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超高效液相色谱-四极杆-飞行时间质谱法快速筛查香橼中180种农药残留

陈婷 张文 刘光瑞 朱仁愿 闫君 王行智 戚鹏飞 陈敏

陈婷, 张文, 刘光瑞, 朱仁愿, 闫君, 王行智, 戚鹏飞, 陈敏. 超高效液相色谱-四极杆-飞行时间质谱法快速筛查香橼中180种农药残留[J]. 农药学学报. doi: 10.16801/j.issn.1008-7303.2021.0188
引用本文: 陈婷, 张文, 刘光瑞, 朱仁愿, 闫君, 王行智, 戚鹏飞, 陈敏. 超高效液相色谱-四极杆-飞行时间质谱法快速筛查香橼中180种农药残留[J]. 农药学学报. doi: 10.16801/j.issn.1008-7303.2021.0188
CHEN Ting, ZHANG Wen, LIU Guangrui, ZHU Renyuan, YAN Jun, WANG Xingzhi, QI Pengfei, CHEN Min. Rapid screening of 180 pesticide residues in Fructus Citri by ultra performance liquid chromatography coupled with quadrupole-time of flight mass spectrometry[J]. Chinese Journal of Pesticide Science. doi: 10.16801/j.issn.1008-7303.2021.0188
Citation: CHEN Ting, ZHANG Wen, LIU Guangrui, ZHU Renyuan, YAN Jun, WANG Xingzhi, QI Pengfei, CHEN Min. Rapid screening of 180 pesticide residues in Fructus Citri by ultra performance liquid chromatography coupled with quadrupole-time of flight mass spectrometry[J]. Chinese Journal of Pesticide Science. doi: 10.16801/j.issn.1008-7303.2021.0188

超高效液相色谱-四极杆-飞行时间质谱法快速筛查香橼中180种农药残留

doi: 10.16801/j.issn.1008-7303.2021.0188
基金项目: 甘肃省药品监督管理局青年科技创新项目(2020GSMPA014);甘肃省市场监督管理局科技计划项目(SSCJG-SP-201910);国家市场监督管理总局科技计划项目 (2021MK110).
详细信息
    通讯作者:

    125731803@qq.com

  • 中图分类号: TQ450.2;O657.72;X592

Rapid screening of 180 pesticide residues in Fructus Citri by ultra performance liquid chromatography coupled with quadrupole-time of flight mass spectrometry

  • 摘要: 建立了QuEChERS法结合超高效液相色谱-四极杆-飞行时间质谱 (UPLC-Q-TOF/MS)快速筛查香橼中180种农药多残留的方法。通过优化样品前处理净化方式及保留时间窗口、精确质量数提取窗口和绝对峰面积阈值 (peak filter)等主要检索参数,建立了精确质量数数据库和高分辨碎片离子谱图库,并对筛查方法的定性及定量结果进行了验证。结果表明:在0.005~1 mg/L质量浓度范围内,180种农药在香橼中的线性关系良好( r>0.99),其中96.6 %的农药筛查限 (SDLs)均低于0.05 mg/kg。在0.02、0.05和0.1 mg/kg 3个添加水平下,180种农药在香橼中的平均回收率分别为58%~129%,68%~131%和66%~132%,相对标准偏差 (RSD)在0.7%~18% (n=5)之间。该方法利用TOF-MS一级精确质荷比筛查并结合高分辨碎片质谱图确证,提高了多农药残留快速筛查的准确性,有效降低了假阳性率,对中药材香橼中农药残留的日常监测具有普遍适用性。
  • 图  1  不同净化方式对香橼中15种农药回收率的影响

    Figure  1.  Effects of cleanup sorbent combinations on recoveries of 15 pesticides in Fructus Citro

    图  2  不同净化方式对香橼中 15种农药响应值的影响

    Figure  2.  Effects of different purification methods on response values of 15 pesticides in Fructus Citri

    图  3  不同精确质量数窗口下提取乙螨唑 (m/z=304.11322) 离子的结果

    Figure  3.  Extracted ion chromatogram of etoxazole at different mass width (m/z=304.11322)

    图  4  检出样品中甲拌磷亚砜的色谱图和质谱图

    Figure  4.  Chromatogram and mass spectra of phorate sulfoxide in positive sample

