1. 前处理方法
1.1 样品提取
称取10 g已均质好的白菜样品,置于50 ml 离心管中,加入10 ml乙腈,加入4颗玻璃珠均质子,再加入mas-q提取包(ms-nms5050),剧烈震荡1 min,8000 r/min离心5 min,取上层清液1 ml做为待净化液。
1.2 样品净化
将上述1 ml待净化液加入mas-quechers净化管(ms-pa0251)中,涡旋振荡1 min,8000 r/min离心5 min,取上层清液适量过0.22 µm针式过滤器,供lc/ms/ms检测。
1.3 基质混合标准工作溶液配制
取高浓度农药混合标准溶液,用空白样品基质溶液稀释成0.05 µg/ml的基质混合标准工作溶液。
2. 实验条件
液相条件
色谱柱:venusil asb c18,5 μm,150 å,2.1 × 150 mm
流动相:a: 0.1%甲酸水溶液;b: 0.1%甲酸乙腈,使用前经微孔滤膜过滤
柱 温:30℃
进样量:10 µl
质谱条件
离子源:esi ;电喷雾电压:5500 v;雾化气压力:50 psi;气帘气压力: 15 psi;辅助气压力:50 psi;离子源温度:400℃;采集方式:多反应监测(mrm)。
梯度洗脱:见表1
表1. 液相色谱梯度洗脱条件
时间/min | 流速/(ml/min) | a/% | b/% |
0.00 | 0.30 | 99 | 1 |
3.00 | 0.30 | 70 | 30 |
6.00 | 0.30 | 60 | 40 |
9.00 | 0.30 | 60 | 40 |
15.00 | 0.30 | 40 | 60 |
19.00 | 0.30 | 1 | 99 |
23.00 | 0.30 | 1 | 99 |
23.01 | 0.30 | 99 | 1 |
40.00 | 0.30 | 99 | 1 |
质谱参数:见表2
表2. 105种农药质谱参数
物质名称 | q1 | q3 | dp/v | ce/v |
氧环唑 (azaconazole) | 300 | 231 | 106 | 25 |
159 | 101 | 25 | ||
甲基吡恶磷 (azamethiphos) | 325 | 183 | 106 | 23 |
139 | 96 | 23 | ||
四唑嘧磺隆 (azimsulfuron) | 425 | 182 | 86 | 23 |
156 | 86 | 23 | ||
地散磷 (bensulide) | 398 | 158 | 121 | 33 |
314 | 136 | 33 | ||
唑草胺/苯酮唑 (cafenstrole) | 351 | 100 | 71 | 15 |
72 | 71 | 15 | ||
氯草敏 (chloridazon) | 222 | 104 | 96 | 37 |
77 | 101 | 37 | ||
氯嘧磺隆 (chlorimuron-ethyl) | 415 | 314 | 51 | 23 |
218 | 51 | 23 | ||
枯草隆 (chloroxuron) | 291 | 218 | 96 | 35 |
72 | 101 | 35 | ||
吲哚酮草酯 (cinidon-ethyl) | 394 | 348 | 101 | 27 |
107 | 101 | 27 | ||
醚黄隆 (cinosulfuron) | 414 | 183 | 96 | 33 |
157 | 96 | 33 | ||
四螨嗪 (clofentezine) | 303 | 138 | 96 | 21 |
102 | 96 | 21 | ||
二苯隆 (cumyluron) | 303 | 185 | 96 | 19 |
125 | 96 | 19 | ||
环丙嘧磺隆 (cyclosulfamuron) | 422 | 261 | 76 | 25 |
218 | 151 | 25 | ||
除虫脲 (diflubenzuron) | 311 | 158 | 56 | 19 |
141 | 56 | 19 | ||
吡氟酰草胺 (diflufenican) | 395 | 266 | 91 | 35 |
246 | 96 | 35 | ||
呋虫胺 (dinotefuran) | 203 | 129 | 56 | 17 |
87 | 56 | 17 | ||
乙虫腈 (ethiprole) | 397 | 351 | 96 | 29 |
255 | 96 | 49 | ||
苯线磷 (fenamiphos) | 304 | 217 | 96 | 31 |
202 | 96 | 47 | ||
腈苯唑 (fenbuconazole) | 337 | 125 | 96 | 43 |
70 | 96 | 41 | ||
丰索磷 (fensulfothion) | 309 | 253 | 86 | 25 |
