Residues of 21 fungicides in Fragaria ananassa by modified QuEChERS and gas chromatography-tandem mass spectrometry
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摘要: 采用改进的QuEChERS气相色谱-串联质谱法建立了检测草莓中21种杀菌剂（螺环菌胺、甲霜灵、四氟醚唑、酞菌酯、嘧菌环胺、戊菌唑、氟吡菌酰胺、氟菌唑、嘧菌胺、E-苯氧菌胺、抑霉唑、腈菌唑、醚菌酯、环氟菌胺、肟菌酯、丙环唑、环酰菌胺、氟环唑、咪唑菌酮、啶酰菌胺、嘧菌酯）残留的方法。样品经乙腈提取，采用N-丙基乙二胺（primary secondary amine，PSA）和石墨化碳黑（graphitized carbon blacks，GCB）作为分散固相萃取（dispersive solid phase extraction，DSPE）的吸附材料，净化液经氮气吹干、用V（正己烷）：V（丙酮）=9：1混合溶液定容，采用气相色谱-串联质谱（gas chromatography-tandem mass spectrometry，GC-MS/MS）测定。结果表明：在质量浓度0.005~0.2 mg/kg范围内，21种杀菌剂与对应的峰面积间呈良好的线性关系；在0.01、0.05和0.1 mg/kg 3个添加水平下，21种杀菌剂的平均回收率均在70%~122%之间，RSD < 20%。该方法适用于草莓中21种杀菌剂残留的快速、高效和准确分析。Abstract: In order to determine 21 fungicides (spiroxamine, metalaxyl, tetraconazole, nitrothal-isopropyl, cyprodinil, penconazole, fluopyram, triflumizole, mepanipyrim, E-metominostrobin, imazalil, myclobutanil, kresoxim-methyl, cyflufenamid, trifloxystrobin, propiconazol, fenhexamid, epoxiconazole, fenamidone, boscalid, azoxystrobin) in Fragaria ananassa, the sample preparation method and GC-MS/MS analysis parameters were optimized. The sample was first extracted by acetonitrile. During the DSPE procedure, PSA and GCB were used as sorbents. After concentrated, the extract was dissolved by a mixed solvent V (hexane):V (acetone)=9:1. The extract was then determined with GC-MS/MS. Linear relationships between peak area and mass concentration of 21 fungicides were obtained in the range of 0.005-0.2 mg/kg. When the spiked levels were 0.01, 0.05 and 0.1mg/kg, the average recoveries all ranged from 70 to 122% with RSD < 20% (n=5). This method is suitable for the rapid and accurate detection of 21 fungicides in F. ananassa.
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Key words:
- QuEChERS /
- gas chromatography-tandem mass spectrometry /
- Fragaria ananassa Duch /
- fungicide /
- residue
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图 1 不同PSA用量下21种杀菌剂的回收率(A) 和相对标准偏差(B) (n=5)
Figure 1. Recoveries (A) and RSDs (B) of 21 fungicides purified with different amount of PSA
图 2 不同GCB用量下21种杀菌剂的回收率(A) 和相对标准偏差(B) (n=5)
Figure 2. Recoveries (A) and RSDs (B) of 21 fungicides purified with different amount of GCB
图 3 草莓中21种杀菌剂在多反应监测模式扫描下的色谱图(0.10 mg/kg)
Figure 3. Ion chromatogram of 21 fungicides (0.10 mg/kg) using MRM mode in strawberry
表 1 21种杀菌剂串联质谱多反应监测模式下的检测条件
Table 1. Multiple reaction monitoring conditions for the determination of 21 fungicides using GC-MS/MS
序号No. 杀菌剂Fungicide 保留时间Retention time/min 定量离子对Quantitative ion pair, m/z 碰撞能量Collision energy/eV 定性离子对Qualitative ion pair, m/z 碰撞能量Collision energy/eV 1 螺环菌胺spiroxamine 13.18，13.80 100 > 72 8 100 > 58 12 2 甲霜灵metalaxyl 13.42 249 > 190 8 249 > 146 22 3 四氟醚唑tetraconazole 14.39 336 > 204 28 159 > 123 16 4 酞菌酯nitrothal-isopropyl 14.47 254 > 212 10 254 > 165 22 5 嘧菌环胺cyprodinil 14.98 224 > 208 16 224 > 197 22 6 戊菌唑penconazole 15.10 248 > 192 14 248 > 157 26 7 氟吡菌酰胺fluopyram 15.13 223 > 196 10 173 > 145 10 8 氟菌唑triflumizole 15.39 278 > 73 6 268 > 55 12 9 嘧菌胺mepanipyrim 15.99 222 > 207 15 222 > 206 15 10 E-苯氧菌胺E-metominostrobin 