Chinese Journal of Chromatography ›› 2025, Vol. 43 ›› Issue (7): 805-814.DOI: 10.3724/SP.J.1123.2024.09009
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ZHANG Quan1, WU Yutian1, PENG Lei1, BI Shan1, ZHOU Yibing1, LIN Ye1, LIU Liya1, CHEN Qingyuan1,*(
), ZHOU Xue2,*(
)
Received:2024-08-19
Online:2025-07-08
Published:2025-07-04
Supported by:CLC Number:
ZHANG Quan, WU Yutian, PENG Lei, BI Shan, ZHOU Yibing, LIN Ye, LIU Liya, CHEN Qingyuan, ZHOU Xue. Rapid screening of 125 pesticide residues in tea substitutes by multi-plug filtration cleanup method combined with gas chromatography-tandem mass spectrometry[J]. Chinese Journal of Chromatography, 2025, 43(7): 805-814.
| No. | Pesticide | tR/min | Chemical formula | Mr | CAS No. | Ion pairs (m/z) | CEs/eV |
|---|---|---|---|---|---|---|---|
| IS | heptachlor epoxide (环氧七氯) | 23.080 | C10H5Cl7O | 389.3 | 1024-57-3 | 353>263*, 353>282 | 15, 15 |
| 1 | isoprocarb (异丙威) | 7.481+14.510 | C11H15O2N | 193.2 | 2631-40-5 | 121>77*, 136>121 | 20, 10 |
| 2 | dichlorvos (敌敌畏) | 7.986 | C4H7Cl2O4P | 221.0 | 62-73-7 | 185>109*, 185>63 | 20, 15 |
| 3 | fenobucarb (仲丁威) | 8.710 | C12H17NO2 | 207.3 | 3766-81-2 | 121>77*, 121>104 | 20, 15 |
| 4 | methamidophos (甲胺磷) | 9.925 | C₂H₈NO₂PS | 141.1 | 10265-92-6 | 141>95*, 141>79 | 10, 15 |
| 5 | dichlorobenzonitrile(敌草腈) | 10.208 | C7H3Cl2N | 172.0 | 1194-65-6 | 171>100*, 171>136 | 25, 15 |
| 6 | molinate (禾草敌) | 12.643 | C9H17NOS | 187.3 | 2212-67-1 | 126>55*, 126>83 | 10, 5 |
| 7 | tecnazene (四氯硝基苯) | 14.387 | Cl4C6HNO2 | 260.9 | 117-18-0 | 259>201*, 259>141 | 10, 30 |
| 8 | ethoprophos (灭线磷) | 15.308 | C8H19O2PS2 | 242.3 | 13194-48-4 | 158>97*, 158>81 | 18, 15 |
| 9 | diphenylamine (二苯胺) | 15.393 | C12H11N | 169.2 | 122-39-4 | 169>168*, 169>167 | 10, 15 |
| 10 | phorate (甲拌磷) | 16.413 | C₇HO₂PS3 | 260.4 | 298-02-2 | 260>231*, 260>171 | 10, 20 |
| 11 | chlorpropham (氯苯胺灵) | 16.668 | C10H12ClNO2 | 213.7 | 101-21-3 | 213>127*, 213>171 | 20, 10 |
| 12 | sulfotep (治螟磷) | 16.700 | C8H20O5P2S2 | 322.3 | 3689-24-5 | 322>266*, 322>146 | 10, 10 |
| 13 | pentachloronitrobenzene (五氯硝基苯) | 17.688 | C₆Cl₅NO2 | 295.3 | 82-68-8 | 249>214*, 237>143 | 15, 20 |
| 14 | terbufos (特丁硫磷) | 17.874 | C9H21O2PS3 | 288.4 | 13071-79-9 | 231>129*, 231>175 | 20, 10 |
| 15 | clomazone (异噁草酮) | 18.021 | C12H14ClNO2 | 239.7 | 81777-89-1 | 125>89*, 204>107 | 15, 20 |
| 16 | triallate (野麦畏) | 18.066 | C10H16Cl3NOS | 304.7 | 2303-17-5 | 268>184*, 142.9>83 | 20, 15 |
| 17 | diazinon (二嗪磷) | 18.159 | C12H21N2O3PS | 304.3 | 333-41-5 | 304>137*, 304>164 | 35, 35 |
| 18 | fonofos (地虫硫膦) | 18.312 | C10H15OPS2 | 246.3 | 944-22-9 | 246>109*, 246>137 | 18, 10 |
| 19 | pyrimethanil (嘧霉胺) | 18.355 | C12H13N3 | 199.3 | 53112-28-0 | 198>156*, 198>182 | 25, 18 |
| 20 | simazine (西玛津) | 19.129 | C₇HClN5 | 201.7 | 122-34-9 | 201>138*, 201>172 | 10, 15 |
| 21 | dicloran (氯硝胺) | 19.175 | C6H4Cl2N2O2 | 207.0 | 99-30-9 | 176>148*, 206>176 | 10, 10 |
| 22 | atrazine (莠去津) | 19.227 | C8H14ClN5 | 221.7 | 1912-24-9 | 215>200*, 215>172 | 10, 15 |
| 23 | terbuthylazine (特丁津) | 19.313 | C9H16ClN5 | 229.7 | 5915-41-3 | 214>104*, 214>119 | 15, 10 |
| 24 | iprobenfos (异稻瘟净) | 19.831 | C13H21O3PS | 288.3 | 26087-47-8 | 204>91*, 201>122 | 10, 15 |
| 25 | triazophos (三唑磷) | 19.976 | C12H16N3O3PS | 313.0 | 24017-47-8 | 257>119*, 257>134 | 25, 20 |
| 26 | pronamide (炔苯酰草胺) | 20.030 | C12H11Cl2NO | 256.1 | 23950-58-5 | 254>226*, 254>191 | 10, 15 |
| 27 | pirimicarb (抗蚜威) | 20.108 | C11H18N4O2 | 238.3 | 23103-98-2 | 166>96*, 166>83 | 10, 15 |