157 | 91 | 33 | ||
氟噻甲草酯 (fluthiacet-methyl) | 404 | 215 | 111 | 57 |
274 | 121 | 41 | ||
氯吡脲 (forchlorfenuron) | 248 | 129 | 86 | 23 |
93 | 86 | 47 | ||
福拉比 (furametpyr) | 334 | 157 | 101 | 45 |
290 | 116 | 25 | ||
氯吡嘧磺隆 (halosulfuron methyl) | 435 | 182 | 106 | 29 |
92 | 111 | 29 | ||
氟铃脲 (hexaflumuron) | 461 | 158 | 106 | 25 |
141 | 101 | 63 | ||
咪草酸甲酯 (imazamethabenz methyl) | 289 | 229 | 161 | 29 |
86 | 161 | 33 | ||
亚胺唑 (imibenconazole) | 411 | 125 | 61 | 41 |
342 | 71 | 23 | ||
异噁隆 (isouron) | 212 | 72 | 36 | 35 |
167 | 36 | 12 | ||
双苯恶唑酸 (isoxadifen-ethyl) | 296 | 232 | 76 | 23 |
105 | 76 | 33 | ||
噁唑磷 (isoxathion) | 314 | 170 | 76 | 21 |
113 | 71 | 39 | ||
氟吗啉 (flumorph) | 372 | 165 | 56 | 43 |
123 | 56 | 47 | ||
氟啶虫酰胺 (flonicamid) | 230 | 203 | 71 | 25 |
174 | 71 | 27 | ||
双炔酰菌胺 (mandipropamid) | 412 | 328 | 76 | 21 |
125 | 76 | 45 | ||
环草定 (lenacil) | 235 | 153 | 71 | 23 |
136 | 71 | 45 | ||
苯噻酰草胺 (mefenacet) | 299 | 148 | 111 | 21 |
120 | 111 | 37 | ||
氧化萎锈灵 (oxycarboxin) | 268 | 175 | 61 | 21 |
147 | 61 | 33 | ||
戊菌隆 (pencycuron) | 329 | 125 | 61 | 37 |
218 | 106 | 23 | ||
吡唑硫磷 (pyraclofos) | 361 | 257 | 101 | 37 |
140 | 101 | 37 | ||
吡唑醚菌酯 (pyraclostrobin) | 388 | 163 | 56 | 35 |
194 | 56 | 35 | ||
苄草唑 (pyrazoxyfen) | 404 | 91 | 81 | 61 |
105 | 76 | 61 | ||
乙黄隆 (sulfosulfuron) | 471 | 218 | 116 | 39 |
156 | 116 | 39 | ||
丁噻隆 (tebuthiuron) | 229 | 172 | 76 | 25 |
116 | 76 | 25 | ||
噻苯隆 (thidiazuron) | 221 | 102 | 56 | 23 |
182 | 61 | 23 | ||
三甲苯草酮 (tralkoxydim) | 330 | 284 | 76 | 19 |
138 | 76 | 19 | ||
杀铃脲 (triflumuron) | 359 | 156 | 116 | 25 |
139 | 80 | 35 | ||
酰嘧磺隆 (amidosulfuron) | 370 | 261 | 56 | 21 |
279 | 56 | 17 | ||
仲丁灵 (butralin) | 296 | 240 | 36 | 19 |
222 | 36 | 31 | ||
氯虫苯甲酰胺 (chlorantraniliprole) | 484 | 453 | 51 | 21 |
286 | 56 | 19 | ||
绿麦隆 (chlortoluron) | 213 | 72 | 76 | 35 |
140 | 86 | 33 | ||
蝇毒磷 (coumaphos) | 363 | 227 | 56 | 35 |
307 | 46 | 25 | ||
内吸磷 (demeton2) | 259 | 61 | 31 | 47 |
89 | 31 | 17 | ||
双氟磺草胺 (florasulam) | 360 | 129 | 91 | 35 |
192 | 91 | 35 | ||
