ± 5 24 0.009 0.003
204. Imibenkonazol (F) + 0.01 69 ± 3 -28 0.01 0.003
205. Metkonazol (F) + 0.05 89 ± 10 29 0.02 0.006
206. Myclobutanyl (F) ++ + 0.01 82 ± 5 13 0.01 0.003
207. Paclobutrazol (F) + 0.01 70 ± 8 -42 0.01 0.003
208. Penconazole1 (F) ++ + 0.01 92 ± 14 15 0.009 0.003
209. Propiconazole (F) ++ + 0.01 90 ± 6 14 0.01 0.003
210. Prothioconazole (F) ++ + 0.01 61 ± 17 11 0.01 0.003
211. Tebuconazole (F) + 0.01 86 ± 7 2 0.01 0.003
212. Tetraconazole (F) ++ + 0.01 74 ± 6 10 0.01 0.003
213. Triadimefon (F) ++ + 0.01 90 ± 8 6 0.01 0.003
214. Triadimenol (F) + 0.05 77 ± 4 8 0.03 0.009
215. Triticonazole (F) ++ + 0.01 54 ± 3 -3 0.01 0.003
216. Buprofezin (I) Unclassified + 0.01 100 ± 5 22 0.01 0.003
217. DEET N.N-dietylo-m-toluamid (I)
+ 0.05 54 ± 3 197 0.03 0.009
218. Difenyloamina (F) + 0.01 81 ± 5 -9 0.01 0.003
219. Fenazaquin (I) + 0.01 90 ± 9 9 0.01 0.003
ContinuedSuppementary Table 1: Validation parameters and matrix effect of LSE method in tobacco studied by GC-µECD/NPD. Negative values of matrix effects mean suppression of the signal and positives values enhancement.
S46 Bozena Lozowicka, Ewa Rutkowska, Izabela Hrynko
Active substance (Pesticide type)
Substance group EC NP Spiking level (mg/kg)
Mean recovery ± RSD(%)
Matrix effect (%)
LOQ(mg/kg)
LOD (mg/kg)
LSE
220. Flurochloridone (H) Unclassified + 0.01 84 ± 8 11 0.009 0.003
221. Pyriproxyfen (I) + 0.05 78 ± 11 29 0.02 0.006
222. Quinoclamine (H) + 0.01 81 ± 2 72 0.01 0.003
223. Lenacil (H) Uracil + 0.05 75 ± 4 2819 0.02 0.006
*LOQ - Limit of quantification**LOD - Limit of detection1 List of the pesticides employed for tobacco (CORESTA)2 Pesticides recommended for tobacco cultivation++ Preferred GC detectorn.d. not detected
ContinuedSuppementary Table 1: Validation parameters and matrix effect of LSE method in tobacco studied by GC-µECD/NPD. Negative values of matrix effects mean suppression of the signal and positives values enhancement.
Supplementary Table 2: Validation parameters and matrix effect of MSPD and QuEChERS methods in tobacco studied by GC-µECD/NPD. Negative values of matrix effects mean suppression of the signal and positives values enhancement.
Active substance (Pesticide type)
Spiking level (mg/kg)
Mean recovery ± RSD(%)
Matrix effect (%)
LOQ(mg/kg)
LOD (mg/kg)
Mean recovery ± RSD(%)
Matrix effect (%)
LOQ(mg/kg)
LOD (mg/kg)
MSPD QuEChERS
1. Napropamide (H) 0.05 85 ± 11 12 0.01 0.003 88 ± 6 8 0.01 0.003
2. Cyflufenamid (F) 0.01 81 ± 9 20 0.01 0.003 117 ± 3 10 0.01 0.003