| 28 | dimethoate (乐果) | 20.498 | C5H12NO3PS2 | 229.3 | 60-51-5 | 125>79*, 125>93 | 10, 40 |
| 29 | chlorpyrifos-methyl (甲基毒死蜱) | 20.499 | C7H7Cl3NO3PS | 322.5 | 5598-13-0 | 286>241*, 286>208 | 25, 10 |
| 30 | monocrotophos (久效磷) | 20.665 | C7H14NO5P | 223.2 | 6923-22-4 | 127>109*, 127>95 | 15, 18 |
| 31 | phosphamidon (磷胺) | 20.665+22.432 | C10H19ClNO5P | 299.7 | 13171-21-6 | 264>193*, 127>109 | 8,12 |
| 32 | acetochlor (乙草胺) | 20.896 | C14H20ClNO2 | 269.8 | 34256-82-1 | 146>131*, 146>130 | 20, 20 |
| 33 | alachlor (甲草胺) | 21.312+25.131 | C14H20ClNO2 | 269.8 | 15972-60-8 | 188>160*, 188>130 | 10, 40 |
| 34 | Prometryn (扑草净) | 21.374 | C10H19N5S | 241.4 | 7287-19-6 | 242>184*, 242>199 | 10, 10 |
| 35 | pirimiphos-methy (甲基嘧啶磷) | 21.470 | C11H20N3O3PS | 305.3 | 29232-93-7 | 290>125*, 290>151 | 20, 20 |
| 36 | ametryn (莠灭净) | 21.579 | C9H17N5S | 227.3 | 834-12-8 | 227>58*, 227>170 | 10, 10 |
| 37 | vinclozolin (乙烯菌核利) | 21.735 | C12H9Cl2NO3 | 286.1 | 50471-44-8 | 212>172*, 212>145 | 15, 20 |
| 38 | thiobencarb (禾草丹) | 21.737 | C12H16ClNOS | 257.8 | 28249-77-6 | 125>89*,125>99 | 20, 11 |
| 39 | metribuzin (嗪草酮) | 21.826 | C7H11N3O2 | 169.2 | 21087-64-9 | 198>82*, 198>55 | 18, 30 |
| 40 | metalaxyl (甲霜灵) | 21.934 | C15H21NO4 | 279.3 | 57837-19-1 | 206>132*, 206>162 | 20, 10 |
| 41 | chlorpyrifos (毒死蜱) | 22.058 | C9H11Cl3NO3PS | 350.6 | 2921-88-2 | 314>258*, 314>166 | 15, 35 |
| 42 | parathion-methyl (甲基对硫磷) | 22.332 | C8H10NO5PS | 263.2 | 298-00-0 | 263>109*, 263>246 | 15, 5 |
| 43 | dicofol (三氯杀螨醇) | 22.564 | C14H9Cl5O | 370.5 | 115-32-2 | 251>139*, 251>111 | 10, 35 |
| 44 | metolachlor (异丙甲草胺) | 22.598 | C15H22ClNO2 | 283.8 | 51218-45-2 | 162>133*, 238>162 | 15, 10 |
| 45 | methoprene (烯虫酯) | 22.807 | C19H34O3 | 310.5 | 40596-69-8 | 111>55*, 153>111 | 15, 5 |
| 46 | malathion (马拉硫磷) | 22.904 | C10H19O6PS2 | 330.4 | 121-75-5 | 173>99*, 173>117 | 18, 10 |
| 47 | fenthion (倍硫磷) | 22.918 | C10H15O3PS2 | 278.3 | 55-38-9 | 278>109*, 278>125 | 20, 18 |
| 48 | cyprodinil (嘧菌环胺) | 23.094 | CHN3 | 225.3 | 121552-61-2 | 224>208*, 224>118 | 18, 40 |
| 49 | fenitrothion (杀螟硫磷) | 23.230 | C9H12NO5PS | 277.2 | 122-14-5 | 260>125*, 260>109 | 15, 10 |
| 50 | ethofumesate (乙氧呋草黄) | 23.354 | C13H18O5S | 286.3 | 26225-79-6 | 286>207*, 286>161 | 10, 20 |
| 51 | triadimefon (三唑酮) | 23.675 | C14H16ClN3O2 | 293.8 | 43121-43-3 | 208>181*, 208>127 | 10, 15 |
| 52 | pendimethalin (二甲戊灵) | 23.880 | C13H19N3O4 | 281.3 | 40487-42-1 | 251>162*, 252>118 | 10, 30 |
| 53 | parathion (对硫磷) | 23.909 | CHNO₅PS | 291.3 | 56-38-2 | 291>109*, 291>137 | 15, 10 |
| 54 | isofenphos-methyl (甲基异柳磷) | 24.003 | C14H22NO4PS | 331.4 | 99675-03-3 | 241>199*, 199>121 | 10, 10 |
| 55 | quinalphos (喹硫磷) | 24.467 | C12H15N2O3PS | 298.3 | 13593-03-8 | 298>156*, 298>129 | 10, 30 |
| 56 | isocarbophos (水胺硫磷) | 24.552 | C11H16NO4PS | 289.3 | 24353-61-5 | 230>212*, 230>197 | 5, 10 |
| 57 | propanil (敌稗) | 24.648 | C9H9Cl2NO | 218.1 | 709-98-8 | 161>90*, 161>126 | 20, 15 |
| 58 | penconazole (戊菌唑) | 24.648 | C13H15Cl2N3 | 284.2 | 66246-88-6 | 248>157*, 248>192 | 25, 15 |
| 59 | phorate sulfoxide (甲拌磷亚砜) | 25.039 | C7H17O3PS3 | 276.4 | 2588-03-6 | 199>143*, 97>65 | 10, 20 |
| 60 | phorate sulfone (甲拌磷砜) | 25.040 | C7H17O4PS3 | 292.4 | 2588-04-7 | 125>97*, 153>97 | 5, 10 |
| 61 | fenothiocarb (苯硫威) | 25.063 | C13H19NO2S | 253.4 | 62850-32-2 | 160>72*, 160>106 | 10, 12 |
| 62 | fosthiazate (噻唑膦) | 25.100 | C9H18NO3PS2 | 283.3 | 98886-44-3 | 195>103*, 195>139 | 10, 5 |
| 63 | tetraconazole (四氟醚唑) | 25.127 | C13H11Cl2F4N3O | 372.2 | 112281-77-3 | 336>218*, 336>204 | 15, 40 |
