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固相萃取-气相色谱-串联质谱法测定大豆油中126种农药残留

汪春明 张洋 王东斌 施鹏斐 杨波

汪春明, 张洋, 王东斌, 施鹏斐, 杨波. 固相萃取-气相色谱-串联质谱法测定大豆油中126种农药残留[J]. 农药学学报, 2021, 23(2): 405-413. doi: 10.16801/j.issn.1008-7303.2021.0047
引用本文: 汪春明, 张洋, 王东斌, 施鹏斐, 杨波. 固相萃取-气相色谱-串联质谱法测定大豆油中126种农药残留[J]. 农药学学报, 2021, 23(2): 405-413. doi: 10.16801/j.issn.1008-7303.2021.0047
Chunming WANG, Yang ZHANG, Dongbin WANG, Pengfei SHI, Bo YANG. Determination of 126 pesticides residues in soybean oil by solid phase extraction-gas chromatography-tandem mass spectrometry[J]. Chinese Journal of Pesticide Science, 2021, 23(2): 405-413. doi: 10.16801/j.issn.1008-7303.2021.0047
Citation: Chunming WANG, Yang ZHANG, Dongbin WANG, Pengfei SHI, Bo YANG. Determination of 126 pesticides residues in soybean oil by solid phase extraction-gas chromatography-tandem mass spectrometry[J]. Chinese Journal of Pesticide Science, 2021, 23(2): 405-413. doi: 10.16801/j.issn.1008-7303.2021.0047

固相萃取-气相色谱-串联质谱法测定大豆油中126种农药残留

doi: 10.16801/j.issn.1008-7303.2021.0047
详细信息
    通讯作者:

    汪春明,通信作者 (Author for correspondence),男,检测工程师,主要从事农药残留检测,E­mail:598898364@qq.com

  • 中图分类号: TS207.5;O657.63;TQ450.263

Determination of 126 pesticides residues in soybean oil by solid phase extraction-gas chromatography-tandem mass spectrometry

  • 摘要: 建立了同时测定大豆油中126种农药残留的检测方法。样品经乙腈饱和的正己烷溶解并初次除油后用正己烷饱和的乙腈萃取,于 −5 ℃、20000 r/min下离心5 min,Captiva EMR-Lipid固相萃取柱净化,乙酸乙酯复溶后采用气相色谱-质谱联用仪 (GC-MS/MS) 多反应监测 (MRM) 模式检测,外标法定量。结果表明:在0.003~0.2 mg/L范围内,126种农药的质量浓度与其对应的峰面积间线性关系良好,R2均大于0.995,在0.005、0.01和0.05 mg/kg 3个添加水平下,126种农药的回收率在60%~119%之间,其中122种农药的RSD低于20%,另外4种农药的RSD低于25%。该方法能够有效除去大豆油中甘油及亲脂性干扰物,方法灵敏度、准确度和精密度均符合农药残留检测的要求,为监测大豆油中农药残留含量、有效防范健康风险提供了一种高效、可靠的分析手段。
  • 图  1  多反应监测总离子流色谱图 (0.05 mg/kg)

    A. 68 种A组农药;B. 58 种B组农药。

    Figure  1.  Total ions chromatograms of multiple reaction monitoring (0.05 mg/kg)

    A. 68 pesticides of A group; B. 58 pesticides of B group.

    图  2  不同种类固相萃取柱净化后剩余油的含量

    Figure  2.  Residual oil after different types of SPE columns clean-up

    图  3  不同种类固相萃取柱净化后色谱图对比

    Figure  3.  Comparison of chromatograms using different SPE columns

    A:未净化 (Without purifying);B:ENVI-18;C:AL-N;D:Captiva EMR-Lipid;E:FL;F:HLB;G:PRiME-HLB;H:PRiME-Short;I:Si;J:PEP.