氟虫双酰胺 (flubendiamide) | 683 | 408 | 61 | 13 |
274 | 56 | 13 | ||
氟唑磺隆 (flucarbazone-sodium) | 419 | 341 | 121 | 21 |
152 | 116 | 21 | ||
氟吡菌胺 (fluopicolide) | 383 | 173 | 91 | 31 |
305 | 91 | 31 | ||
氟吡乙禾灵 (haloxyfop-r-methyl) | 376 | 316 | 46 | 25 |
91 | 41 | 25 | ||
硫环磷 (phosfolan) | 256 | 140 | 71 | 33 |
228 | 71 | 33 | ||
异丙草胺 (propisochlor) | 284 | 224 | 61 | 15 |
212 | 61 | 15 | ||
烯禾定 (sethoxydim) | 328 | 178 | 71 | 27 |
282 | 81 | 27 | ||
乙基多杀菌素 (spinetoram) | 748 | 142 | 116 | 41 |
374 | 136 | 41 | ||
螺甲螨酯 (spiromesifen) | 371 | 273 | 46 | 33 |
255 | 46 | 33 | ||
螺虫乙酯 (spirotetramat) | 374 | 216 | 46 | 47 |
173 | 46 | 47 | ||
双硫磷 (temephos) | 467 | 125 | 51 | 37 |
155 | 111 | 37 | ||
鱼藤酮 (rotenone) | 395 | 192 | 101 | 33 |
213 | 111 | 33 | ||
啶虫脒 (acetamiprid) | 223 | 126 | 66 | 29 |
56 | 66 | 29 | ||
涕灭威 (aldicarb) | 213 | 89 | 56 | 23 |
116 | 61 | 23 | ||
涕灭砜威 (aldicarb-sulfone) | 223 | 148 | 71 | 13 |
76 | 71 | 13 | ||
涕灭威亚砜 (aldicarb-sulfoxide) | 207 | 132 | 56 | 11 |
89 | 56 | 11 | ||
嘧菌酯 (azoxystrobin) | 404 | 372 | 51 | 21 |
344 | 51 | 21 | ||
啶酰菌胺 (boscalid) | 343 | 307 | 41 | 29 |
140 | 36 | 29 | ||
多菌灵 (carbendazim) | 192 | 160 | 81 | 27 |
132 | 86 | 27 | ||
3-羟基克百威 (carbofuran-3-hydroxy) | 238 | 163 | 61 | 21 |
107 | 61 | 21 | ||
灭幼脲 (chlorbenzuron) | 309 | 156 | 76 | 21 |
139 | 76 | 21 | ||
噻虫胺 (clothianidin) | 250 | 169 | 31 | 19 |
132 | 31 | 23 | ||
氰草津 (cyanazine) | 241 | 132 | 46 | 35 |
174 | 36 | 35 | ||
霜脲氰 (cymoxanil) | 199 | 128 | 51 | 13 |
111 | 56 | 13 | ||
乐果 (dimethoate) | 230 | 199 | 31 | 15 |
171 | 31 | 15 | ||
敌瘟磷 (edifenphos) | 311 | 283 | 81 | 19 |
109 | 81 | 19 | ||
环酰菌胺 (fenhexamid) | 302 | 97 | 76 | 33 |
55 | 76 | 33 | ||
苯氧威 (fenoxycarb) | 302 | 116 | 76 | 17 |
88 | 81 | 17 | ||
唑螨酯 (fenpyroximate) | 422 | 135 | 51 | 45 |
336 | 61 | 45 | ||
氟虫脲 (flufenoxuron) | 489 | 158 | 40 | 30 |
141 | 40 | 30 | ||
氟线威 (furathiocarb) | 383 | 195 | 91 | 25 |
252 | 91 | 19 | ||
抑霉唑 (imazalil) | 298 | 159 | 156 | 31 |
255 | 156 | 25 | ||
茚虫威 (indoxacarb) | 528 | 218 | 41 | 31 |
150 | 41 | 33 | ||
缬霉威 (iprovalicarb) | 321 | 119 | 66 | 25 |