3. Amitraz (I) 0.01 41 ± 5 -35 0.01 0.003 41 ± 9 -26 0.01 0.003
4. Cyprodinil (F) 0.01 94 ± 9 23 0.009 0.003 86 ± 8 7 0.008 0.002
5. Mepanipirym (F) 0.01 85 ± 6 16 0.01 0.003 86 ± 6 7 0.01 0.003
6. Pyrimethanil (F) 0.01 85 ± 4 11 0.01 0.003 81 ± 6 4 0.008 0.002
7. Chlorantraniliprole1 (I) 0.01 86 ± 2 -56 0.01 0.003 64 ± 8 -15 0.01 0.003
8. Fenoxaprop-p-ethyl (H) 0.05 94 ± 9 6 0.03 0.009 72 ± 4 31 0.02 0.006
9. Fluazifop-p-butyl1 (H) 0.01 100 ± 8 51 0.03 0.009 124 ± 5 16 0.02 0.006
10. Propaquizafop (H) 0.05 107 ± 8 -26 0.03 0.009 87 ± 3 -11 0.03 0.009
11. Quizalofop-p-ethyl (H) 0.01 95 ± 4 7 0.01 0.003 93 ± 9 6 0.01 0.003
12. Fluopicolide (F) 0.01 85 ± 5 31 0.01 0.003 82 ± 2 8 0.01 0.003
13. Propyzamide (H) 0.01 93 ± 4 26 0.01 0.003 94 ± 5 11 0.01 0.003
14. Bromopropylate (A) 0.01 96 ± 5 121 0.01 0.003 120 ± 5 21 0.01 0.003
15. Fuberidazole (F) 0.01 n.d. 14 - - 43 ± 6 9 0.01 0.003
16. Thiabendazole (I) 0.01 n.d. 35 - - 43 ± 3 17 0.01 0.003
17. Dichlobenil (H) 0.01 86 ± 4 1 0.01 0.003 84 ± 5 1 0.01 0.003
18. Metrafenone (F) 0.01 107 ± 8 30 0.01 0.003 68 ± 2 4 0.009 0.003
19. Teflubenzuron (I) 0.05 109 ± 5 228 0.02 0.006 102 ± 6 49 0.02 0.006
20. Tetradifon (I) 0.01 91 ± 3 35 0.01 0.003 85 ± 5 10 0.01 0.003
21. Carbaryl1 (I) 0.01 88 ± 4 146 0.02 0.006 81 ± 5 169 0.01 0.003
22. Carbofuran1 (I) 0.01 85 ± 6 110 0.02 0.006 88 ± 2 215 0.01 0.003
23. Carbosulfan (I) 0.01 n.d. -40 - - 90 ± 5 -8 0.01 0.003
24. Chlorpropham (H) 0.05 94 ± 5 -112 0.01 0.003 120 ± 5 -17 0.01 0.003
25. Fenoxycarb (I) 0.01 98 ± 2 38 0.01 0.003 93 ± 5 95 0.01 0.003
26. Iprowalikarb (F) 0.05 82 ± 7 30 0.01 0.003 116 ± 5 25 0.01 0.003
Supplement: Determination of pesticides in tobacco and nitrogen-phosphorous detection by MS S47
Active substance (Pesticide type)
Spiking level (mg/kg)
Mean recovery ± RSD(%)
Matrix effect (%)
LOQ(mg/kg)
LOD (mg/kg)
Mean recovery ± RSD(%)
Matrix effect (%)
LOQ(mg/kg)
LOD (mg/kg)
MSPD QuEChERS
27. Isoprocarb (I) 0.01 97 ± 9 -77 0.01 0.003 92 ± 4 -30 0.01 0.003
28. Pirimicarb1.2 (I) 0.01 75 ± 8 -2 0.01 0.003 52 ± 7 -6 0.01 0.003
29. Pirimicarb desmethyl (I) 0.01 108 ± 18 10 0.01 0.003 79 ± 6 1 0.01 0.003
30. Propham (H) 0.05 77 ± 3 0.3 0.02 0.006 107 ± 6 1 0.01 0.003
31. Propoxur1 (I) 0.01 111 ± 1 -3 0.02 0.006 91 ± 4 -48 0.01 0.003
32. Boscalid (F) 0.01 86 ± 5 12 0.01 0.003 97 ± 3 2 0.008 0.002
33. Diflufenican (DFF) (H) 0.01 100 ± 9 166 0.01 0.003 120 ± 5 35 0.01 0.003
34. Hexythiazox (A) 0.05 69 ± 6 -50 0.04 0.012 93 ± 1 -19 0.04 0.012