    表  1  126种农药保留时间及气相色谱-串联质谱检测参数

    Table  1.   Retention time and GC-MS/MS detection parameters of 126 pesticides

    序号
    No.
    农药
    Pesticide
    保留时间
    Retention time/min
    定量离子对
    Quantitative ion pair, m/z
    碰撞电压
    Collision energy/eV
    定性离子对
    Qualitaive ion pair, m/z
    碰撞电压
    Collision energy/eV
    A组 A group
    1 2,4-滴丁酯 2,4-D butylate 8.775 184.9 > 154.9 15 174.9 > 111.0 10
    2 邻苯基苯酚 2-phenylphenol 6.312 169.0 > 115.1 25 169.0 > 141.1 15
    3 杀螨特 aramite 11.513 185.0 > 63.0 10 175.0 > 107.1 20
    4 草除灵 benazolin-ethyl 10.246 198.0 > 170.0 10 170.0 > 134.0 15
    5 甲羧除草醚 bifenox 13.741 189.1 > 126.0 20 340.9 > 309.9 10
    6 生物苄呋菊酯 bioresmethrin 12.935 123.0 > 81.1 15 171.0 > 143.1 15
    7 溴硫磷 bromophos 10.387 124.9 > 47.0 10 330.8 > 315.8 15
    8 乙嘧酚磺酸酯 bupirimate 11.417 272.9 > 193.1 5 208.0 > 165.1 10
    9 丁草胺 butachlor 10.830 188.1 > 160.2 10 176.1 > 147.1 10
    10 氯虫苯甲酰胺 chlorantraniliprole 13.732 277.8 > 249.0 15 277.8 > 215.0 15
    11 毒虫畏 chlorfenvinphos 10.322 266.9 > 159.1 15 322.8 > 266.8 10
    12 乙酯杀螨醇 chlorobenzilate 11.765 251.1 > 139.1 15 139.1 > 111.0 10
    13 氯苯胺灵 chlorpropham 7.065 153.0 > 90.0 25 153.0 > 125.1 10
    14 七氟菊酯 cis-Tefluthrin 8.203 177.1 > 127.1 15 197.0> 141.1 10
    15 杀螟腈 cyanophos 8.020 242.9 > 109.0 10 124.9 > 47.0 15
    16 嘧菌环胺 cyprodinil 10.136 225.2 > 224.3 10 224.2 > 208.2 20
    17 苯氟磺胺 dichlofluanid 9.481 223.9 > 123.1 10 123.0 > 77.1 20
    18 禾草灵 diclofop-methyl 12.821 253 > 162.1 15 339.9 > 252.9 10
    19 吡氟酰草胺 diflufenican 12.847 266.0 > 238.1 15 393.9 > 265.9 10
    20 二甲吩草胺 dimethenamid 8.789 230.0 > 154.1 10 154.1 > 111.1 10
    21 噻节因 dimethipin 7.837 118.0 > 58.0 5 124.0 > 76.0 5
    22 敌杀磷 dioxathion 8.312 124.9 > 96.9 5 152.9 > 96.9 10
    23 氟环唑 epoxiconazole 13.125 192.0 > 111.0 25 165.0 > 138.0 10
    24 丁氟硝草 ethalfluralin 7.036 275.9 > 202.1 15 315.9 > 275.9 10
    25 醚菊酯 etofenprox 16.219 163.0 > 107.0 20 163.0 > 135.1 10
    26 乙螨唑 etoxazole 13.592 141.0 > 113.0 15 204.0 > 176.1 10
    27 噁唑菌酮 (恶唑菌酮) famoxadone 17.876 223.9 > 196.2 10 197.0 > 141.1 15
    28 苯硫威 fenothiocarb 10.773 160.1 > 72.1 10 72.0 > 56.0 10
    29 稻瘟酰胺 fenoxanil 11.682 189.0 > 125.1 10 189.0 > 154.1 10
    30 精噁唑禾草灵 fenoxaprop-p-ethyl 14.837 360.8 > 287.8 10 287.8 > 90.9 20
    31 咯菌腈 fludioxonil 11.284 248.0 > 154.1 20 248.0 > 182.1 10
    32 乙羧氟草醚 fluoroglycofen-ethyl 14.611 343.9 > 222.8 15 343.8 > 299.8 10
    33 氟啶草酮 fluridone 16.910 328.0 > 258.9 30 328.9 > 238.1 15
    34 氯氟吡氧乙酸异辛酯 fluroxypyr-meptyl 12.848 208.9 > 181.0 10 237.0 > 209.0 5
    35 氟酰胺 flutolanil 11.031 173.0 > 145.1 15 280.9 > 173.0 10
    36 粉唑醇 flutriafol 10.977 123.1 > 95.0 15 123.1 > 75.1 25
    37 灭菌丹 folpet 10.534 259.8 > 130.1 15 261.8 > 130.1 15
    38 噻唑磷 (噻唑硫磷) fosthiazate 9.981 195.0 > 103.0 10 195.0 > 60.0 22
    39 亚胺唑 imibenconazole 17.017 124.9 > 89.0 20 252.8 > 82.0 5