| 64 | butachlor (丁草胺) | 25.135 | C17H26ClNO2 | 311.8 | 23184-66-9 | 237>160*, 237>188 | 5, 10 |
| 65 | terbufos sulfone (特丁硫磷砜) | 25.696 | C9H21O4PS3 | 320.4 | 56070-16-7 | 153>97*, 199>97 | 10, 20 |
| 66 | triadimenol (三唑醇) | 25.805 | C14H18ClN3O2 | 295.8 | 55219-65-3 | 168>70*, 128>65 | 10, 25 |
| 67 | procymidone (腐霉利) | 25.942 | C13H11Cl2NO2 | 284.1 | 32809-16-8 | 283>96*, 283>177 | 10, 30 |
| 68 | profenofos (丙溴磷) | 26.061 | CHBrClO₃PS | 373.6 | 41198-08-7 | 339>269*, 339>251 | 10, 25 |
| 69 | methidathion (杀扑磷) | 26.101 | C6H11N2O4PS3 | 302.3 | 950-37-8 | 145>85*, 145>58 | 10, 15 |
| 70 | pretilachlor (丙草胺) | 26.150 | C17H26ClNO2 | 311.8 | 51218-49-6 | 162>147*,176>134 | 15, 15 |
| 71 | napropamide (敌草胺) | 26.156 | C17H21NO2 | 271.4 | 15299-99-7 | 271>72*, 271>128 | 10, 5 |
| 72 | hexaconazole (己唑醇) | 26.244 | C14H17Cl2N3O | 314.2 | 79983-71-4 | 214>152*, 214>124 | 25, 25 |
| 73 | oxadiazon (噁草酮) | 26.419 | C15H18Cl2N2O3 | 345.2 | 19666-30-9 | 258>175*,258>112 | 10, 25 |
| 74 | fluazifop-butyl (吡氟禾草灵) | 26.696 | C19H20F3NO4 | 383.4 | 69806-50-4 | 383>282*, 383>254 | 10, 30 |
| 75 | imazalil (抑霉唑) | 26.798 | C14H14Cl2N2O | 297.2 | 35554-44-0 | 215>173*, 215>145 | 5, 20 |
| 76 | paclobutrazol (多效唑) | 26.800 | C15H20ClN3O | 293.8 | 76738-62-0 | 236>125*, 236>132 | 10, 5 |
| 77 | isoprothiolane (稻瘟灵) | 26.956 | C12H18O4S2 | 290.4 | 50512-35-1 | 290>118*, 290>204 | 15, 10 |
| 78 | phosfolan (硫环磷) | 27.076 | C7H14NO3PS2 | 255.3 | 947-02-4 | 196>140*, 168>140 | 10, 5 |
| 79 | bupirimate (乙嘧酚磺酸酯) | 27.430 | C13H24O3N4S | 316.5 | 41483-43-6 | 273>108*, 273>150 | 18, 10 |
| 80 | oxyfluorfen (乙氧氟草醚) | 27.743 | C15H11CIF3NO4 | 361.7 | 42874-03-3 | 300>223*, 300>167 | 20, 25 |
| 81 | flutolanil (氟酰胺) | 27.885 | C17H16F3NO2 | 323.3 | 66332-96-5 | 173>145*, 281>173 | 15, 10 |
| 82 | ethion (乙硫磷) | 28.139 | C9H22O4P2S4 | 384.5 | 563-12-2 | 231>129*, 231>175 | 25, 10 |
| 83 | quinoxyfen (喹氧灵) | 28.255 | C15H8Cl2FNO | 308.1 | 124495-18-7 | 307>237*, 307>272 | 20, 10 |
| 84 | diniconazole (烯唑醇) | 28.755 | C15H17Cl2N3O | 326.2 | 83657-24-3 | 267>232*, 267>232 | 10, 10 |
| 85 | piperonyl butoxide (增效醚) | 28.765 | C19H30O5 | 338.4 | 51-03-6 | 176>131*, 176>117 | 10, 18 |
| 86 | trifloxystrobin (肟菌酯) | 28.777 | C20H19F3N2O4 | 408.4 | 141517-21-7 | 222>162*, 222>190 | 10, 5 |
| 87 | cyproconazole (环丙唑醇) | 28.845 | C15H18ClN3O | 291.8 | 94361-06-5 | 222>125*, 139>111 | 15, 15 |
| 88 | myclobutanil (腈菌唑) | 28.856 | C15H17ClN4 | 288.8 | 88671-89-0 | 179>125*, 179>129 | 15, 20 |
| 89 | benalaxyl (苯霜灵) | 28.875 | C20H23NO3 | 325.4 | 71626-11-4 | 206>132*, 206>162 | 18, 10 |
| 90 | diclofop-methyl (禾草灵) | 29.352 | C15H12Cl2O4 | 327.2 | 51338-27-3 | 253>162*, 340>253 | 15, 10 |
| 91 | edifenphos (敌瘟磷) | 29.416 | C14H15O2PS2 | 310.4 | 17109-49-8 | 173>109*, 310>173 | 10, 15 |
| 92 | fipronil (氟虫腈) | 29.424 | C12H4Cl2F6N4OS | 437.1 | 120068-37-3 | 367>213*, 367>215 | 30, 25 |
| 93 | propiconazole (丙环唑) | 29.508 | C15H17Cl2N3O2 | 342.2 | 60207-90-1 | 259>173*, 259>145 | 20, 40 |
| 94 | epoxiconazole (氟环唑) | 29.683+31.022 | C17H13ClFN3O | 329.8 | 133855-98-8 | 192>138*, 192>111 | 10, 25 |
| 95 | fenthion sulfoxide (倍硫磷亚砜) | 29.824 | C10H15O4PS2 | 294.3 | 3761-41-9 | 278>109*, 278>169 | 15, 15 |
| 96 | isazofos (氯唑磷) | 29.834 | C9H17ClN3O3PS | 313.7 | 42509-80-8 | 161>119*, 161>103 | 10, 15 |
| 97 | fenthion sulfone (倍硫磷砜) | 30.462 | C10H15O5PS2 | 310.3 | 3761-42-0 | 311>105*, 311>137 | 20, 20 |
| 98 | bromopropylate (溴螨酯) | 30.755 | C17H16Br2O3 | 428.1 | 18181-80-1 | 341>185*, 341>183 | 15, 15 |