35. Acetochlor (H) 0.01 83 ± 5 8 0.01 0.003 95 ± 4 8 0.01 0.003
36. Dimethenamid (H) 0.05 90 ± 6 66 0.02 0.006 71 ± 5 9 0.02 0.006
37. Metazachlor (H) 0.01 89 ± 3 26 0.01 0.003 84 ± 2 9 0.008 0.002
38. Metolachlor (H) 0.05 83 ± 15 2 0.02 0.006 109 ± 7 17 0.02 0.006
39. Propachlor (H) 0.05 80 ± 9 29 0.02 0.006 95 ± 5 17 0.02 0.006
40. Chlorothalonil1 (F) 0.01 92 ± 6 124 0.01 0.003 88 ± 4 23 0.01 0.003
41. Dicloran1 (F) 0.01 105 ± 3 -4 0.01 0.003 78 ± 3 -2 0.01 0.003
42. HCB (Hexachlorobenzene)1 (F)
0.01 81 ± 4 -45 0.005 0.001 84 ± 7 -11 0.005 0.001
43. Quintozene (PCNB) (F) 0.01 83 ± 6 3 0.01 0.003 84 ± 9 2 0.01 0.003
44. Tecnazene (TCNB) (F) 0.01 92 ± 9 7 0.009 0.003 105 ± 6 9 0.009 0.003
45. Tolclofos methyl (F) 0.01 75 ± 4 11 0.01 0.003 79 ± 5 10 0.01 0.003
46. Cymoxanil1 (F) 0.05 61 ± 3 30 0.04 0.012 72 ± 5 16 0.04 0.012
47. Iprodione1 (F) 0.05 101 ± 5 3161 0.02 0.006 112 ± 8 619 0.02 0.006
48. Procymidone (F) 0.01 106 ± 11 30 0.01 0.003 96 ± 16 9 0.01 0.003
49. Pendimethalin1 (H) 0.01 87 ± 8 15 0.01 0.003 92 ± 5 2 0.01 0.003
50. Trifluralin1 (H) 0.01 94 ± 1 7 0.01 0.003 98 ± 13 2 0.01 0.003
51. Nitrofen1 (H) 0.01 94 ± 3 -26 0.009 0.003 96 ± 4 -4 0.009 0.003
52. Oxyflurofen (H) 0.01 76 ± 7 14 0.009 0.003 101 ± 6 2 0.008 0.002
53. Fenhexamid (F) 0.05 97 ± 6 -44 0.02 0.006 76 ± 6 -91 0.02 0.006
54. Fenamidon (F) 0.01 102 ± 4 1 0.01 0.003 108 ± 7 18 0.01 0.003
55. Imazalil (F) 0.01 49 ± 5 5 0.02 0.006 44 ± 4 12 0.02 0.006
56. Prochloraz (F) 0.01 35 ± 3 -21 0.01 0.003 111 ± 8 -4 0.01 0.003
57. Triflumizole (F) 0.01 82 ± 6 35 0.02 0.006 74 ± 4 15 0.01 0.003
58. Isoxaflutole (H) 0.05 84 ± 5 30 0.02 0.006 95 ± 2 17 0.02 0.006
59. Clomazone1.2 (H) 0.01 73 ± 6 2 0.01 0.003 76 ± 5 2 0.01 0.003
60. Dimethomorph1 (F) 0.05 99 ± 3 -36 0.03 0.009 104 ± 1 -48 0.03 0.009
61. Fenpropimorph (F) 0.05 41 ± 9 3 0.02 0.006 92 ± 5 14 0.02 0.006
62. Acetamiprid1 (I) 0.01 41 ± 4 14 0.01 0.003 76 ± 5 14 0.01 0.003
63. Thiacloprid (I) 0.01 75 ± 3 15 0.01 0.003 71 ± 9 7 0.01 0.003
64. Thiametoxam1 (I) 0.01 62 ± 10 29 0.02 0.006 43 ± 2 3 0.01 0.003
65. Aldrine1 (I) 0.01 87 ± 7 -54 0.005 0.001 72 ± 8 -15 0.005 0.001
66. Alpha endosulfan1 (I) 0.01 89 ± 5 -7 0.008 0.002 87 ± 3 -18 0.007 0.002
ContinuedSupplementary Table 2: Validation parameters and matrix effect of MSPD and QuEChERS methods in tobacco studied by GC-µECD/NPD. Negative values of matrix effects mean suppression of the signal and positives values enhancement.