    表  1  180种农药的保留时间、基质效应及质谱信息

    Table  1.   Retention times,matrix effects and mass parameters of 180 pesticides

    No.化合物
    Compound
    保留时间
    Retention time/min
    理论质量数
    Theoretical mass,
    m/z
    实测质量数
    Measured mass,
    m/z
    产物离子
    Product ion,
    m/z
    质量误差
    Mass
    error/ppm
    基质效应
    Matrix
    effect/%
    1 涕灭威 aldicarb* 4.75 190.0776 190.0780 116.0528, 89.0420 2.1 138
    2 莠灭净 ametryn 7.05 227.1205 227.1214 186.0808, 96.0556 4.0 141
    3 酰嘧磺隆 amidosulfuron 6.17 369.0413 369.0410 261.0288, 218.0230 −0.8 150
    4 灭害威 aminocarb 2.33 208.1212 208.1210 152.1069, 137.0835 −1.0 123
    5 环丙嘧啶醇 ancymidol 5.32 256.1212 256.1208 135.0440, 81.0447 −1.6 126
    6 莠去通 atraton 4.63 211.1433 211.1430 170.1036, 100.0505 −1.4 99
    7 氟氯氰菊酯 cyfluthrin 3.05 173.0468 173.0466 132.0323, 96.0556 −1.2 121
    8 保棉磷 azinphos-methyl 9.63 317.0058 317.0062 132.0444, 77.0389 1.3 126
    9 苯霜灵 benalaxyl 14.23 325.1678 325.1675 208.1332, 148.1120 −0.9 168
    10 麦锈灵 benodanil 8.51 322.9807 322.9811 230.9301, 202.9352 1.2 135
    11 地散磷 bensulide 15.32 397.0605 397.0610 218.0304, 158.0270 1.3 138
    12 新燕灵 benzoylprop-ethyl 15.36 365.0586 365.0585 320.0239.105.0335 −0.3 169
    13 联苯三唑醇 bitertanol 12.88 337.1790 337.1781 99.0804, 70.0399 −2.7 92
    14 啶酰菌胺 boscalid 11.26 342.0327 342.0324 271.0865, 139.9898 −0.9 123
    15 除草定 bromacil 4.93 260.0160 260.0155 204.9607, 161.9549 −1.9 195
    16 溴丁酰草胺 bromobutide 13.92 311.0885 311.0879 194.0175, 119.0855 −1.9 138
    17 乙嘧酚磺酸酯 bupirimate 12.96 316.1569 316.1555 317.1641, 272.1063 −4.4 147
    18 氟丙嘧草酯 butafenacil# 14.33 474.0806 474.0804 331.0091, 127.0753 −0.4 136
    19 抑草磷 butamifos 16.62 332.0960 332.0954 152.0293, 95.9667 −1.8 133
    20 唑草胺 cafenstrole 12.94 350.1413 350.1412 100.0756, 72.0443 −0.3 173
    21 环丙酰菌胺 carpropamid 14.77 333.0454 333.0460 139.0309, 81.0698 1.8 107
    22 萎锈灵 carboxin 6.63 235.0667 235.0666 208.0426, 143.0161 −0.4 139
    23 氯草敏 chloridazon 3.74 221.0356 221.0351 193.0289, 104.0494 −2.3 122
    24 氯嘧磺隆 chlorimuron-ethyl 10.92 414.0401 414.0418 186.0060, 83.0239 4.1 128
    25 氯磺隆 chlorsulfuron 6.11 357.0299 357.0286 141.0770, 56.0494 −3.6 141
    26 异噁草酮 clomazone 8.08 239.0713 239.0709 125.0152, 89.0385 −1.7 144
    27 氯甲酰草胺 clomeprop 16.71 323.0480 323.0486 203.0025, 148.0756 1.9 123
    28 氯酯磺草胺 cloransulam-methyl 7.87 429.0310 429.0317 398.0120, 306.0184 1.6 136
    29 育畜磷 crufomate 10.92 291.0791 291.0784 236.0237, 108.0208 −2.4 147
    30 氰草津 cyanazine 5.32 240.0890 240.0881 214.0854, 174.0540 −3.7 144
    31 氰霜唑 cyazofamid 14.25 324.0448 324.0447 216.0323, 108.0113 −0.3 127
    32 环莠隆 cycluron 6.55 198.1732 198.1731 111.1168, 89.0709 −0.5 134
    33 环氟菌胺 cyflufenamid 16.71 412.1210 412.1211 295.0864, 241.0383 0.2 123