203 | 71 | 13 | ||
异丙隆 (isoproturon) | 207 | 72 | 86 | 31 |
165 | 86 | 21 | ||
利谷隆 (linuron) | 249 | 160 | 56 | 25 |
182 | 56 | 21 | ||
苯嗪草酮 (metamitron) | 203 | 132 | 86 | 45 |
65 | 91 | 61 | ||
甲硫威 (methiocarb) | 226 | 169 | 56 | 13 |
121 | 56 | 25 | ||
甲氧虫酰肼 (methoxyfenozide) | 369 | 149 | 56 | 23 |
133 | 51 | 35 | ||
异丙甲草胺 (metolachlor) | 284 | 252 | 66 | 21 |
176 | 66 | 35 | ||
氧乐果 (omethoate) | 214 | 125 | 61 | 31 |
183 | 61 | 31 | ||
磷胺 (phosphamidon ) | 300 | 174 | 51 | 19 |
127 | 51 | 19 | ||
咪鲜胺 (prochloraz) | 377 | 308 | 46 | 25 |
70 | 46 | 25 | ||
猛杀威 (promecarb) | 208 | 109 | 61 | 23 |
151 | 61 | 23 | ||
喹禾灵 (quizalofop-ethyl) | 373 | 299 | 46 | 27 |
74 | 46 | 27 | ||
虫酰肼 (tebufenozide) | 353 | 133 | 96 | 27 |
297 | 96 | 13 | ||
噻菌灵 (thiabendazole) | 202 | 175 | 116 | 37 |
131 | 116 | 47 | ||
硫双灭多威 (thiodicarb) | 355 | 88 | 71 | 21 |
108 | 81 | 21 | ||
久效威砜 (thiofanox-sulfone) | 251 | 57 | 61 | 11 |
76 | 61 | 11 | ||
久效威亚砜 (thiofanox-sulfoxide) | 235 | 57 | 61 | 27 |
104 | 61 | 27 | ||
醚苯磺隆 (triasulfuron) | 402 | 141 | 51 | 29 |
167 | 51 | 29 | ||
敌百虫 (trichlorfon) | 259 | 127 | 96 | 25 |
109 | 91 | 25 | ||
蚜灭磷 (vamidothion) | 288 | 118 | 89 | 21 |
86 | 81 | 21 |
3. 实验结果
表3.白菜基质加标回收实验结果(添加水平0.05 mg/kg)
物质名称 | 平均回收率/% | rsd/% | 物质名称 | 平均回收率/% | rsd/% |
氧环唑 | 109.9 | 19.2 | 氟唑磺隆 | 66.4 | 12.1 |
(azaconazole) | (flucarbazone-sodium) | ||||
甲基吡恶磷 | 112.0 | 6.4 | 氟吡菌胺 | 83.6 | 3.1 |
(azamethiphos) | (fluopicolide) | ||||
四唑嘧磺隆 | 74.2 | 11.2 | 氟吡乙禾灵 | 101.2 | 4.9 |
(azimsulfuron) | (haloxyfop-r-methyl) | ||||
地散磷 | 88.7 | 7.5 | 硫环磷 | 100.2 | 15.9 |
(bensulide) | (phosfolan) | ||||
唑草胺/苯酮唑 | 84.1 | 13.8 | 异丙草胺 | 92.9 | 14.4 |
(cafenstrole) | (propisochlor) | ||||
氯草敏 | 91.5 | 14.5 | 烯禾定 | 92.8 | 15.2 |
(chloridazon) | (sethoxydim) | ||||
氯嘧磺隆 | 98.0 | 17.0 | 乙基多杀菌素 | 95.4 | 19.3 |
(chlorimuron-ethyl) | (spinetoram) | ||||
枯草隆 | 98.3 | 6.4 | 螺甲螨酯 | 95.8 | 10.5 |
(chloroxuron) | (spiromesifen) | ||||
吲哚酮草酯 | 99.2 | 13.2 | 螺虫乙酯 | 96.8 | 10.7 |
(cinidon-ethyl) | (spirotetramat) | ||||
醚黄隆 | 79.5 | 4.3 | 双硫磷 | 91.8 | 4.8 |