S48 Bozena Lozowicka, Ewa Rutkowska, Izabela Hrynko
Active substance (Pesticide type)
Spiking level (mg/kg)
Mean recovery ± RSD(%)
Matrix effect (%)
LOQ(mg/kg)
LOD (mg/kg)
Mean recovery ± RSD(%)
Matrix effect (%)
LOQ(mg/kg)
LOD (mg/kg)
MSPD QuEChERS
67. Alpha HCH1 (I) 0.01 90 ± 6 -50 0.005 0.001 112 ± 9 -31 0.005 0.001
68. Beta endosulfan1 (I) 0.01 90 ± 8 -15 0.008 0.002 93 ± 3 -11 0.008 0.002
69. Beta HCH1 (I) 0.01 90 ± 6 -59 0.005 0.002 93 ± 5 -31 0.005 0.001
70. Dicofol (A) 0.01 82 ± 6 13 0.01 0.003 75 ± 6 2 0.009 0.003
71. Dieldrin1 (I) 0.01 95 ± 7 -56 0.005 0.001 84 ± 10 -18 0.005 0.001
72. Sulfate endosulfan1 (I) 0.01 96 ± 5 82 0.008 0.002 95 ± 4 10 0.008 0.002
73. Endrin1 (I) 0.01 110 ± 5 27 0.005 0.001 87 ± 13 28 0.005 0.001
74. Heptachlor1 (I) 0.01 92 ± 5 -27 0.005 0.001 76 ± 5 -3 0.005 0.001
75. Heptachlor epoxide1 (I) 0.01 95 ± 6 -55 0.005 0.001 81 ± 13 -20 0.005 0.001
76. Methoxychlor (DMDT)1 (I) 0.01 119 ± 6 1295 0.01 0.003 116 ± 3 14 0.01 0.003
77. o.p’-DDT1 (I) 0.01 120 ± 1 -79 0.005 0.001 115 ± 6 -22 0.005 0.001
78. p.p’-DDD1 (I) 0.01 104 ± 9 -76 0.005 0.001 102 ± 3 -20 0.005 0.001
79. p.p’-DDE1 (I) 0.01 91 ± 4 -56 0.005 0.001 83 ± 13 -21 0.005 0.001
80. p.p’-DDT1 (I) 0.01 125 ± 11 1148 0.005 0.001 115 ± 4 4 0.005 0.001
81. Azinphos ethyl1 (I) 0.01 87 ± 4 48 0.01 0.003 85 ± 3 30 0.01 0.003
82. Azinphos methyl1 (I) 0.01 84 ± 4 143 0.01 0.003 88 ± 9 47 0.01 0.003
83. Chlorfenvinphos1 (I) 0.01 82 ± 4 8 0.008 0.002 84 ± 4 7 0.008 0.002
84. Bromofos ethyl1 (I) 0.01 85 ± 3 10 0.009 0.003 78 ± 9 4 0.009 0.003
85. Bromofos methyl (I) 0.01 100 ± 6 9 0.009 0.003 86 ± 5 6 0.009 0.003
86. Cadusafos (I) 0.01 94 ± 9 20 0.008 0.002 104 ± 12 5 0.006 0.002
87. Chlorpyrifos1 (I) 0.01 90 ± 7 4 0.005 0.001 84 ± 4 1 0.005 0.001
88. Chlorpyrifos methyl1 (I) 0.01 88 ± 7 2 0.005 0.001 88 ± 8 5 0.005 0.001
89. Coumphos (I) 0.05 89 ± 5 52 0.03 0.009 80 ± 9 36 0.03 0.009
90. Diazinon1 (I) 0.01 81 ± 12 41 0.01 0.003 79 ± 6 5 0.01 0.003
91. Dichlorvos1 (I) 0.01 105 ± 14 90 0.01 0.003 95 ± 11 30 0.01 0.003
92. Dicrotophos (I) 0.01 61 ± 2 203 0.01 0.003 62 ± 9 42 0.01 0.003
93. Dimethoate1 (I) 0.01 104 ± 12 39 0.01 0.003 74 ± 2 25 0.01 0.003
94. EPN (I) 0.01 78 ± 10 23 0.008 0.002 85 ± 8 2 0.007 0.002
95. Ethion (I) 0.01 87 ± 6 27 0.008 0.002 92 ± 4 8 0.01 0.003
96. Ethoprophos1 (I) 0.01 112 ± 5 29 0.01 0.003 110 ± 6 9 0.01 0.003
97. Fenchlorfos1 (I) 0.01 76 ± 6 3 0.01 0.003 82 ± 7 5 0.01 0.003
98. Fenitrothion1 (I) 0.01 91 ± 9 12 0.01 0.003 85 ± 9 2 0.009 0.003
99. Fention1 (I) 0.01 74 ± 5 25 0.01 0.003 80 ± 4 5 0.01 0.003
100. Formothion1 (I) 0.01 104 ± 4 9 0.01 0.003 109 ± 5 2 0.01 0.003
101. Fostiazate (I) 0.01 97 ± 2 142 0.01 0.003 82 ± 3 41 0.008 0.002
102. Heptenophos (I) 0.01 78 ± 2 57 0.01 0.003 79 ± 6 13 0.01 0.003
103. Isocarbophos (A) 0.01 90 ± 3 83 0.01 0.003 93 ± 10 69 0.01 0.003
104. Isofenphos (I) 0.01 91 ± 4 55 0.01 0.003 84 ± 8 11 0.01 0.003
105. Isofenfos methyl (I) 0.01 88 ± 16 41 0.01 0.003 78 ± 8 7 0.01 0.003
106. Malaoxon (I) 0.01 99 ± 4 44 0.01 0.003 71 ± 7 20 0.01 0.003
107. Malathion1 (I) 0.01 90 ± 13 80 0.01 0.003 93 ± 6 22 0.01 0.003
ContinuedSupplementary Table 2: Validation parameters and matrix effect of MSPD and QuEChERS methods in tobacco studied by GC-µECD/NPD. Negative values of matrix effects mean suppression of the signal and positives values enhancement.