    40 缬霉威 iprovalicarb 11.421 116.0 > 98.1 5 119.1 > 91.1 15
    41 异柳磷 isofenphos 10.311 212.9 > 121.1 10 185.0 > 121.1 5
    42 异丙隆 isoproturon 4.706 146.1 > 128.1 10 161.1 > 146.1 5
    43 醚菌酯 kresoxim-methyl 11.415 116.0 > 89.0 15 116.0 > 63.0 30
    44 灭锈胺 mepronil 12.136 119.1 > 91.0 10 119.1 > 65.1 25
    45 异丙甲草胺 metolachlor 9.599 238.0 > 162.2 10 162.2 > 133.2 15
    46 速灭磷 mevinphos 5.787 127.0 > 109.0 10 192.0 > 127.0 10
    47 酞菌酯 nitrothal-isopropyl 9.725 236.0> 194.1 10 194.0 > 148.1 10
    48 噁霜灵 (恶霜灵) oxadixyl 12.038 163.0 > 132.1 5 163.0 > 117.1 25
    49 戊菌唑 penconazole 10.238 248.0 > 157.1 25 248.0 > 192.1 15
    50 氟吡酰草胺 picolinafen 13.476 376.0 > 238.1 20 238.1 > 145.1 25
    51 啶氧菌酯 picoxystrobin 10.921 145.0 > 102.1 25 145.0 > 115.1 15
    52 增效醚 piperonyl butoxide 12.907 176.1 > 103.1 25 176.1 > 131.1 15
    53 丙草胺 pretilachlor 11.192 162.1 > 147.2 10 162.1 > 132.2 20
    54 丙溴磷 profenofos 11.174 338.8 > 268.7 15 207.9 > 63.0 30
    55 丙环唑 propiconazole 12.612 172.9 > 145.0 15 172.9 > 109.0 30
    56 异丙草胺 propisochlor 9.052 162.0 > 120.1 15 162.0 > 147.1 15
    57 吡丙醚 pyriproxyfen 14.123 136.1 > 78.1 20 136.1 > 96.0 15
    58 喹氧灵 quinoxyfen 12.501 237.0 > 208.1 30 271.9 > 237.1 10
    59 喹禾灵 quizalofop-ethyl 16.151 371.8 > 298.9 10 163.0 > 136.0 10
    60 氟胺氰菊酯 tau-fluvalinate 17.021 181.0 > 152.0 40 250.0 > 55.0 40
    61 噻草啶 thiazopyr 9.573 327.1 > 277.0 30 349.0 > 329.0 10
    62 甲基立枯磷 tolclofos-methyl 8.987 265.0 > 250.0 15 265.0 > 93.0 25
    63 甲苯氟磺胺 tolylfluanid 10.299 237.9 > 137.0 15 136.9 > 91.1 20
    64 三唑醇 triadimenol 10.404 168.0 > 70.0 10 128.0 > 65.0 25
    65 肟菌酯 (布洛芬) trifloxystrobin 12.491 116.0 > 89.0 15 172.0 > 145.1 15
    66 氟菌唑 triflumizole 10.547 206.0 > 179.0 15 206.0 > 186.0 10
    67 乙烯菌核利 vinclozolin 8.874 187.0 > 124.0 20 197.9 > 145.0 15
    68 苯酰菌胺 zoxamide 13.087 187.0 > 159.1 15 189.0 > 161.1 15
    B组 B group
    1 氧环唑 azaconazole 11.495 217.0 > 173.1 15 219.0 > 175.0 15
    2 苯霜灵 benalaxyl 12.436 148.0 > 105.1 20 266.0 > 148.1 5
    3 乙基溴硫磷 bromophos-ethyl 10.662 358.7 > 302.8 15 302.8 > 284.7 15
    4 溴螨酯 bromopropylate 13.441 183.0 > 155.0 15 185.0 > 157.0 15
    5 噻嗪酮 buprofezin 11.388 105.0 > 104.1 10 119.0 > 91.0 15
    6 硫线磷 cadusafos 7.330 158.8 > 131.0 5 157.9 > 96.9 15
    7 虫螨腈 chlorfenapyr 11.645 136.9 > 102.0 15 246.9 > 227.0 15
    8 毒死蜱 chlorpyrifos 9.650 196.9 > 169.0 15 198.9 > 171.0 15
    9 甲基毒死蜱 chlorpyrifos-methyl 8.902 285.9 > 92.9 20 124.9 > 78.9 5
    10 氟氯氰菊酯 cyfluthrin 15.713 162.9 > 127.0 5 198.9 > 170.1 25
    11 氯氟氰菊酯 cyhalothrin 14.371 197.0 > 141.1 10 208.9 > 116.0 15
    12 氯氰菊酯 cypermethrin 16.021 163.1 > 127.1 5 165.1 > 91.1 15
    13 内吸磷 demeton 7.267 171.0 > 115.0 10 88.0 > 60.0 5
    14 二嗪磷 diazinon 8.088 137.1 > 84.0 10 199.1 > 93.0 15
    15 三氯杀螨醇 dicofol 9.754 139.0 > 111.0 15 141.0 > 113.0 15