    34 环丙津 cyprazine 6.52 227.0938 227.0935 186.0540, 108.0556 −1.3 123
    35 酯菌胺 cyprofuram 7.02 279.0662 279.0668 166.0413, 69.0339 2.2 136
    36 敌草净 desmetryn 5.47 213.1048 213.1052 172.0651, 82.0399 1.9 124
    37 燕麦敌 diallate 16.83 269.0408 269.0413 228.0011, 128.1069 1.9 159
    38 二嗪磷 diazinon 15.20 304.1011 304.1005 249.0454, 169.0793 −2.0 85
    39 双氯磺草胺 diclosulam 8.35 404.9865 404.9863 314.0006, 160.9791 −0.5 132
    40 苯醚甲环唑 difenoconazole 14.73 405.0647 405.0638 337.0392, 251.0025 −2.2 122
    41 敌蝇威 dimetilan* 3.94 240.1222 240.1220 196.0716, 72.0443 −0.8 163
    42 二甲吩草胺 dimethenamid 9.81 275.0747 275.0745 244.0557, 168.0841 −0.7 134
    43 双苯酰草胺 diphenamid 8.08 239.1310 239.1313 167.0855, 134.0964 1.3 129
    44 肼菌酮 drazoxolon 12.33 237.0305 237.0304 220.0272, 177.0214 −0.4 170
    45 氟环唑 epoxiconazole 11.36 329.0731 329.0725 121.0448, 70.0399 −1.8 54
    46 戊草丹 esprocarb 17.32 265.1500 265.1504 196.0791, 91.0542 1.5 173
    47 甲基胺苯磺隆 ethametsulfuron-methyl 6.53 410.1009 410.1002 196.0829, 142.0723 −1.7 127
    48 乙硫苯威砜 ethiofencarb-sulfone 3.60 257.0722 257.0715 107.0491, 77.0385 −2.7 142
    49 乙硫苯威亚砜 ethiofencarb-sulfoxide 3.28 241.0773 241.0769 107.0491, 77.0385 −1.7 158
    50 乙螨唑 etoxazole 18.28 359.1697 359.1700 304.1132, 141.0146 0.8 149
    51 乙嘧硫磷 etrimfos 14.74 292.0647 292.0655 164.0468, 124.9820 2.7 136
    52 伐灭磷 famphur 9.53 325.0208 325.0214 280.9701, 217.0082 1.8 130
    53 咪唑菌酮 fenamidone 11.04 311.1092 311.1088 236.1182, 165.0481 −1.3 153
    54 喹螨醚 fenazaquin 18.55 306.1732 306.1725 161.1324, 105.0698 −2.3 129
    55 甲呋酰胺 fenfuram 6.85 201.0790 201.0791 109.0284, 83.0491 0.5 126
    56 环酰菌胺 fenhexamid 11.27 301.0636 301.0633 142.0054, 97.1011 −1.0 123
    57 苯硫威 fenothiocarb 13.00 253.1137 253.1128 160.0790, 106.0321 −3.6 134
    58 噁唑禾草灵 fenoxaprop-ethyl 16.77 361.0717 361.0715 288.0422, 121.0647 −0.6 160
    59 苯氧威 fenoxycarb 13.13 301.1314 301.1318 256.0968, 211.0753 1.3 193
    60 双氟磺草胺 florasulam 5.99 359.0300 359.0305 296.0753, 129.0384 1.4 207
    61 氟环脲 flucycloxuron 17.90 483.1161 483.1165 289.0783, 132.0443 0.8 156
    62 氟噻草胺 flufenacet 13.24 363.0665 363.0660 194.0975, 152.0506 −1.4 80
    63 氟甲喹 flumequine 5.74 261.0801 261.0809 244.0768, 202.0287 3.1 294
    64 唑嘧磺草胺 flumetsulam 4.23 325.0445 325.0440 262.0898, 129.0384 −1.5 143
    65 氟吡菌酰胺 fluopyram 12.44 396.0464 396.0470 208.1353, 173.0208 1.5 240
    66 乙羧氟草醚 fluoroglycofen-ethyl# 17.26 447.0333 447.0339 343.9931, 300.0033 1.3 152
    67 氟喹唑 fluquinconazole 11.62 375.0090 375.0089 349.0053, 306.9835 −0.3 134
    68 氟咯草酮 flurochloridone 13.15 311.0092 311.0088 292.0101, 240.0630 −1.3 221
    69 呋嘧醇 flurprimidol 9.70 312.1086 312.1090 270.0610, 185.0709 1.3 86
    70 氟硅唑 flusilazole 12.48 315.1003 315.1004 247.0749, 165.0696 0.3 148
    71 氟酰胺 flutolanil 13.08 323.1133 323.1139 262.0662, 173.0197 1.9 86