Supplement: Determination of pesticides in tobacco and nitrogen-phosphorous detection by MS S49
Active substance (Pesticide type)
Spiking level (mg/kg)
Mean recovery ± RSD(%)
Matrix effect (%)
LOQ(mg/kg)
LOD (mg/kg)
Mean recovery ± RSD(%)
Matrix effect (%)
LOQ(mg/kg)
LOD (mg/kg)
MSPD QuEChERS
108. Mecarbam (I) 0.01 89 ± 3 -1 0.01 0.003 80 ± 2 7 0.01 0.003
109. Methacrifos (F) 0.01 84 ± 3 30 0.01 0.003 88 ± 8 4 0.01 0.003
110. Methidathion1 (I) 0.01 76 ± 4 21 0.01 0.003 72 ± 1 9 0.01 0.003
111. Mevinphos (I) 0.01 92 ± 6 37 0.01 0.003 81 ± 14 14 0.01 0.003
112. Paraoxon ethyl (I) 0.01 83 ± 6 -14 0.01 0.003 79 ± 7 -12 0.009 0.003
113. Paraoxon methyl (I) 0.01 83 ± 13 78 0.01 0.003 78 ± 9 61 0.009 0.003
114. Parathion ethyl1 (I) 0.01 86 ± 5 7 0.01 0.003 80 ± 8 3 0.009 0.003
115. Parathion methyl1 (I) 0.01 81 ± 4 9 0.01 0.003 81 ± 9 7 0.009 0.003
116. Phentoate (I) 0.01 81 ± 6 61 0.01 0.003 79 ± 7 1 0.01 0.003
117. Phorate1 (I) 0.01 86 ± 5 50 0.01 0.003 116 ± 5 29 0.01 0.003
118. Phosalone1 (I) 0.01 97 ± 15 25 0.01 0.003 85 ± 11 3 0.01 0.003
119. Phosmet (I) 0.01 93 ± 13 102 0.01 0.003 111 ± 3 30 0.01 0.003
120. Pirimiphos ethyl (I) 0.01 74 ± 6 49 0.009 0.003 79 ± 4 5 0.009 0.003
121. Pirimiphos methyl1 (I) 0.01 75 ± 5 35 0.009 0.003 87 ± 8 4 0.009 0.003
122. Profenofos1 (I) 0.01 81 ± 6 42 0.01 0.003 81 ± 4 25 0.01 0.003
123. Quinalphos (I) 0.01 83 ± 3 31 0.008 0.002 79 ± 7 4 0.007 0.002
124. Tetrachlorwinfos1 (I) 0.01 86 ± 15 157 0.01 0.003 90 ± 11 45 0.008 0.002
125. Triazophos (I) 0.01 77 ± 9 62 0.01 0.003 92 ± 8 23 0.01 0.003
126. Indoxacarb1 (I) 0.01 86 ± 6 -22 0.01 0.003 112 ± 6 -26 0.01 0.003
127. Flutolanil (F) 0.05 70 ± 3 258 0.03 0.009 97 ± 6 1 0.02 0.006
128. Famoksadone1 (F) 0.05 82 ± 6 30 0.01 0.003 78 ± 5 25 0.01 0.003
129. Vinclozolin (F) 0.01 93 ± 14 4 0.01 0.003 82 ± 4 1 0.01 0.003
130. Chlozolinate (F) 0.01 92 ± 3 -8 0.01 0.003 75 ± 5 -6 0.01 0.003
131. Flufenacet (H) 0.01 91 ± 15 19 0.01 0.003 95 ± 12 2 0.01 0.003
132. Benalaxyl1 (F) 0.01 90 ± 6 13 0.01 0.003 117 ± 4 50 0.01 0.003
133. Metalaxyl1.2 (F) 0.01 61 ± 4 123 0.01 0.003 90 ± 10 0.4 0.01 0.003
134. Oksadixyl1 (F) 0.01 96 ± 5 8 0.01 0.003 90 ± 7 24 0.01 0.003
135. Fipronil (I) 0.01 76 ± 16 364 0.009 0.003 80 ± 7 57 0.009 0.003