| 99 | etoxazole (乙螨唑) | 30.931 | CHF₂NO₂ | 359.4 | 153233-91-1 | 359>187*, 359>340 | 15, 12 |
| 100 | iprodione (异菌脲) | 30.931 | C13H13Cl2N3O3 | 330.2 | 36734-19-7 | 314>245*, 314>56 | 10, 25 |
| 101 | oxadixyl (噁霜灵) | 30.995 | C14H18N2O4 | 278.3 | 77732-09-3 | 163>132*, 163>117 | 5, 25 |
| 102 | fludioxonil (咯菌腈) | 31.003 | C12H6F2N2O2 | 248.2 | 131341-86-1 | 248>182*, 248>154 | 10, 15 |
| 103 | fenpropathrin (甲氰菊酯) | 31.152 | C22H23NO3 | 349.4 | 39515-41-8 | 265>210*, 265>181 | 10, 20 |
| 104 | tebuconazole (戊唑醇) | 31.272 | C16H22ClN3O | 307.8 | 107534-96-3 | 250>125*, 250>153 | 15, 10 |
| 105 | pyriproxyfen (吡丙醚) | 31.420 | C20H19NO3 | 321.4 | 95737-68-1 | 136>96*, 131>78 | 15, 20 |
| 106 | anilofos (莎稗磷) | 31.420 | C13H19ClNO3PS2 | 367.9 | 64249-01-0 | 226>157*, 226>157 | 15, 10 |
| 107 | fenamidone (咪唑菌酮) | 32.206 | C17H17N3OS | 311.4 | 161326-34-7 | 238>237*, 268>180 | 10, 20 |
| 108 | pyridaphenthion (哒嗪硫磷) | 32.210 | C14H17N2O4PS | 340.3 | 119-12-0 | 340>199*, 340>109 | 10, 20 |
| 109 | phosmet (亚胺硫磷) | 32.436 | C11H12NO4PS2 | 317.3 | 732-11-6 | 160>77*, 160>105 | 25, 18 |
| 110 | bifenox (甲羧除草醚) | 32.642 | C14H9Cl2NO5 | 342.1 | 42576-02-3 | 341>189*, 341>281 | 20, 20 |
| 111 | tetradifon (三氯杀螨砜) | 32.655 | C12H6Cl4O2S | 356.1 | 116-29-0 | 229>201*, 229>16 | 15, 20 |
| 112 | lambda-cyhalothrin (高效氯氟氰菊酯) | 33.090+33.461 | C23H19ClF3NO3 | 449.9 | 91465-08-6 | 181>152*, 181>127 | 20, 30 |
| 113 | phosalone (伏杀硫磷) | 33.479 | C12H15ClNO4PS2 | 367.8 | 2310-17-0 | 367>182*, 367>111 | 10, 30 |
| 114 | permethrin (氯菊酯) | 33.765 | C21H20Cl2O3 | 391.3 | 52645-53-1 | 183>168*, 183>152 | 10, 20 |
| 115 | mefenacet (苯噻酰草胺) | 33.825 | C16H14N2O2S | 298.4 | 73250-68-7 | 192>136*, 192>109 | 15, 30 |
| 116 | fenarimol (氯苯嘧啶醇) | 33.849 | C17H12Cl2N2O | 331.2 | 60168-88-9 | 330>139*, 330>111 | 10, 30 |
| 117 | pyridaben (哒螨灵) | 34.271 | C19H25ClN2OS | 364.9 | 96489-71-3 | 309>147*, 309>132 | 12, 25 |
| 118 | coumaphos (蝇毒磷) | 36.824 | C14H16ClO5PS | 362.8 | 56-72-4 | 362>109*, 362>226 | 15, 15 |
| 119 | cyfluthrin (氟氯氰菊酯) | 37.053 | CHCl₂FNO3 | 434.3 | 68359-37-5 | 206>151*, 206>177 | 15, 20 |
| 120 | cypermethrin (氯氰菊酯) | 37.089 | C22H19Cl2NO3 | 416.3 | 52315-07-8 | 163>91*, 163>127 | 10, 5 |
| 121 | flucythrinate (氟氰戊菊酯) | 37.930 | C26H23F2NO4 | 451.5 | 70124-77-5 | 225>147*, 225>118 | 10, 25 |
| 122 | fenvalerate (氰戊菊酯) | 40.018 | CHClNO3 | 419.9 | 51630-58-1 | 225>119*, 225>91 | 18, 25 |
| 123 | fluvalinate (氟胺氰菊酯) | 41.132 | CHClF3N2O3 | 502.9 | 102851-06-9 | 250>55*, 250>200 | 20, 20 |
| 124 | difenoconazole (苯醚甲环唑) | 41.782 | C19H17Cl2N3O3 | 406.3 | 119446-68-3 | 323>265*, 323>201 | 15, 30 |
| 125 | deltamethrin (溴氰菊酯) | 42.334 | C22H19Br2NO3 | 505.2 | 52918-63-5 | 253>172*, 253>199 | 10, 25 |
Table 1 Retention times and MS parameters of the 125 target compounds and internal standard (IS)
| No. | Pesticide | tR/min | Chemical formula | Mr | CAS No. | Ion pairs (m/z) | CEs/eV |
|---|---|---|---|---|---|---|---|
| IS | heptachlor epoxide (环氧七氯) | 23.080 | C10H5Cl7O | 389.3 | 1024-57-3 | 353>263*, 353>282 | 15, 15 |
| 1 | isoprocarb (异丙威) | 7.481+14.510 | C11H15O2N | 193.2 | 2631-40-5 | 121>77*, 136>121 | 20, 10 |
| 2 | dichlorvos (敌敌畏) | 7.986 | C4H7Cl2O4P | 221.0 | 62-73-7 | 185>109*, 185>63 | 20, 15 |
| 3 | fenobucarb (仲丁威) | 8.710 | C12H17NO2 | 207.3 | 3766-81-2 | 121>77*, 121>104 | 20, 15 |
| 4 | methamidophos (甲胺磷) | 9.925 | C₂H₈NO₂PS | 141.1 | 10265-92-6 | 141>95*, 141>79 | 10, 15 |