    72 粉唑醇 flutriafol 6.53 301.1027 301.1022 233.0772, 123.0238 −1.7 167
    73 氟唑菌酰胺 fluxapyroxad 11.70 381.0901 381.0910 362.0910, 234.0525 2.4 184
    74 甲酰氨基嘧磺隆 foramsulfuron 5.12 452.1114 452.1116 255.0427, 182.0560 0.4 145
    75 麦穗宁 fuberidazole 3.21 184.0637 184.0633 157.0760, 130.0651 −2.2 149
    76 呋霜灵 furalaxyl 9.51 301.1314 301.1310 242.1175, 95.0127 −1.3 178
    77 呋线威 furathiocarb 17.43 382.1562 382.1561 252.0682, 195.0474 −0.3 210
    78 氯吡嘧磺隆 halosulfuron-methyl 10.01 434.0412 434.0413 221.9729, 182.0560 0.2 137
    79 氟吡乙禾灵 haloxyfop-2-ethoxyethyl 17.21 433.0904 433.0908 316.0346, 117.0910 0.9 130
    80 氟吡甲禾灵 haloxyfop-methyl 16.41 375.0485 375.0482 316.0346, 272.0084 −0.8 205
    81 氯虫酰肼 halofenozide* 10.64 330.1135 330.1138 138.9945, 105.0334 0.9 123
    82 环嗪酮 hexazinone 4.78 252.1586 252.1587 171.0876, 101.0345 0.4 147
    83 咪草酸 imazamethabenz-methyl 4.97 288.1474 288.1473 215.0815, 144.0443 −0.3 136
    84 亚胺唑 imibenconazole 16.59 409.9927 409.9914 341.9672, 171.0029 −3.2 46
    85 唑吡嘧磺隆 imazosulfuron 7.97 412.0357 412.0359 257.9734, 156.0767 0.5 128
    86 抗倒胺 inabenfide 7.99 338.0822 338.0820 321.0789, 214.0418 −0.6 123
    87 异菌脲 iprodione 12.53 329.0334 329.0337 244.9879, 161.9871 0.9 216
    88 丁嗪草酮 isomethiozin 13.53 268.1358 268.1360 200.0852, 130.0433 0.7 188
    89 稻瘟灵 isoprothiolane 12.42 290.0647 290.0644 231.0144, 188.9674 −1.0 137
    90 异柳磷 isofenphos* 16.65 345.1164 345.1163 216.9712, 121.0284 −0.3 125
    91 异丙隆 isoproturon 6.81 206.1419 206.1415 165.1022, 72.0443 −1.9 153
    92 异噁唑草酮 isoxaflutole 4.47 359.0439 359.0440 250.9984, 219.9800 0.3 145
    93 特胺灵 karbutilate 5.69 279.1583 279.1581 224.1029, 181.0971 −0.7 132
    94 苯噻酰草胺 mefenacet 11.09 298.0776 298.0778 192.0081, 148.0756 0.7 121
    95 嘧菌胺 mepanipyrim 11.69 223.1110 223.1117 182.0838, 106.0651 3.1 97
    96 灭锈胺 mepronil 12.41 269.1416 269.1412 228.1019, 119.0491 −1.5 203
    97 甲霜灵 metalaxyl 6.84 279.1471 279.1478 160.1120, 105.0698 2.5 144
    98 甲基苯噻隆 methabenzthiazuron 6.07 221.0623 221.0619 165.0481, 150.0246 −1.8 137
    99 甲氧丙净 methoprotryne 6.92 271.1467 271.1469 240.1277, 198.0808 0.7 289
    100 溴谷隆 metobromuron 7.20 258.0004 258.0007 227.9892, 169.9599 1.2 57
    101 嗪草酮 metribuzin 5.40 214.0888 214.0884 187.1012, 84.0807 −1.9 135
    102 绿谷隆 monolinuron 6.74 214.0509 214.0506 183.0319, 126.0100 −1.4 147
    103 灭草隆 monuron 5.07 198.0560 198.0569 154.0054, 72.0443 4.5 193
    104 腈菌唑 myclobutanil 10.75 288.1142 288.1146 220.0887, 125.0152 1.4 134
    105 萘乙酰胺1-naphthyl acetamide 4.57 185.0841 185.0842 141.0699, 115.0542 0.5 90
    106 草不隆 neburon 13.32 274.0640 274.0638 187.9664, 88.1120 −0.7 155
    107 呋酰胺 ofurace 6.82 281.0819 281.0811 160.1120, 121.0886 −2.8 137
    108 坪草丹 orbencarb 14.99 257.0641 257.0639 125.0125, 72.0443 −0.8 136