136. Fluazinam (F) 0.01 101 ± 2 -22 0.01 0.003 82 ± 4 -28 0.01 0.003
137. Fludioxonil (F) 0.01 91 ± 4 -18 0.01 0.003 98 ± 5 -2 0.01 0.003
138. Pencycuron (F) 0.05 85 ± 4 -71 0.02 0.006 85 ± 8 -9 0.01 0.003
139. Isoprothiolane (F) 0.01 87 ± 5 12 0.01 0.003 102 ± 4 15 0.01 0.003
140. Pyrazofos (I) 0.01 103 ± 8 44 0.01 0.003 76 ± 7 13 0.01 0.003
141. Captafol (F) 0.01 79 ± 11 965 0.01 0.003 71 ± 8 765 0.01 0.003
142. Captan1 (F) 0.01 89 ± 13 1874 0.01 0.003 96 ± 3 1101 0.01 0.003
143. Folpet1 (F) 0.01 87 ± 2 85 0.01 0.003 85 ± 5 25 0.01 0.003
144. Tebufenpyrad (A) 0.01 79 ± 4 -7 0.01 0.003 80 ± 5 -3 0.01 0.003
145. Acrinathrin (I) 0.01 62 ± 4 716 0.01 0.003 86 ± 8 66 0.01 0.003
146. Bifenthrin1 (I) 0.01 67 ± 6 74 0.01 0.003 75 ± 5 5 0.01 0.003
147. Cyfluthrin1 (I) 0.05 95 ± 8 161 0.02 0.006 85 ± 4 33 0.02 0.006
148. Cypermethrin1.2 (I) 0.05 109 ± 13 -113 0.01 0.003 97 ± 12 -30 0.01 0.003
ContinuedSupplementary Table 2: Validation parameters and matrix effect of MSPD and QuEChERS methods in tobacco studied by GC-µECD/NPD. Negative values of matrix effects mean suppression of the signal and positives values enhancement.
S50 Bozena Lozowicka, Ewa Rutkowska, Izabela Hrynko
Active substance (Pesticide type)
Spiking level (mg/kg)
Mean recovery ± RSD(%)
Matrix effect (%)
LOQ(mg/kg)
LOD (mg/kg)
Mean recovery ± RSD(%)
Matrix effect (%)
LOQ(mg/kg)
LOD (mg/kg)
MSPD QuEChERS
149. Deltamethrin1 (I) 0.05 110 ± 10 39 0.01 0.003 90 ± 14 11 0.01 0.003
150. Esfenvalerate1 (I) 0.01 90 ± 5 80 0.01 0.003 100 ± 5 14 0.01 0.003
151. Fenpropathrin (I) 0.01 100 ± 1 4 0.01 0.003 105 ± 5 1 0.01 0.003
152. Fenvalerate1 (I) 0.01 92 ± 5 -21 0.01 0.003 86 ± 11 -20 0.01 0.003
153. Gamma HCH (Lindane)1 (I) 0.01 96 ± 11 -50 0.005 0.001 88 ± 3 -17 0.005 0.001
154. Lambda cyhalothrin1 (I) 0.01 82 ± 5 99 0.01 0.003 81 ± 7 8 0.01 0.003
155. Permethrin1 (I) 0.05 96 ± 5 225 0.04 0.012 114 ± 54 21 0.03 0.009
156. Pyrethrin1 (I) 0.05 90 ± 6 25 0.04 0.012 64 ± 8 16 0.03 0.009
157. Tau-Fluvalinate (I) 0.01 92 ± 13 379 0.01 0.003 83 ± 11 284 0.009 0.003
158. Tefluthrin1 (I) 0.01 84 ± 8 9 0.009 0.003 89 ± 1 6 0.007 0.002
159. Tetramethrin (I) 0.05 91 ± 3 657 0.03 0.009 86 ± 2 137 0.02 0.006
160. Zoxamide (F) 0.01 113 ± 5 -48 0.009 0.003 73 ± 5 -76 0.007 0.002