    16 狄氏剂 dieldrin 11.341 262.9 > 193.0 35 277.0 > 241.0 5
    17 苯醚甲环唑 difenoconazole 17.322 322.8 > 264.8 15 264.9 > 202.0 20
    18 乐果 dimethoate 7.729 86.9 > 46.0 15 92.9 > 63.0 10
    19 二苯胺 diphenylamine 6.964 169.0 > 168.2 15 168.0 > 167.2 15
    20 硫丹硫酸酯 endosulfan-sulfate 12.603 271.9 > 237.0 15 273.8 > 238.9 15
    21 异狄氏剂 endrin 11.722 262.8 > 193.0 35 244.8 > 173.0 30
    22 S-氰戊菊酯 esfenvalerate 17.012 167.0 > 125.1 10 181.0 > 152.1 25
    23 灭线磷 ethoprophos 6.981 157.9 > 114.0 5 125.9 > 65.0 10
    24 甲氰菊酯 fenpropathrin 13.557 207.9 > 181.0 5 181.1 > 152.1 25
    25 氰戊菊酯 fenvalerate 16.825 167.0 > 125.1 5 208.9 > 141.1 15
    26 丙炔氟草胺 flumioxazin 16.904 354.0 > 325.9 5 287.0 > 258.7 15
    27 氟硅唑 flusilazole 11.413 233.0 > 165.1 15 220.0 > 139.0 20
    28 地虫硫磷 fonofos 8.083 136.9 > 109.0 5 108.9 > 80.9 5
    29 氯唑磷 isazofos 8.318 161.0 > 146.0 5 207.9 > 165.9 10
    30 甲基异柳磷 isofenphos-methyl 10.073 199.0 > 120.9 10 241.0 > 120.9 15
    31 马拉硫磷 malathion 9.439 126.9 > 99.0 5 172.9 > 99.0 15
    32 除草醚 nithophen 11.631 282.9 > 253.0 10 202.0 > 139.1 20
    33 噁草酮 (恶草酮) oxadiazone 11.248 174.9 > 112.0 15 257.8 > 175.1 5
    34 对硫磷 parathion 9.671 138.9 > 109.0 5 290.9 > 109.0 10
    35 甲基对硫磷 parathion-methyl 8.916 262.9 > 109.0 10 109.0 > 79.0 5
    36 二甲戊灵 pendimethalin 10.188 251.8 > 162.2 10 161.9 > 161.1 10
    37 氯菊酯 permethrin 15.195 163.0 > 127.0 5 183.1 > 168.1 10
    38 伏杀硫磷 phosalone 14.101 182.0 > 111.0 15 184.0 > 113.0 15
    39 甲基嘧啶磷 pirimiphos-methyl 9.298 290.0 > 125.0 20 232.9 > 151.0 5
    40 腐霉利 procymidone 10.503 282.8 > 96.0 10 96.0 > 67.1 10
    41 哒螨灵 pyridaben 15.238 147.2 > 132.2 10 132.1 > 117.1 10
    42 嘧霉胺 pyrimethanil 8.151 198.0 > 183.1 15 198.0 > 118.1 35
    43 喹硫磷 quinalphos 10.390 146.0 > 118.0 10 157.0 > 129.1 15
    44 五氯硝基苯 quintozene 8.068 248.8 > 213.8 15 295.0 > 236.8 20
    45 皮蝇灵 ronnel 9.128 285.0 > 269.9 15 286.9 > 272.0 15
    46 西玛津 simazine 7.719 201.1 > 173.1 5 203.1 > 175.1 10
    47 治螟磷 sulfotep 7.267 201.8 > 145.9 10 237.8 > 145.9 10
    48 杀螟硫磷 fenitrothion 9.324 277.0 > 260.1 5 125.1 > 79.0 5
    49 四氯硝基苯 tecnazene 6.832 260.9 > 203.0 10 214.9 > 179.0 10
    50 三氯杀螨砜 tetradifon 13.943 158.9 > 131.0 10 226.9 > 199.0 15
    51 三唑磷 triazophos 12.247 161.2 > 134.2 5 257.0 > 162.1 5
    52 氟乐灵 Trifluralin 7.131 305.9 > 264.0 5 289.9 > 201.9 15
    53 alpha-六六六 α-HCH 7.518 216.9 > 181.0 5 218.9 > 183.0 5
    54 alpha-硫丹 α-endosulfan 10.909 194.9 > 160.0 5 236.8 > 118.9 25
    55 beta-六六六 β-HCH 7.924 216.9 > 181.1 5 181.0 > 145.0 15
    56 beta-硫丹 β-endosulfan 11.885 206.9 > 172.0 15 194.9 > 158.9 10
    57 gamma-六六六 γ-HCH 7.993 216.9 > 181.0 5 181.0 > 145.0 15
    58 delta-六六六 δ-HCH 8.363 217.0 > 181.1 5 181.1 > 145.1 15
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  • 收稿日期:  2020-02-18
  • 录用日期:  2020-08-07
  • 刊出日期:  2021-04-10

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