GC-MS/MSによる食品中残留農薬の定量分析 -人参抽出液中農薬の定量分析-
MSTips No.260
今日『食の安全』は世界的な規模で取り組むべき重要な課題であり、各国においては食品中残留農薬の基準値を設定し、独自の残留農薬規制を策定している。日本では平成18年5月末日にポジティブリスト制が施行されたが、人の健康を損なう恐れのない量、いわゆる一律基準としては10ppbが採用されている。ポジティブリスト制により測定対象農薬数は増え、食品中の残留農薬を精度良く、且つ一斉に分析可能な手法が求められている。質量分析計（MS）は検出感度が高い特長を有しているが、その中でも特に感度と選択性に優れたMS/MS法が農薬分析の主流となりつつある。 JMS-TQ4000GCはMS/MSのコリジョンセルに独自のイオン蓄積/排出機構を備え、また新規開発したファームウェアにより最大36,000トランジションによるMS/MS測定が可能な最新のGC-MS/MSである。今回、JMS-TQ4000GCを用いて、人参抽出液に添加した農薬成分の定量分析を実施したので報告する。
測定条件
標準溶液の調整には富士フイルム和光純薬株式会社製の農薬混合標準液PLシリーズを用いた。PL1、2、3、4、5、6、11、12を等量混合したものを準備し、それを段階的に希釈して1、5、10、50、100ppbの標準溶液を作製した。また、Analyte Protectants にはPEG300を用いた。
測定試料は人参15gをAOAC法で処理して得た抽出液と標準溶液100ppbを9:1で混合したものを用いた。今回は150成分の農薬について定量分析を実施した。今回使用した測定条件をTable1に示す。
GC-MS/MS, JMS-TQ4000GC
Table1 Measurement condition
[GC-TQMS condition]
| System | JMS-TQ4000GC (JEOL) |
| Ionization mode | EI+: 70eV, 50µA |
| GC column | VF-5ms, 30m × 0.25mm, 0.25µm |
| Oven temp. | 50°C (1min) → 25°C/min → 125°C → 10°C/min → 300°C |
| Inlet temp. | 250°C |
| Inlet mode | Splitless, 2µL |
| He flow | 1.0mL/min (Constant Flow) |
| MS/MS mode | Peak Dependent SRM |
結果
得られた測定結果の中から、4成分の農薬のSRMクロマトグラムをFig.1に示す。上段が人参抽出液のみのデータで、下段が農薬を添加した人参抽出液のデータである。MS/MS法の高選択性により、人参抽出液中の夾雑成分の影響を受けることなく農薬成分を検出できることを確認した。次頁のTable2には、農薬150成分の定量値（n=5）とその再現性（CV）を示す。ほとんどすべての農薬成分において定量値7~12ppb（回収率70~120%）、CV10%以下を達成しており、JMS-TQ4000GCが農薬分析に有効であることを確認した。
Fig.1 SRM chromatograms,
upper: Carrot extract solution only, lower: 10ppb pesticides in the carrot extract solution
Table 2 Quantitative result 150 pesticides in the carrot extract solution (n=5)
| No. | Compound | RT (min) | Quantitative values (ppb) | Ave. (ppb) | CV(%) | ||||
|---|---|---|---|---|---|---|---|---|---|
| No.1 | No.2 | No.3 | No.4 | No.5 | |||||
|
1 |
Atrazine |
12.37 | 9.1 | 10.1 | 9.6 | 9.8 | 9.1 | 9.5 | 4.5 |
|
2 |
Benthiocarb |
14.68 | 10.7 | 10.9 | 11.8 | 11.2 | 10.9 | 11.1 | 4.0 |
|
3 |
cis-Permethrin |
20.68 | 11.0 | 10.8 | 11.5 | 11.2 | 11.0 | 11.1 | 2.5 |
| 4 | Diflufenican | 18.31 | 9.7 | 8.7 | 10.6 | 9.9 | 9.3 | 9.7 | 7.3 |
| 5 | Fenamiphos | 16.24 | 8.9 | 8.2 | 9.4 | 9.0 | 9.4 | 9.0 | 5.6 |
| 6 | Fenarimol | 20.20 | 10.2 | 10.2 | 10.1 | 10.5 | 10.4 | 10.3 | 1.6 |