    109 噁霜灵 oxadixyl 5.13 278.1267 278.1266 219.1128, 133.0859 −0.4 62
    110 氧化萎锈灵 oxycarboxin 4.54 267.0565 267.0563 175.0059, 83.0127 −0.7 150
    111 克草敌 pebulate 15.47 203.1344 203.1347 176.1467, 128.1069 1.5 146
    112 五氟磺草胺 penoxsulam 8.15 483.0636 483.0633 326.0872, 195.0750 −0.6 141
    113 甲拌磷 phorate 15.79 260.0128 260.0125 142.9384, 75.0263 −1.2 128
    114 甲拌磷砜 phorate-Sulfone 8.65 292.0027 292.0033 199.0010, 142.9384 2.2 138
    115 甲拌磷亚砜 phorate-Sulfoxide 6.37 276.0077 276.0069 142.9384, 96.9507 −3.0 130
    116 氟吡酰草胺 picolinafen 17.18 376.0835 376.0822 238.0462, 145.0259 −3.5 163
    117 甲基氟嘧磺隆 primisulfuron-methyl 12.07 468.0363 468.0366 254.0178, 199.0052 0.6 134
    118 猛杀威 promecarb 9.93 207.1259 207.1254 151.1117, 109.0647 −2.4 145
    119 扑灭通 prometon 5.68 225.1590 225.1593 184.1192, 142.0723 1.3 197
    120 扑草净 prometryn 9.25 241.1361 241.1366 200.0964, 158.0495 2.1 174
    121 噁草酸 propaquizafop 17.06 443.1248 443.1252 371.0793, 100.0756 0.9 168
    122 扑灭津 propazine 8.24 229.1094 229.1093 188.0697, 146.0228 −0.4 170
    123 异丙草胺 propisochlor 14.47 283.1339 283.1341 224.0831, 148.1120 0.7 178
    124 炔苯酰草胺 propyzamide 11.22 255.0218 255.0211 189.9821, 144.9606 −2.7 197
    125 丙氧喹啉 proquinazid 18.43 372.0335 372.0327 330.9938, 288.9382 −2.2 157
    126 苄草丹 prosulfocarb 16.67 251.1344 251.1350 128.1069, 91.0542 2.4 138
    127 丙硫菌唑 prothioconazole 12.53 343.0313 343.0314 326.0280, 290.0513 0.3 127
    128 发硫磷 prothoate 7.97 285.0622 285.0628 142.9384, 96.9507 2.1 141
    129 吡唑硫磷 pyraclofos 14.83 360.0464 360.0466 256.9874, 195.0314 0.6 161
    130 吡草醚 pyraflufen-ethyl 15.15 412.0205 412.0202 338.9898, 253.0163 −0.7 145
    131 唑菌酯 pyraoxystrobin 15.07 205.0859 205.0852 145.0647, 117.0698 −3.4 141
    132 磺酰草吡唑 pyrasulfotole 4.34 362.0548 362.0554 250.9984, 113.0709 1.7 139
    133 苄草唑 pyrazoxyfen 14.06 402.0538 402.0540 403.0610, 105.0334 0.5 168
    134 吡嘧磺隆 pyrazosulfuron-ethyl 9.83 414.0958 414.0954 182.0560, 139.0652 −1.0 105
    135 哒嗪硫磷 pyridaphenthion 11.76 340.0647 340.0649 285.0090, 189.0658 0.6 140
    136 环酯草醚 pyriftalid 10.68 318.0674 318.0677 269.0379, 179.0161 0.9 153
    137 嘧霉胺 pyrimethanil 7.85 199.1110 199.1108 143.0603, 107.0603 −1.0 195
    138 嘧硫磷 pyrimitate 14.90 305.0963 305.0966 154.0974, 96.9507 1.0 98
    139 吡丙醚 pyriproxyfen 17.59 321.1365 321.1364 185.0597, 96.0443 −0.3 125
    140 喹硫磷 quinalphos 14.13 298.0541 298.0537 242.9985, 96.9508 −1.4 103
    141 喹氧灵 quinoxyfen 16.93 306.9967 306.9961 272.0272, 196.9788 −2.0 92
    142 乙基喹禾灵 quizalofop-ethyl 16.76 372.0877 372.0871 299.0577, 91.0542 −1.6 133
    143 吡咪唑 rabenzazole 6.61 212.1062 212.1068 172.0863, 118.0525 2.8 124
    144 另丁津 sebuthylazine 8.07 229.1094 229.1091 174.0540, 132.0323 −1.3 272
    145 仲丁通 secbumeton 5.60 225.1590 225.1587 170.1036, 142.0723 −1.3 153