161. Chloridazon (H) 0.01 87 ± 3 -1 0.009 0.003 44 ± 4 -15 0.007 0.002
162. Flurtamone (H) 0.01 89 ± 9 -10 0.01 0.003 88 ± 6 -5 0.009 0.003
163. Pyridaben (A) 0.05 90 ± 4 375 0.02 0.006 82 ± 7 3 0.01 0.003
164. Flonicamid (I) 0.01 42 ± 5 -1 0.01 0.003 46 ± 4 -1 0.01 0.003
165. Fenarimol (F) 0.01 97 ± 3 23 0.01 0.003 81 ± 14 6 0.009 0.003
166. Bupirimate (F) 0.01 103 ± 6 10 0.01 0.003 61 ± 6 5 0.007 0.002
167. Quinoxyfen (F) 0.01 98 ± 6 12 0.009 0.003 111 ± 5 16 0.008 0.002
168. Azoxystrobin (F) 0.01 83 ± 5 -19 0.01 0.003 73 ± 1 -3 0.01 0.003
169. Dimoksystrobina (F) 0.01 86 ± 12 123 0.01 0.003 78 ± 6 20 0.01 0.003
170. Fluoxastrobin (F) 0.01 105 ± 19 1025 0.01 0.003 100 ± 13 57 0.01 0.003
171. Kresoxim methyl (F) 0.01 99 ± 7 31 0.01 0.003 87 ± 7 4 0.008 0.002
172. Picoxystrobin (F) 0.05 104 ± 6 -4 0.03 0.009 90 ± 3 -3 0.01 0.003
173. Pyraklostrobina (F) 0.05 91 ± 4 32 0.05 0.015 91 ± 3 29 0.05 0.015
174. Trifloxystrobin (F) 0.01 104 ± 2 18 0.01 0.003 101 ± 10 13 0.007 0.002
175. Propargite (A) 0.05 59 ± 6 363 0.05 0.015 128 ± 14 252 0.05 0.015
176. Tritosulfuron (H) 0.01 86 ± 5 78 0.01 0.003 90 ± 3 56 0.009 0.003
177. Dichlofluanid (F) 0.01 91 ± 8 20 0.01 0.003 86 ± 12 0.4 0.01 0.003
178. Tolylfluanid (F) 0.01 94 ± 7 31 0.01 0.003 84 ± 5 8 0.01 0.003
179. Spirodiclofen (A) 0.01 90 ± 9 -7 0.01 0.003 92 ± 5 -11 0.008 0.002
180. Atrazine (H) 0.01 81 ± 5 13 0.01 0.003 82 ± 3 13 0.009 0.003
181. Cyanazine (H) 0.01 80 ± 5 3 0.01 0.003 77 ± 3 10 0.009 0.003
182. Cyprazine (H) 0.01 78 ± 3 9 0.01 0.003 104 ± 4 9 0.009 0.003
183. Procyazine (H) 0.01 124 ± 12 -4 0.01 0.003 110 ± 6 -30 0.009 0.003
184. Prometrine (H) 0.01 73 ± 10 10 0.01 0.003 82 ± 5 16 0.009 0.003
185. Propazine (H) 0.01 85 ± 10 5 0.01 0.003 92 ± 13 5 0.009 0.003
186. Simazine (H) 0.01 72 ± 6 2 0.01 0.003 78 ± 2 2 0.008 0.002
187. Terbuthylazine (H) 0.01 118 ± 17 5 0.009 0.003 87 ± 9 3 0.009 0.003
188. Terbutryn (H) 0.01 67 ± 8 0.4 0.009 0.003 77 ± 4 1 0.009 0.003
189. Metamitron (H) 0.01 60 ± 9 128 0.01 0.003 108 ± 6 10 0.01 0.003
ContinuedSupplementary Table 2: Validation parameters and matrix effect of MSPD and QuEChERS methods in tobacco studied by GC-µECD/NPD. Negative values of matrix effects mean suppression of the signal and positives values enhancement.