16.18 238 > 210 6 238 > 197 24 11 抑霉唑imazalil 16.23 215 > 173 6 215 > 159 6 12 腈菌唑myclobutanil 16.50 179 > 125 15 179 > 152 8 13 醚菌酯kresoxim-methyl 16.53 206 > 116 6 206 > 131 14 14 环氟菌胺cyflufenamid 16.68 412 > 295 9 412 > 118 26 15 肟菌酯trifloxystrobin 17.72 116 > 89 15 186 > 145 15 16 丙环唑propiconazol 17.88，17.99 259 > 69 14 259 > 191 8 17 环酰菌胺fenhexamid 18.07 177 > 113 15 177 > 78 28 18 氟环唑epoxiconazole 18.51 192 > 138 4 192 > 111 26 19 咪唑菌酮fenamidone 18.96 268 > 180 16 268 > 77 28 20 啶酰菌胺boscalid 21.24 342 > 140 14 342 > 112 28 21 嘧菌酯azoxystrobin 23.37 344 > 183 24 344 > 329 16 
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表 2 21种杀菌剂的线性回归方程、相关系数和定量限
Table 2. Linear regression equations, correlation coefficients and detection limits of 21 fungicides
杀菌剂Fungicide 线性回归方程Linear regression equation 相关系数Correlation coefficent, r 定量限LOQs/(mg/kg) 螺环菌胺spiroxamine y=995 601.6x -1 106.2 0.9992 0.005 甲霜灵metalaxyl y=161 700.6x -989.9206 0.9994 0.005 四氟醚唑tetraconazole y=13 891.6x -2 306.133 0.9987 0.01 酞菌酯nitrothal-isopropyl y=72 203.08x -1 003.136 0.9980 0.005 嘧菌环胺cyprodinil y=506 188.4x -1 128.379 0.9993 0.005 戊菌唑penconazole y=451 006.4x -5 194.768 0.9980 0.005 氟吡菌酰胺fluopyram y=90 450.3x -8 280.071 0.9980 0.005 氟菌唑triflumizole y=85 213.69x -2 311.785 0.9996 0.01 嘧菌胺mepanipyrim y=429 533.5x -3 781.358 0.9991 0.005 E-苯氧菌胺E-metominostrobin y=107 545.7x -1 431.165 0.9993 0.005 抑霉唑imazalil y=258 748.4x -5 113.12 0.9981 0.005 腈菌唑myclobutanil y=719 354.5x -9 413.479 0.9985 0.005 醚菌酯kresoxim-methyl y=364 189.4x -3 565.531 0.9982 0.005 环氟菌胺cyflufenamid y=67 845.78x -858.7651 0.9987 0.005 肟菌酯trifloxystrobin y=726 739.x -6 576.669 0.9983 0.005 丙环唑propiconazol y=280 822.6x -2 841.622 0.9987 0.01 环酰菌胺fenhexamid y=396 363.8x -2 187.864 0.9988 0.01 氟环唑epoxiconazole y=209 558.1x -1 581.861 0.9988 0.005 咪唑菌酮fenamidone y=334 973.0x -1 951.045 0.9992 0.005 啶酰菌胺boscalid y=215 087.5x -2 210.33 0.9988 0.005 嘧菌酯azoxystrobin y=359 836.4x -3 859.674 0.9983 0.005
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表 3 21种杀菌剂的添加回收率和相对标准偏差(n=5)
Table 3. Recoveries and RSDs of 21 fungicides (n=5)
杀菌剂Fungicide 添加水平Spike level/(mg/kg) 0.01 0.05 0.1 回收率Recovery/% 相对标准偏差RSDs/% 回收率Recovery/% 相对标准偏差RSDs/% 回收率Recovery/% 相对标准偏差RSDs/% 螺环菌胺spiroxamine 70 3.2 96 12.4 93 3.9 甲霜灵metalaxyl 95 2.6 84 10.5 82 2.8 四氟醚唑tetraconazole 94 8.1 81.2 10.3 92 2.7 酞菌酯nitrothal-isopropyl 83 4.8 77 10.3 89 3.3 嘧菌环胺cyprodinil 76 5.9 79 14.6 79 2.6 戊菌唑penconazole 99 5.4 81 13.5 87 3.8 氟吡菌酰胺fluopyram 111 5.4 84 11.2 90 3.1 氟菌唑triflumizole 92 5.3 77 7.9 99 3.2 嘧菌胺mepanipyrim 76 6.6 78 14.4 78 3.0 E-苯氧菌胺E-metominostrobin 88 6.1 81 9.8 95 2.0 抑霉唑imazalil 104 7.5 70 5.0 87 3.2 腈菌唑myclobutanil 105 7.1 73 10.8 81 1.9 醚菌酯kresoxim-methyl 96 8.8 87 12.1 91 2.8 环氟菌胺cyflufenamid 88 6.4 87 12.5 93 4.0 肟菌酯trifloxystrobin 115 10.8 86 11.5 90 3.3 丙环唑propiconazol 95 17.6 72 11.2 89 4.5 环酰菌胺fenhexamid 77 10.8 103 15.4 966 3.7 氟环唑epoxiconazole 87 6.6 90 7.4 90 4.3 咪唑菌酮fenamidone 89 4.0 87 12.4 90 2.1 啶酰菌胺boscalid 122 14.9 91 13.7 88 2.3 嘧菌酯azoxystrobin 76 7.4 75 14.7 78 2.1
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