| 5 | dichlorobenzonitrile(敌草腈) | 10.208 | C7H3Cl2N | 172.0 | 1194-65-6 | 171>100*, 171>136 | 25, 15 |
| 6 | molinate (禾草敌) | 12.643 | C9H17NOS | 187.3 | 2212-67-1 | 126>55*, 126>83 | 10, 5 |
| 7 | tecnazene (四氯硝基苯) | 14.387 | Cl4C6HNO2 | 260.9 | 117-18-0 | 259>201*, 259>141 | 10, 30 |
| 8 | ethoprophos (灭线磷) | 15.308 | C8H19O2PS2 | 242.3 | 13194-48-4 | 158>97*, 158>81 | 18, 15 |
| 9 | diphenylamine (二苯胺) | 15.393 | C12H11N | 169.2 | 122-39-4 | 169>168*, 169>167 | 10, 15 |
| 10 | phorate (甲拌磷) | 16.413 | C₇HO₂PS3 | 260.4 | 298-02-2 | 260>231*, 260>171 | 10, 20 |
| 11 | chlorpropham (氯苯胺灵) | 16.668 | C10H12ClNO2 | 213.7 | 101-21-3 | 213>127*, 213>171 | 20, 10 |
| 12 | sulfotep (治螟磷) | 16.700 | C8H20O5P2S2 | 322.3 | 3689-24-5 | 322>266*, 322>146 | 10, 10 |
| 13 | pentachloronitrobenzene (五氯硝基苯) | 17.688 | C₆Cl₅NO2 | 295.3 | 82-68-8 | 249>214*, 237>143 | 15, 20 |
| 14 | terbufos (特丁硫磷) | 17.874 | C9H21O2PS3 | 288.4 | 13071-79-9 | 231>129*, 231>175 | 20, 10 |
| 15 | clomazone (异噁草酮) | 18.021 | C12H14ClNO2 | 239.7 | 81777-89-1 | 125>89*, 204>107 | 15, 20 |
| 16 | triallate (野麦畏) | 18.066 | C10H16Cl3NOS | 304.7 | 2303-17-5 | 268>184*, 142.9>83 | 20, 15 |
| 17 | diazinon (二嗪磷) | 18.159 | C12H21N2O3PS | 304.3 | 333-41-5 | 304>137*, 304>164 | 35, 35 |
| 18 | fonofos (地虫硫膦) | 18.312 | C10H15OPS2 | 246.3 | 944-22-9 | 246>109*, 246>137 | 18, 10 |
| 19 | pyrimethanil (嘧霉胺) | 18.355 | C12H13N3 | 199.3 | 53112-28-0 | 198>156*, 198>182 | 25, 18 |
| 20 | simazine (西玛津) | 19.129 | C₇HClN5 | 201.7 | 122-34-9 | 201>138*, 201>172 | 10, 15 |
| 21 | dicloran (氯硝胺) | 19.175 | C6H4Cl2N2O2 | 207.0 | 99-30-9 | 176>148*, 206>176 | 10, 10 |
| 22 | atrazine (莠去津) | 19.227 | C8H14ClN5 | 221.7 | 1912-24-9 | 215>200*, 215>172 | 10, 15 |
| 23 | terbuthylazine (特丁津) | 19.313 | C9H16ClN5 | 229.7 | 5915-41-3 | 214>104*, 214>119 | 15, 10 |
| 24 | iprobenfos (异稻瘟净) | 19.831 | C13H21O3PS | 288.3 | 26087-47-8 | 204>91*, 201>122 | 10, 15 |
| 25 | triazophos (三唑磷) | 19.976 | C12H16N3O3PS | 313.0 | 24017-47-8 | 257>119*, 257>134 | 25, 20 |
| 26 | pronamide (炔苯酰草胺) | 20.030 | C12H11Cl2NO | 256.1 | 23950-58-5 | 254>226*, 254>191 | 10, 15 |
| 27 | pirimicarb (抗蚜威) | 20.108 | C11H18N4O2 | 238.3 | 23103-98-2 | 166>96*, 166>83 | 10, 15 |
| 28 | dimethoate (乐果) | 20.498 | C5H12NO3PS2 | 229.3 | 60-51-5 | 125>79*, 125>93 | 10, 40 |
| 29 | chlorpyrifos-methyl (甲基毒死蜱) | 20.499 | C7H7Cl3NO3PS | 322.5 | 5598-13-0 | 286>241*, 286>208 | 25, 10 |
| 30 | monocrotophos (久效磷) | 20.665 | C7H14NO5P | 223.2 | 6923-22-4 | 127>109*, 127>95 | 15, 18 |
| 31 | phosphamidon (磷胺) | 20.665+22.432 | C10H19ClNO5P | 299.7 | 13171-21-6 | 264>193*, 127>109 | 8,12 |
| 32 | acetochlor (乙草胺) | 20.896 | C14H20ClNO2 | 269.8 | 34256-82-1 | 146>131*, 146>130 | 20, 20 |
| 33 | alachlor (甲草胺) | 21.312+25.131 | C14H20ClNO2 | 269.8 | 15972-60-8 | 188>160*, 188>130 | 10, 40 |
| 34 | Prometryn (扑草净) | 21.374 | C10H19N5S | 241.4 | 7287-19-6 | 242>184*, 242>199 | 10, 10 |
| 35 | pirimiphos-methy (甲基嘧啶磷) | 21.470 | C11H20N3O3PS | 305.3 | 29232-93-7 | 290>125*, 290>151 | 20, 20 |
| 36 | ametryn (莠灭净) | 21.579 | C9H17N5S | 227.3 | 834-12-8 | 227>58*, 227>170 | 10, 10 |
| 37 | vinclozolin (乙烯菌核利) | 21.735 | C12H9Cl2NO3 | 286.1 | 50471-44-8 | 212>172*, 212>145 | 15, 20 |
| 38 | thiobencarb (禾草丹) | 21.737 | C12H16ClNOS | 257.8 | 28249-77-6 | 125>89*,125>99 | 20, 11 |
| 39 | metribuzin (嗪草酮) | 21.826 | C7H11N3O2 | 169.2 | 21087-64-9 | 198>82*, 198>55 | 18, 30 |
| 40 | metalaxyl (甲霜灵) | 21.934 | C15H21NO4 | 279.3 | 57837-19-1 | 206>132*, 206>162 | 20, 10 |