Supplement: Determination of pesticides in tobacco and nitrogen-phosphorous detection by MS S51
Active substance (Pesticide type)
Spiking level (mg/kg)
Mean recovery ± RSD(%)
Matrix effect (%)
LOQ(mg/kg)
LOD (mg/kg)
Mean recovery ± RSD(%)
Matrix effect (%)
LOQ(mg/kg)
LOD (mg/kg)
MSPD QuEChERS
190. Metribuzin (H) 0.01 85 ± 6 5 0.009 0.003 77 ± 7 5 0.009 0.003
191. Azaconazole (F) 0.01 120 ± 5 -4 0.01 0.003 102 ± 11 12 0.008 0.002
192. Bitertanol (F) 0.05 57 ± 2 23 0.02 0.006 89 ± 15 24 0.01 0.003
193. Bromuconazole (F) 0.01 108 ± 1 213 0.01 0.003 91 ± 6 8 0.01 0.003
194. Cyproconazole (F) 0.01 82 ± 7 -28 0.01 0.003 74 ± 4 -6 0.01 0.003
195. Difenoconazole (F) 0.05 55 ± 2 -17 0.01 0.003 76 ± 9 -23 0.01 0.003
196. Dinikonazol (F) 0.01 96 ± 7 6 0.009 0.003 85 ± 11 20 0.008 0.002
197. Epoxiconazole (F) 0.01 92 ± 7 102 0.009 0.003 110 ± 6 16 0.009 0.003
198. Etaconazole (F) 0.01 69 ± 14 -10 0.01 0.003 89 ± 14 -1 0.009 0.003
199. Fenbuconazole (F) 0.01 49 ± 6 -12 0.01 0.003 77 ± 2 -8 0.01 0.003
200. Fluquinconazole (F) 0.01 80 ± 6 3 0.01 0.003 74 ± 2 2 0.008 0.002
201. Flusilazole (F) 0.01 60 ± 6 18 0.009 0.003 91 ± 14 14 0.008 0.002
202. Flutriafol (F) 0.05 43 ± 5 -23 0.02 0.006 57 ± 6 18 0.01 0.003
203. Hexaconazole (F) 0.01 102 ± 8 17 0.009 0.003 82 ± 12 5 0.009 0.003
204. Imibenkonazol (F) 0.01 60 ± 13 -36 0.01 0.003 71 ± 5 -41 0.008 0.002
205. Metkonazol (F) 0.05 63 ± 8 38 0.02 0.006 87 ± 7 31 0.01 0.003
206. Myclobutanyl (F) 0.01 103 ± 5 18 0.01 0.003 90 ± 11 13 0.009 0.003
207. Paclobutrazol (F) 0.01 74 ± 5 -14 0.01 0.003 70 ± 5 -2 0.01 0.003
208. Penconazole1 (F) 0.01 62 ± 7 18 0.009 0.003 80 ± 17 7 0.008 0.002
209. Propiconazole (F) 0.01 76 ± 9 8 0.01 0.003 86 ± 4 13 0.01 0.003
210. Prothioconazole (F) 0.01 45 ± 15 16 0.01 0.003 86 ± 3 8 0.01 0.003
211. Tebuconazole (F) 0.01 50 ± 9 12 0.01 0.003 124 ± 4 30 0.009 0.003
212. Tetraconazole (F) 0.01 60 ± 5 18 0.01 0.003 75 ± 18 1 0.009 0.003
213. Triadimefon (F) 0.01 0.008 6 0.01 0.003 0.008 4 0.01 0.003
214. Triadimenol (F) 0.05 74 ± 7 22 0.03 0.009 83 ± 9 5 0.01 0.003
215. Triticonazole (F) 0.01 87 ± 6 -7 0.01 0.003 115 ± 5 -2 0.01 0.003
216. Buprofezin (I) 0.01 83 ± 8 77 0.01 0.003 88 ± 3 11 0.01 0.003
217. DEET N.N-dietylo-m-toluamid (I)
0.05 84 ± 7 197 0.03 0.009 95 ± 4 30 0.01 0.003
218. Difenyloamina (F) 0.01 82 ± 8 -6 0.01 0.003 96 ± 6 -1 0.01 0.003
219. Fenazaquin (I) 0.01 95 ± 4 13 0.01 0.003 111 ± 5 69 0.01 0.003
220. Flurochloridone (H) 0.01 76 ± 5 15 0.009 0.003 112 ± 10 3 0.006 0.002
221. Pyriproxyfen (I) 0.05 88 ± 3 35 0.02 0.006 85 ± 5 23 0.01 0.003
222. Quinoclamine (H) 0.01 90 ± 5 81 0.01 0.003 84 ± 12 11 0.009 0.003
223. Lenacil (H) 0.05 90 ± 3 342 0.02 0.006 95 ± 11 329 0.01 0.003
*LOQ - Limit of quantification**LOD - Limit of detection1 List of the pesticides employed for tobacco (CORESTA)2 Pesticides recommended for tobacco cultivationn.d. not detected
ContinuedSupplementary Table 2: Validation parameters and matrix effect of MSPD and QuEChERS methods in tobacco studied by GC-µECD/NPD. Negative values of matrix effects mean suppression of the signal and positives values enhancement.