    146 去乙基另丁津 sebuthylazine-desethyl 4.59 201.0781 201.0782 146.0228, 104.0010 0.5 90
    147 西玛津 simazine 5.11 201.0781 201.0788 174.0540, 124.0869 3.5 162
    148 西玛通 simeton 3.69 197.1277 197.1275 170.1036, 128.0818 −1.0 142
    149 西草净 simetryn 5.53 213.1048 213.1044 124.0868, 96.0556 −1.9 174
    150 螺螨酯 spirodiclofen 19.08 410.1052 410.1058 313.0392, 71.0855 1.5 145
    151 螺虫乙酯 spirotetramat 10.48 373.1889 373.1885 302.1751, 216.0990 −1.1 137
    152 菜草畏 sulfallate 14.77 223.0256 223.0255 188.0562, 116.0528 −0.4 173
    153 氟啶虫胺腈 sulfoxaflor 4.68 277.0497 277.0499 174.0524, 105.0117 0.7 135
    154 硫丙磷 sulprofos 18.11 322.0285 322.0288 218.9697, 139.0212 0.9 144
    155 吡螨胺 tebufenpyrad 16.79 333.1608 333.1610 278.1054, 147.1168 0.6 136
    156 牧草胺 tebutam 12.54 233.1780 233.1782 192.1382, 91.0542 0.9 167
    157 丁噻隆 tebuthiuron 4.66 228.1045 228.1044 172.0903, 116.0276 −0.4 157
    158 双硫磷 temephos# 17.85 465.9897 465.9899 341.0065, 124.9820 0.4 162
    159 特草灵 terbucarb 15.93 277.2042 277.2048 222.1488, 166.0862 2.2 142
    160 特丁通 terbumeton 5.94 225.1590 225.1597 170.1036, 142.0723 3.1 129
    161 氧特丁硫磷砜 terbufos-oxon-sulfone 5.29 304.0568 304.0556 174.9283, 109.0049 −3.9 127
    162 特丁津 terbuthylazine 8.94 229.1094 229.1088 174.0540, 132.0323 −2.6 136
    163 杀虫威 tetrachlorvinphos 12.81 363.8993 363.8988 238.8982, 127.0155 −1.4 130
    164 四氟醚唑 tetraconazole 11.97 371.0215 371.0211 184.9919, 158.9762 −1.1 143
    165 噻吩草胺 thenylchlor 13.11 323.0747 323.0745 288.1053, 127.0212 −0.6 172
    166 噻氟隆 thiazafluron 5.21 240.0293 240.0299 184.0150, 74.0059 2.5 139
    167 禾草丹 thiobencarb 15.32 257.0641 257.0643 125.0152, 72.0443 0.8 133
    168 硫双威 thiodicarb 5.89 354.0490 354.0485 107.9902, 88.0188 −1.4 135
    169 虫线磷 thionazin 8.24 248.0385 248.0387 192.9831, 153.0133 0.8 129
    170 仲草丹 tiocarbazil 18.40 279.1657 279.1662 224.1103, 91.0542 1.8 150
    171 甲基立枯磷 tolclofos-mehyl 15.79 299.9544 299.9548 174.9710, 124.9820 1.3 68
    172 唑虫酰胺 tolfenpyrad 17.04 383.1401 383.1411 197.0960, 145.0527 2.6 139
    173 抑芽唑 triapenthenol 11.56 263.1998 263.1995 109.1011, 70.0399 −1.1 133
    174 醚苯磺隆 triasulfuron 6.16 401.0561 401.0560 218.9858, 167.0536 −0.2 133
    175 草达津 trietazine 11.61 229.1094 229.1091 202.0854, 132.0323 −1.3 134
    176 氟菌唑 triflumizole 15.17 345.0856 345.0857 278.0553, 73.0647 0.3 154
    177 氟胺磺隆 triflusulfuron-methyl 12.08 492.1039 492.1046 264.0698, 238.0907 1.4 200
    178 3,4,5-混杀威 3,4,5-trimethacarb 7.37 193.1103 193.1109 137.0961, 122.0726 3.1 116
    179 烯效唑 uniconazole 10.73 291.1138 291.1139 125.0152, 70.0399 0.3 139
    180 苯酰菌胺 zoxamide 15.09 335.0247 335.0241 186.9711, 158.9762 −1.8 126
    注:加合离子形式:*:[M + Na]+#:[M + NH4]+;未标注:[M + H]+.Note: adduct ion form: *:[M + Na]+; #: [M + NH4]+; not marked:[M + H]+.
    下载: 导出CSV