| 7 | Fenpropimorph | 14.74 | 10.9 | 11.0 | 11.1 | 11.8 | 10.8 | 11.1 | 3.5 |
| 8 | Norflurazon | 17.94 | 9.5 | 9.5 | 9.5 | 10.2 | 10.0 | 9.7 | 3.3 |
| 9 | Oxadiazon | 16.50 | 9.5 | 9.2 | 10.4 | 9.6 | 9.8 | 9.7 | 4.8 |
| 10 | Penconazole | 15.45 | 10.8 | 10.6 | 11.0 | 11.0 | 10.8 | 10.8 | 1.6 |
| 11 | Pendimethalin | 15.29 | 11.5 | 11.4 | 11.3 | 11.4 | 13.1 | 11.7 | 6.7 |
| 12 | Procymidone | 15.70 | 10.9 | 10.5 | 9.1 | 12.1 | 9.7 | 10.5 | 10.7 |
| 13 | Spiroxamine 1 | 13.78 | 9.7 | 9.9 | 10.2 | 10.8 | 10.5 | 10.2 | 4.3 |
| 14 | Spiroxamine 2 | 14.31 | 10.0 | 9.3 | 10.2 | 10.1 | 10.2 | 10.0 | 4.0 |
| 15 | Tefluthrine | 12.92 | 10.6 | 10.1 | 10.8 | 11.6 | 10.5 | 10.7 | 5.4 |
| 16 | Terbufos | 12.63 | 8.3 | 8.0 | 8.7 | 9.2 | 8.4 | 8.5 | 5.3 |
| 17 | Terbutryn | 14.31 | 10.0 | 9.7 | 10.5 | 10.4 | 10.4 | 10.2 | 3.6 |
| 18 | trans-Permethrin | 20.68 | 11.0 | 10.8 | 11.5 | 11.2 | 11.0 | 11.1 | 2.5 |
| 19 | Alachlor | 13.84 | 9.1 | 9.0 | 9.9 | 10.1 | 9.3 | 9.5 | 5.2 |
| 20 | Buprofezin | 16.68 | 12.0 | 9.8 | 10.5 | 11.5 | 11.8 | 11.1 | 8.5 |
| 21 | cis-Chlorfenvinphos | 15.49 | 8.2 | 7.8 | 9.1 | 8.8 | 8.8 | 8.6 | 5.9 |
| 22 | Cyproconazole 1 | 17.03 | 9.3 | 10.0 | 10.8 | 9.8 | 8.4 | 9.7 | 9.1 |
| 23 | Cyproconazole 2 | 17.03 | 11.3 | 10.2 | 10.2 | 11.8 | 12.6 | 11.2 | 9.3 |
| 24 | Difenoconazole 1 | 23.10 | 10.5 | 10.4 | 10.5 | 10.5 | 10.4 | 10.5 | 0.7 |
| 25 | Difenoconazole 2 | 23.18 | 10.6 | 10.5 | 10.5 | 10.6 | 10.6 | 10.6 | 0.5 |
| 26 | Ethion | 17.34 | 9.1 | 8.4 | 9.7 | 8.9 | 8.7 | 9.0 | 5.6 |
| 27 | Fenitrothion | 14.33 | 7.9 | 6.9 | 7.3 | 7.4 | 6.6 | 7.2 | 7.2 |
| 28 | Fenthion | 14.73 | 9.3 | 7.9 | 8.5 | 9.1 | 8.2 | 8.6 | 7.2 |
| 29 | Fluridone | 22.18 | 11.2 | 11.4 | 11.5 | 11.5 | 10.1 | 11.2 | 5.5 |
| 30 | Hexazinone | 18.24 | 8.3 | 8.0 | 9.1 | 8.9 | 8.8 | 8.6 | 4.8 |
| 31 | Isofenphos oxon | 14.79 | 9.3 | 9.3 | 10.1 | 10.4 | 9.2 | 9.7 | 5.6 |
| 32 | Isophenphos | 15.43 | 9.8 | 9.6 | 10.3 | 9.5 | 9.9 | 9.8 | 3.0 |
| 33 | Isoprothiolane | 16.44 | 10.2 | 9.9 | 10.9 | 10.2 | 9.6 | 10.2 | 4.4 |
| 34 | Propargite 1 | 18.31 | 7.7 | 7.4 | 8.8 | 8.1 | 8.1 | 8.0 | 6.8 |
| 35 | Propargite 2 | 18.31 | 8.4 | 7.8 | 9.1 | 8.7 | 8.4 | 8.5 | 6.0 |
| 36 | Propiconazole 1 | 17.93 | 11.5 | 10.4 | 10.8 | 11.5 | 10.8 | 11.0 | 4.5 |