| 41 | chlorpyrifos (毒死蜱) | 22.058 | C9H11Cl3NO3PS | 350.6 | 2921-88-2 | 314>258*, 314>166 | 15, 35 |
| 42 | parathion-methyl (甲基对硫磷) | 22.332 | C8H10NO5PS | 263.2 | 298-00-0 | 263>109*, 263>246 | 15, 5 |
| 43 | dicofol (三氯杀螨醇) | 22.564 | C14H9Cl5O | 370.5 | 115-32-2 | 251>139*, 251>111 | 10, 35 |
| 44 | metolachlor (异丙甲草胺) | 22.598 | C15H22ClNO2 | 283.8 | 51218-45-2 | 162>133*, 238>162 | 15, 10 |
| 45 | methoprene (烯虫酯) | 22.807 | C19H34O3 | 310.5 | 40596-69-8 | 111>55*, 153>111 | 15, 5 |
| 46 | malathion (马拉硫磷) | 22.904 | C10H19O6PS2 | 330.4 | 121-75-5 | 173>99*, 173>117 | 18, 10 |
| 47 | fenthion (倍硫磷) | 22.918 | C10H15O3PS2 | 278.3 | 55-38-9 | 278>109*, 278>125 | 20, 18 |
| 48 | cyprodinil (嘧菌环胺) | 23.094 | CHN3 | 225.3 | 121552-61-2 | 224>208*, 224>118 | 18, 40 |
| 49 | fenitrothion (杀螟硫磷) | 23.230 | C9H12NO5PS | 277.2 | 122-14-5 | 260>125*, 260>109 | 15, 10 |
| 50 | ethofumesate (乙氧呋草黄) | 23.354 | C13H18O5S | 286.3 | 26225-79-6 | 286>207*, 286>161 | 10, 20 |
| 51 | triadimefon (三唑酮) | 23.675 | C14H16ClN3O2 | 293.8 | 43121-43-3 | 208>181*, 208>127 | 10, 15 |
| 52 | pendimethalin (二甲戊灵) | 23.880 | C13H19N3O4 | 281.3 | 40487-42-1 | 251>162*, 252>118 | 10, 30 |
| 53 | parathion (对硫磷) | 23.909 | CHNO₅PS | 291.3 | 56-38-2 | 291>109*, 291>137 | 15, 10 |
| 54 | isofenphos-methyl (甲基异柳磷) | 24.003 | C14H22NO4PS | 331.4 | 99675-03-3 | 241>199*, 199>121 | 10, 10 |
| 55 | quinalphos (喹硫磷) | 24.467 | C12H15N2O3PS | 298.3 | 13593-03-8 | 298>156*, 298>129 | 10, 30 |
| 56 | isocarbophos (水胺硫磷) | 24.552 | C11H16NO4PS | 289.3 | 24353-61-5 | 230>212*, 230>197 | 5, 10 |
| 57 | propanil (敌稗) | 24.648 | C9H9Cl2NO | 218.1 | 709-98-8 | 161>90*, 161>126 | 20, 15 |
| 58 | penconazole (戊菌唑) | 24.648 | C13H15Cl2N3 | 284.2 | 66246-88-6 | 248>157*, 248>192 | 25, 15 |
| 59 | phorate sulfoxide (甲拌磷亚砜) | 25.039 | C7H17O3PS3 | 276.4 | 2588-03-6 | 199>143*, 97>65 | 10, 20 |
| 60 | phorate sulfone (甲拌磷砜) | 25.040 | C7H17O4PS3 | 292.4 | 2588-04-7 | 125>97*, 153>97 | 5, 10 |
| 61 | fenothiocarb (苯硫威) | 25.063 | C13H19NO2S | 253.4 | 62850-32-2 | 160>72*, 160>106 | 10, 12 |
| 62 | fosthiazate (噻唑膦) | 25.100 | C9H18NO3PS2 | 283.3 | 98886-44-3 | 195>103*, 195>139 | 10, 5 |
| 63 | tetraconazole (四氟醚唑) | 25.127 | C13H11Cl2F4N3O | 372.2 | 112281-77-3 | 336>218*, 336>204 | 15, 40 |
| 64 | butachlor (丁草胺) | 25.135 | C17H26ClNO2 | 311.8 | 23184-66-9 | 237>160*, 237>188 | 5, 10 |
| 65 | terbufos sulfone (特丁硫磷砜) | 25.696 | C9H21O4PS3 | 320.4 | 56070-16-7 | 153>97*, 199>97 | 10, 20 |
| 66 | triadimenol (三唑醇) | 25.805 | C14H18ClN3O2 | 295.8 | 55219-65-3 | 168>70*, 128>65 | 10, 25 |
| 67 | procymidone (腐霉利) | 25.942 | C13H11Cl2NO2 | 284.1 | 32809-16-8 | 283>96*, 283>177 | 10, 30 |
| 68 | profenofos (丙溴磷) | 26.061 | CHBrClO₃PS | 373.6 | 41198-08-7 | 339>269*, 339>251 | 10, 25 |
| 69 | methidathion (杀扑磷) | 26.101 | C6H11N2O4PS3 | 302.3 | 950-37-8 | 145>85*, 145>58 | 10, 15 |
| 70 | pretilachlor (丙草胺) | 26.150 | C17H26ClNO2 | 311.8 | 51218-49-6 | 162>147*,176>134 | 15, 15 |
| 71 | napropamide (敌草胺) | 26.156 | C17H21NO2 | 271.4 | 15299-99-7 | 271>72*, 271>128 | 10, 5 |
| 72 | hexaconazole (己唑醇) | 26.244 | C14H17Cl2N3O | 314.2 | 79983-71-4 | 214>152*, 214>124 | 25, 25 |
| 73 | oxadiazon (噁草酮) | 26.419 | C15H18Cl2N2O3 | 345.2 | 19666-30-9 | 258>175*,258>112 | 10, 25 |
| 74 | fluazifop-butyl (吡氟禾草灵) | 26.696 | C19H20F3NO4 | 383.4 | 69806-50-4 | 383>282*, 383>254 | 10, 30 |
| 75 | imazalil (抑霉唑) | 26.798 | C14H14Cl2N2O | 297.2 | 35554-44-0 | 215>173*, 215>145 | 5, 20 |
| 76 | paclobutrazol (多效唑) | 26.800 | C15H20ClN3O | 293.8 | 76738-62-0 | 236>125*, 236>132 | 10, 5 |