    表  2  香橼样品定性筛查结果

    Table  2.   Qualitative screening results of Fructus Citri sample

    No.化合物
    Compound
    质量数
    Mass,m/z
    质量数偏差
    Mass Diff/ppm
    保留时间
    Retention time/min
    保留时间偏差
    Retention time Diff/min
    匹配得分
    Score
    1 环莠隆 cycluron 198.17321 1.51 6.676 −0.182 83.85
    2 氟甲喹 flumequine 261.08012 −5.31 5.786 0.219 60.77
    3 氟氯氰菊酯 cyfluthrin 215.09377 3.6 6.53 −0.036 73.46
    4 西玛津 simazine 201.07812 0.49 5.123 0.089 56.39
    5 灭害威 aminocarb 208.12118 1.09 2.204 0.138 56.91
    6 苯醚甲环唑 difenoconazole 405.0647 −2.01 14.817 0.009 95.44
    7 氟环唑 epoxiconazole 329.07312 −3.82 11.491 −0.17 54.81
    8 甲拌磷砜 phorate-Sulfone 292.00266 −4.93 8.647 0.006 91.53
    9 甲拌磷亚砜 phorate-sulfoxide 276.00774 −2.67 6.366 −0.109 80.49
    下载: 导出CSV

    表  3  实际样品检测结果

    Table  3.   Sample test results

    样品序号
    Sample No
    检出农药
    Detected pesticide
    残留量
    Residue/(mg/kg)
    相对误差
    Relative error/%
    UPLC-Q-TOF/MSLC-MS/MS
    3 苯醚甲环唑
    difenoconazole
    0.0042 0.0035 18.2
    乙螨唑
    etoxazole
    0.0098 0.0082 17.8
    7 环莠隆
    cycluron
    0.0109 0.0106 2.8
    氟氯氰菊酯
    cyfluthrin
    0.0075 0.0081 7.7
    20 氟环唑
    epoxiconazole
    0.0052 0.0063 19.1
    唑虫酰胺
    tolfenpyrad
    0.0087 0.0069 23.1
    氟环脲
    flucycloxuron
    0.0123 0.0156 23.7
    29 氟啶虫胺腈
    sulfoxaflor*
    0.5062 0.4985 1.5
    二嗪磷
    diazinon
    0.0062 0.0075 19.0
    36 稻瘟灵
    isoprothiolane
    0.0055 0.0063 13.6
    异菌脲
    iprodione
    0.0070 0.0068 2.9
    二嗪磷
    diazinon
    0.0018 0.0021 15.4
    42 甲拌磷砜
    phorate-sulfone*
    0.0607 0.0589 3.0
    甲拌磷亚砜
    phorate-sulfoxide*
    0.1988 0.1725 14.2
    甲呋酰胺
    fenfuram
    0.0033 0.0029 12.9
    48 环莠隆
    cycluron
    0.0066 0.0057 14.6
    苯醚甲环唑
    difenoconazole
    0.0118 0.0098 18.5
    注:*表示检出该农药含量超出MRL值.Note: * means the pesticide content exceeds the MRL value.
    下载: 导出CSV
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出版历程
  • 收稿日期:  2021-08-23
  • 录用日期:  2021-10-29
  • 网络出版日期:  2021-12-27

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