| 37 | Propiconazole 2 | 18.07 | 11.8 | 11.3 | 11.2 | 11.1 | 10.7 | 11.2 | 3.5 |
| 38 | Propyzamide | 12.73 | 10.6 | 9.8 | 10.6 | 10.9 | 10.5 | 10.5 | 3.9 |
| 39 | Pyriproxyfen | 19.72 | 10.0 | 10.4 | 10.7 | 10.4 | 9.7 | 10.2 | 3.8 |
| 40 | trans-Chlorfenvinphos | 15.25 | 10.6 | 9.5 | 10.2 | 10.6 | 10.5 | 10.3 | 4.3 |
| 41 | Triadimenol 1 | 15.7 | 10.2 | 7.7 | 9.6 | 9.9 | 8.7 | 9.2 | 11.1 |
| 42 | Triadimenol 2 | 15.84 | 10.7 | 9.4 | 9.9 | 10.3 | 9.8 | 10.0 | 4.7 |
| 43 | Triallate | 13.13 | 7.5 | 7.3 | 7.6 | 8.1 | 7.6 | 7.6 | 3.5 |
| 44 | Vinclozoline | 13.76 | 8.1 | 8.2 | 8.1 | 9.2 | 8.6 | 8.4 | 5.6 |
| 45 | Acetamiprid | 18.92 | 10.8 | 8.7 | 9.6 | 9.3 | 10.3 | 9.7 | 8.6 |
| 46 | Allethrin 1 | 15.43 | 12.0 | 9.6 | 11.6 | 11.1 | 11.8 | 11.2 | 8.5 |
| 47 | Allethrin 2 | 15.51 | 6.4 | 6.6 | 7.3 | 7.5 | 7.3 | 7.0 | 7.1 |
| 48 | Bitertanol 1 | 20.66 | 12.1 | 12.1 | 12.5 | 12.3 | 12.2 | 12.3 | 1.2 |
| 49 | Bitertanol 2 | 20.76 | 9.6 | 9.6 | 10.3 | 10.0 | 10.0 | 9.9 | 3.1 |
| 50 | Bromopropylate | 19.00 | 8.7 | 8.3 | 9.1 | 9.3 | 9.2 | 8.9 | 4.4 |
| 51 | Chlorobenzilate | 17.19 | 7.8 | 7.0 | 8.2 | 7.9 | 7.6 | 7.7 | 5.5 |
| 52 | Chlorpyrifos | 14.63 | 8.5 | 8.2 | 8.9 | 9.9 | 9.9 | 9.1 | 8.6 |
| 53 | Oxyfluorfen | 16.59 | 11.6 | 11.1 | 9.1 | 9.5 | 11.2 | 10.5 | 10.7 |
| 54 | Parathion | 14.80 | 9.1 | 8.8 | 7.5 | 7.8 | 8.7 | 8.4 | 8.0 |
| 55 | Pirimiphos methyl | 14.24 | 9.3 | 9.2 | 9.6 | 10.0 | 9.7 | 9.6 | 3.5 |
| 56 | Propanil | 13.67 | 9.8 | 9.2 | 9.8 | 10.0 | 10.6 | 9.9 | 5.0 |
| 57 | Pyridaben | 20.87 | 10.4 | 9.8 | 10.9 | 10.5 | 9.9 | 10.3 | 4.5 |
| 58 | Quinoxyfen | 18.00 | 11.2 | 10.7 | 11.4 | 11.5 | 11.0 | 11.2 | 2.8 |
| 59 | Simazine | 12.29 | 9.3 | 9.8 | 9.7 | 9.8 | 8.7 | 9.5 | 4.9 |
| 60 | Tebuconazole | 18.38 | 10.8 | 10.2 | 9.4 | 10.9 | 10.1 | 10.3 | 5.9 |
| 61 | Triadimefon | 14.87 | 10.4 | 12.5 | 11.5 | 11.1 | 11.0 | 11.3 | 7.0 |
| 62 | Triazophos | 17.65 | 7.7 | 7.3 | 7.6 | 7.2 | 7.0 | 7.3 | 3.7 |
| 63 | Ametryn | 14.00 | 9.7 | 9.9 | 10.2 | 9.9 | 9.8 | 9.9 | 1.6 |
| 64 | Azaconazole | 16.83 | 12.4 | 12.4 | 12.8 | 13.3 | 12.8 | 12.7 | 3.1 |
| 65 | Bupirimate | 16.66 | 10.5 | 10.6 | 11.1 | 11.5 | 11.8 | 11.1 | 5.0 |