| 77 | isoprothiolane (稻瘟灵) | 26.956 | C12H18O4S2 | 290.4 | 50512-35-1 | 290>118*, 290>204 | 15, 10 |
| 78 | phosfolan (硫环磷) | 27.076 | C7H14NO3PS2 | 255.3 | 947-02-4 | 196>140*, 168>140 | 10, 5 |
| 79 | bupirimate (乙嘧酚磺酸酯) | 27.430 | C13H24O3N4S | 316.5 | 41483-43-6 | 273>108*, 273>150 | 18, 10 |
| 80 | oxyfluorfen (乙氧氟草醚) | 27.743 | C15H11CIF3NO4 | 361.7 | 42874-03-3 | 300>223*, 300>167 | 20, 25 |
| 81 | flutolanil (氟酰胺) | 27.885 | C17H16F3NO2 | 323.3 | 66332-96-5 | 173>145*, 281>173 | 15, 10 |
| 82 | ethion (乙硫磷) | 28.139 | C9H22O4P2S4 | 384.5 | 563-12-2 | 231>129*, 231>175 | 25, 10 |
| 83 | quinoxyfen (喹氧灵) | 28.255 | C15H8Cl2FNO | 308.1 | 124495-18-7 | 307>237*, 307>272 | 20, 10 |
| 84 | diniconazole (烯唑醇) | 28.755 | C15H17Cl2N3O | 326.2 | 83657-24-3 | 267>232*, 267>232 | 10, 10 |
| 85 | piperonyl butoxide (增效醚) | 28.765 | C19H30O5 | 338.4 | 51-03-6 | 176>131*, 176>117 | 10, 18 |
| 86 | trifloxystrobin (肟菌酯) | 28.777 | C20H19F3N2O4 | 408.4 | 141517-21-7 | 222>162*, 222>190 | 10, 5 |
| 87 | cyproconazole (环丙唑醇) | 28.845 | C15H18ClN3O | 291.8 | 94361-06-5 | 222>125*, 139>111 | 15, 15 |
| 88 | myclobutanil (腈菌唑) | 28.856 | C15H17ClN4 | 288.8 | 88671-89-0 | 179>125*, 179>129 | 15, 20 |
| 89 | benalaxyl (苯霜灵) | 28.875 | C20H23NO3 | 325.4 | 71626-11-4 | 206>132*, 206>162 | 18, 10 |
| 90 | diclofop-methyl (禾草灵) | 29.352 | C15H12Cl2O4 | 327.2 | 51338-27-3 | 253>162*, 340>253 | 15, 10 |
| 91 | edifenphos (敌瘟磷) | 29.416 | C14H15O2PS2 | 310.4 | 17109-49-8 | 173>109*, 310>173 | 10, 15 |
| 92 | fipronil (氟虫腈) | 29.424 | C12H4Cl2F6N4OS | 437.1 | 120068-37-3 | 367>213*, 367>215 | 30, 25 |
| 93 | propiconazole (丙环唑) | 29.508 | C15H17Cl2N3O2 | 342.2 | 60207-90-1 | 259>173*, 259>145 | 20, 40 |
| 94 | epoxiconazole (氟环唑) | 29.683+31.022 | C17H13ClFN3O | 329.8 | 133855-98-8 | 192>138*, 192>111 | 10, 25 |
| 95 | fenthion sulfoxide (倍硫磷亚砜) | 29.824 | C10H15O4PS2 | 294.3 | 3761-41-9 | 278>109*, 278>169 | 15, 15 |
| 96 | isazofos (氯唑磷) | 29.834 | C9H17ClN3O3PS | 313.7 | 42509-80-8 | 161>119*, 161>103 | 10, 15 |
| 97 | fenthion sulfone (倍硫磷砜) | 30.462 | C10H15O5PS2 | 310.3 | 3761-42-0 | 311>105*, 311>137 | 20, 20 |
| 98 | bromopropylate (溴螨酯) | 30.755 | C17H16Br2O3 | 428.1 | 18181-80-1 | 341>185*, 341>183 | 15, 15 |
| 99 | etoxazole (乙螨唑) | 30.931 | CHF₂NO₂ | 359.4 | 153233-91-1 | 359>187*, 359>340 | 15, 12 |
| 100 | iprodione (异菌脲) | 30.931 | C13H13Cl2N3O3 | 330.2 | 36734-19-7 | 314>245*, 314>56 | 10, 25 |
| 101 | oxadixyl (噁霜灵) | 30.995 | C14H18N2O4 | 278.3 | 77732-09-3 | 163>132*, 163>117 | 5, 25 |
| 102 | fludioxonil (咯菌腈) | 31.003 | C12H6F2N2O2 | 248.2 | 131341-86-1 | 248>182*, 248>154 | 10, 15 |
| 103 | fenpropathrin (甲氰菊酯) | 31.152 | C22H23NO3 | 349.4 | 39515-41-8 | 265>210*, 265>181 | 10, 20 |
| 104 | tebuconazole (戊唑醇) | 31.272 | C16H22ClN3O | 307.8 | 107534-96-3 | 250>125*, 250>153 | 15, 10 |
| 105 | pyriproxyfen (吡丙醚) | 31.420 | C20H19NO3 | 321.4 | 95737-68-1 | 136>96*, 131>78 | 15, 20 |
| 106 | anilofos (莎稗磷) | 31.420 | C13H19ClNO3PS2 | 367.9 | 64249-01-0 | 226>157*, 226>157 | 15, 10 |
| 107 | fenamidone (咪唑菌酮) | 32.206 | C17H17N3OS | 311.4 | 161326-34-7 | 238>237*, 268>180 | 10, 20 |
| 108 | pyridaphenthion (哒嗪硫磷) | 32.210 | C14H17N2O4PS | 340.3 | 119-12-0 | 340>199*, 340>109 | 10, 20 |
| 109 | phosmet (亚胺硫磷) | 32.436 | C11H12NO4PS2 | 317.3 | 732-11-6 | 160>77*, 160>105 | 25, 18 |
| 110 | bifenox (甲羧除草醚) | 32.642 | C14H9Cl2NO5 | 342.1 | 42576-02-3 | 341>189*, 341>281 | 20, 20 |
| 111 | tetradifon (三氯杀螨砜) | 32.655 | C12H6Cl4O2S | 356.1 | 116-29-0 | 229>201*, 229>16 | 15, 20 |