(cinosulfuron) | (temephos) | ||||
四螨嗪 | 98.9 | 13.3 | 鱼藤酮 | 100.4 | 1.6 |
(clofentezine) | (rotenone) | ||||
二苯隆 | 106.6 | 11.2 | 啶虫脒 | 82.2 | 14.8 |
(cumyluron) | (acetamiprid) | ||||
环丙嘧磺隆 | 73.4 | 6.2 | 涕灭威 | 96.6 | 16.4 |
(cyclosulfamuron) | (aldicarb) | ||||
除虫脲 | 77.6 | 16.3 | 涕灭砜威 | 106.6 | 7.1 |
(diflubenzuron) | (aldicarb-sulfone) | ||||
吡氟酰草胺 | 104.3 | 6.8 | 涕灭威亚砜 | 108.4 | 11.7 |
(diflufenican) | (aldicarb-sulfoxide) | ||||
呋虫胺 | 68.4 | 3.1 | 嘧菌酯 | 93.2 | 4.0 |
(dinotefuran) | (azoxystrobin) | ||||
乙虫腈 | 99.3 | 15.3 | 啶酰菌胺 | 95.4 | 10.4 |
(ethiprole) | (boscalid) | ||||
苯线磷 | 107.1 | 12.7 | 多菌灵 | 93.2 | 3.5 |
(fenamiphos) | (carbendazim) | ||||
腈苯唑 | 100.4 | 5.8 | 3-羟基克百威 | 91.6 | 2.2 |
(fenbuconazole) | (carbofuran-3-hydroxy) | ||||
丰索磷 | 70.9 | 17.7 | 灭幼脲 | 100.4 | 15.8 |
(fensulfothion) | (chlorbenzuron) | ||||
氟噻甲草酯 | 94.4 | 4.8 | 噻虫胺 | 89.4 | 5.9 |
(fluthiacet-methyl) | (clothianidin) | ||||
氯吡脲 | 76.7 | 12.1 | 氰草津 | 88.6 | 7.0 |
(forchlorfenuron) | (cyanazine) | ||||
福拉比 | 103.7 | 19.5 | 霜脲氰 | 108.6 | 7.9 |
(furametpyr) | (cymoxanil) | ||||
氯吡嘧磺隆 | 93.7 | 16.2 | 乐果 | 90.5 | 9.9 |
(halosulfuron methyl) | (dimethoate) | ||||
氟铃脲 | 82.1 | 4.1 | 敌瘟磷 | 96.7 | 0.7 |
(hexaflumuron) | (edifenphos) | ||||
咪草酸甲酯 | 108.6 | 13.7 | 环酰菌胺 | 90.7 | 18.9 |
(imazamethabenz methyl) | (fenhexamid) | ||||
亚胺唑 | 83.7 | 16.1 | 苯氧威 | 96.3 | 12.2 |
(imibenconazole) | (fenoxycarb) | ||||
异噁隆 | 88.1 | 15.3 | 唑螨酯 | 93.4 | 7.5 |
(isouron) | (fenpyroximate) | ||||
双苯恶唑酸 | 101.6 | 14.8 | 氟虫脲 | 87.5 | 1.4 |
(isoxadifen-ethyl) | (flufenoxuron) | ||||
噁唑磷 | 88.3 | 14.4 | 氟线威 | 91.6 | 14.7 |
(isoxathion) | (furathiocarb) | ||||
氟吗啉 | 100.5 | 13.0 | 抑霉唑 | 79.7 | 14.8 |
(flumorph) | (imazalil) | ||||
氟啶虫酰胺 | 100.5 | 9.8 | 茚虫威 | 97.5 | 15.0 |
(flonicamid) | (indoxacarb) | ||||
双炔酰菌胺 | 87.4 | 1.3 | 缬霉威 | 97.4 | 11.3 |
(mandipropamid) | (iprovalicarb) | ||||
环草定 | 87.2 | 7.6 | 异丙隆 | 75.8 | 13.7 |
(lenacil) | (isoproturon) | ||||
苯噻酰草胺 | 102.6 | 5.8 | 利谷隆 | 81.5 | 8.8 |
(mefenacet) | (linuron) | ||||
氧化萎锈灵 | 104.5 | 12.7 | 苯嗪草酮 | 84.6 | 11.6 |
(oxycarboxin) | (metamitron) | ||||