| 112 | lambda-cyhalothrin (高效氯氟氰菊酯) | 33.090+33.461 | C23H19ClF3NO3 | 449.9 | 91465-08-6 | 181>152*, 181>127 | 20, 30 |
| 113 | phosalone (伏杀硫磷) | 33.479 | C12H15ClNO4PS2 | 367.8 | 2310-17-0 | 367>182*, 367>111 | 10, 30 |
| 114 | permethrin (氯菊酯) | 33.765 | C21H20Cl2O3 | 391.3 | 52645-53-1 | 183>168*, 183>152 | 10, 20 |
| 115 | mefenacet (苯噻酰草胺) | 33.825 | C16H14N2O2S | 298.4 | 73250-68-7 | 192>136*, 192>109 | 15, 30 |
| 116 | fenarimol (氯苯嘧啶醇) | 33.849 | C17H12Cl2N2O | 331.2 | 60168-88-9 | 330>139*, 330>111 | 10, 30 |
| 117 | pyridaben (哒螨灵) | 34.271 | C19H25ClN2OS | 364.9 | 96489-71-3 | 309>147*, 309>132 | 12, 25 |
| 118 | coumaphos (蝇毒磷) | 36.824 | C14H16ClO5PS | 362.8 | 56-72-4 | 362>109*, 362>226 | 15, 15 |
| 119 | cyfluthrin (氟氯氰菊酯) | 37.053 | CHCl₂FNO3 | 434.3 | 68359-37-5 | 206>151*, 206>177 | 15, 20 |
| 120 | cypermethrin (氯氰菊酯) | 37.089 | C22H19Cl2NO3 | 416.3 | 52315-07-8 | 163>91*, 163>127 | 10, 5 |
| 121 | flucythrinate (氟氰戊菊酯) | 37.930 | C26H23F2NO4 | 451.5 | 70124-77-5 | 225>147*, 225>118 | 10, 25 |
| 122 | fenvalerate (氰戊菊酯) | 40.018 | CHClNO3 | 419.9 | 51630-58-1 | 225>119*, 225>91 | 18, 25 |
| 123 | fluvalinate (氟胺氰菊酯) | 41.132 | CHClF3N2O3 | 502.9 | 102851-06-9 | 250>55*, 250>200 | 20, 20 |
| 124 | difenoconazole (苯醚甲环唑) | 41.782 | C19H17Cl2N3O3 | 406.3 | 119446-68-3 | 323>265*, 323>201 | 15, 30 |
| 125 | deltamethrin (溴氰菊酯) | 42.334 | C22H19Br2NO3 | 505.2 | 52918-63-5 | 253>172*, 253>199 | 10, 25 |
Fig. 1 Quantitative distribution of the 125 pesticides in Dendrobium officinale flowers extracted with different solvents in different recovery ranges
Fig. 2 Photos of solutions after purification using five purification methods1. unpurified; 2. Sin-QuEChERS Nano; 3. MPFC-QuEChERS;4. M-PFC C; 5. M-PFC TD-1; 6. d-SPE.
Fig. 3 Total ion chromatograms in full scan mode of the Dendrobium officinale flower extracts cleaned up by different purification methodsa. unpurified; b. d-SPE; c. Sin-QuEChERS Nano; d. M-PFC TD-1; e. M-PFC C; f. MPFC-QuEChERS.
Matrix effect/% | 100 μg/kg | 10 μg/kg | ||||||||||
|---|---|---|---|---|---|---|---|---|---|---|---|---|
| Unpurified | Sin-QuEChERS Nano | MPFC-QuEChERS | M-PFC C | M-PFC TD-1 | d-SPE | Unpurified | Sin-QuEChERS Nano | MPFC-QuEChERS | M-PFC C | M-PFC TD-1 | d-SPE | |
| 0-100.0 | 8 | 7 | 10 | 7 | 11 | 9 | 5 | 6 | 8 | 11 | 9 | 10 |
| 100.0-121.0 | 7 | 5 | 15 | 15 | 38 | 24 | 9 | 18 | 17 | 23 | 35 | 25 |
| 121.0-151.0 | 14 | 54 | 57 | 65 | 56 | 63 | 24 | 50 | 54 | 55 | 53 | 58 |
| 151.0-201.0 | 80 | 45 | 35 | 29 | 18 | 26 | 74 | 41 | 43 | 34 | 27 | 31 |
| 201.0-300.0 | 16 | 14 | 8 | 9 | 2 | 3 | 13 | 10 | 3 | 2 | 1 | 1 |
Table 2 Distribution of the 125 pesticides in Dendrobium officinale flowers across different matrix effect ranges with five purification methods
Matrix effect/% | 100 μg/kg | 10 μg/kg | ||||||||||
|---|---|---|---|---|---|---|---|---|---|---|---|---|
| Unpurified | Sin-QuEChERS Nano | MPFC-QuEChERS | M-PFC C | M-PFC TD-1 | d-SPE | Unpurified | Sin-QuEChERS Nano | MPFC-QuEChERS | M-PFC C | M-PFC TD-1 | d-SPE | |
| 0-100.0 | 8 | 7 | 10 | 7 | 11 | 9 | 5 | 6 | 8 | 11 | 9 | 10 |
| 100.0-121.0 | 7 | 5 | 15 | 15 | 38 | 24 | 9 | 18 | 17 | 23 | 35 | 25 |
| 121.0-151.0 | 14 | 54 | 57 | 65 | 56 | 63 | 24 | 50 | 54 | 55 | 53 | 58 |
| 151.0-201.0 | 80 | 45 | 35 | 29 | 18 | 26 | 74 | 41 | 43 | 34 | 27 | 31 |
| 201.0-300.0 | 16 | 14 | 8 | 9 | 2 | 3 | 13 | 10 | 3 | 2 | 1 | 1 |
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Abstract 107
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