戊菌隆 | 112.5 | 6.4 | 甲硫威 | 68.0 | 12.6 |
(pencycuron) | (methiocarb) | ||||
吡唑硫磷 | 111.1 | 5.5 | 甲氧虫酰肼 | 101.8 | 6.8 |
(pyraclofos) | (methoxyfenozide) | ||||
吡唑醚菌酯 | 100.0 | 7.5 | 异丙甲草胺 | 103.7 | 9.9 |
(pyraclostrobin) | (metolachlor) | ||||
苄草唑 | 101.5 | 10.6 | 氧乐果 | 109.4 | 11.5 |
(pyrazoxyfen) | (omethoate) | ||||
乙黄隆 | 66.2 | 5.1 | 磷胺 | 107.2 | 12.3 |
(sulfosulfuron) | (phosphamidon) | ||||
丁噻隆 | 90.4 | 5.5 | 咪鲜胺 | 92.7 | 22.0 |
(tebuthiuron) | (prochloraz) | ||||
噻苯隆 | 85.5 | 9.6 | 猛杀威 | 79.3 | 17.8 |
(thidiazuron) | (promecarb) | ||||
三甲苯草酮 | 82.7 | 11.0 | 喹禾灵 | 89.6 | 14.0 |
(tralkoxydim) | (quizalofop-ethyl) | ||||
杀铃脲 | 103.6 | 8.4 | 虫酰肼 | 98.2 | 8.5 |
(triflumuron) | (tebufenozide) | ||||
酰嘧磺隆 | 110.1 | 4.1 | 噻菌灵 | 96.9 | 10.0 |
(amidosulfuron) | (thiabendazole) | ||||
仲丁灵 | 96.5 | 11.3 | 硫双灭多威 | 103.9 | 10.2 |
(butralin) | (thiodicarb) | ||||
氯虫苯甲酰胺 | 115.4 | 17.9 | 久效威砜 | 104.5 | 13.9 |
(chlorantraniliprole) | (thiofanox-sulfone) | ||||
绿麦隆 | 67.5 | 19.4 | 久效威亚砜 | 81.7 | 11.9 |
(chlortoluron) | (thiofanox-sulfoxide) | ||||
蝇毒磷 | 116.2 | 2.4 | 醚苯磺隆 | 69.2 | 15.8 |
(coumaphos) | (triasulfuron) | ||||
内吸磷 | 109.1 | 10.5 | 敌百虫 | 82.1 | 13.8 |
(demeton2) | (trichlorfon) | ||||
双氟磺草胺 | 68.7 | 10.5 | 蚜灭磷 | 108.2 | 5.7 |
(florasulam) | (vamidothion) | ||||
氟虫双酰胺 | 116.5 | 3.0 | |||
(flubendiamide) |
实验谱图
图1. 0.05 μg/ml混合标准工作溶液lc/ms/ms色谱图
图2.白菜基质空白lc/ms/ms色谱图
图3. 0.05 μg/ml白菜基质混合标准工作液lc/ms/ms色谱图
图4. 0.05 mg/kg白菜基质加标lc/ms/ms色谱图
4. 结论
本实验根据en 15662:2008,结合高效液相色谱串联质谱方法进行测定,对加标量为0.05 mg/kg的白菜样品进行了检测。结果表明,105种农药加标回收率在60% ~ 120%, rsd小于20%。 quechers方法较传统方法更为简便,样品处理时间短,可以用于测定白菜中的农药残留。
5. 订货信息
产品名称 | 规格描述 | 包装数量 | 订货号 |
蔬菜水果农残检测mas-q提取管 | 50 ml离心管 | 50支/包 | ms-nms5050 |
简单基质蔬菜水果农残检测mas-q净化管 | 2 ml离心管 | 100支/包 | ms-pa0251 |
玻璃珠均质子 | 直径10 mm | 50个/包 | hg-01 |
1.5 ml样品瓶 | 短螺纹透明带书写处 32 × 11.6 mm | 100/pk | 1109-0519 |
1.5 ml样品瓶盖 | 9 mm中心孔蓝盖,红色橡胶/米色ptfe隔垫 45°shore a; 1.0 mm | 100/pk | 0915-1819 |
尼龙针式过滤器 | 单膜,13 mm,0.22 µm | 200个/包 | as021320 |
一次性注射器 | 2 ml无针头 | 100支/包 | lzsq-2ml |
乙腈 | 4 l/瓶,色谱纯 | 4 × 4 l/箱 | ah015-4 |
应用编号:af10056