| 66 | Butachlor | 16.01 | 9.5 | 9.4 | 9.7 | 9.6 | 9.9 | 9.6 | 1.8 |
| 67 | Chlorthal dimethyl | 14.73 | 9.0 | 8.5 | 9.3 | 9.0 | 9.6 | 9.1 | 4.6 |
| 68 | Dicloran | 12.19 | 8.0 | 7.7 | 9.2 | 8.7 | 8.4 | 8.4 | 7.3 |
| 69 | Diethofencarb | 14.63 | 10.6 | 10.5 | 11.1 | 10.7 | 10.6 | 10.7 | 2.2 |
| 70 | Dimepiperate | 15.74 | 12.0 | 12.2 | 13.3 | 11.3 | 11.7 | 12.1 | 6.2 |
| 71 | Dimethenamid | 13.61 | 10.9 | 10.9 | 11.2 | 11.1 | 10.8 | 11.0 | 1.4 |
| 72 | Etoxazole | 19.03 | 10.7 | 9.2 | 10.8 | 10.6 | 9.5 | 10.2 | 7.3 |
| 73 | Fluacrypyrim | 17.38 | 9.8 | 9.6 | 10.2 | 10.3 | 10.5 | 10.1 | 3.7 |
| 74 | Lenacil | 18.14 | 11.4 | 11.4 | 11.5 | 11.3 | 11.5 | 11.4 | 0.6 |
| 75 | Pyriminobac methyl 1 | 17.96 | 12.3 | 12.0 | 11.4 | 11.8 | 12.0 | 11.9 | 2.7 |
| 76 | Pyriminobac methyl 2 | 12.88 | 10.6 | 10.5 | 10.0 | 11.0 | 10.6 | 10.5 | 3.5 |
| 77 | Pyroquilon | 19.53 | 9.6 | 10.2 | 10.0 | 10.9 | 9.8 | 10.1 | 4.8 |
| 78 | Tetradifon | 13.87 | 7.1 | 7.3 | 8.6 | 8.4 | 7.8 | 7.8 | 8.1 |
| 79 | Tolclofos-methyl | 16.61 | 9.7 | 8.8 | 10.3 | 9.7 | 10.2 | 9.7 | 5.8 |
| 80 | Uniconazole P | 13.66 | 9.7 | 9.9 | 10.5 | 10.5 | 10.1 | 10.2 | 3.7 |
| 81 | Acetochlor | 17.83 | 9.5 | 11.7 | 12.1 | 11.9 | 10.3 | 11.1 | 10.3 |
| 82 | Benalaxyl | 13.57 | 9.2 | 9.2 | 10.4 | 9.4 | 8.5 | 9.3 | 7.3 |
| 83 | Benfuresate | 11.71 | 10.2 | 9.1 | 9.9 | 9.8 | 9.3 | 9.6 | 4.6 |
| 84 | Cadusafos | 11.37 | 8.1 | 9.0 | 8.9 | 9.4 | 8.9 | 8.9 | 5.7 |
| 85 | Chlorpropham | 15.61 | 9.2 | 8.7 | 8.9 | 9.4 | 9.0 | 9.0 | 3.1 |
| 86 | Diclocymet 1 | 15.91 | 10.3 | 10.6 | 10.5 | 10.6 | 9.7 | 10.3 | 3.6 |
| 87 | Diclocymet 2 | 15.40 | 10.0 | 9.4 | 9.3 | 10.2 | 9.8 | 9.7 | 3.7 |
| 88 | Dimethametryn | 14.49 | 11.3 | 11.4 | 11.5 | 11.2 | 10.9 | 11.3 | 2.0 |
| 89 | Esprocarb | 21.83 | 9.2 | 9.3 | 9.8 | 9.3 | 8.9 | 9.3 | 3.3 |
| 90 | Etofenprox | 16.08 | 11.5 | 11.8 | 11.7 | 11.5 | 11.5 | 11.6 | 1.0 |
| 91 | Fenothiocarb | 13.27 | 10.7 | 10.2 | 10.3 | 10.3 | 10.5 | 10.4 | 1.8 |
| 92 | Iprobenfos | 16.92 | 9.2 | 9.3 | 9.8 | 9.8 | 9.6 | 9.5 | 2.6 |
| 93 | Isoxathion | 17.61 | 6.9 | 6.0 | 7.5 | 7.4 | 7.0 | 7.0 | 8.4 |
| 94 | Mepronil | 14.04 | 10.7 | 10.2 | 10.3 | 10.0 | 10.4 | 10.3 | 2.5 |
| 95 | Prometryn | 10.85 | 10.1 | 9.6 | 10.3 | 10.4 | 9.7 | 10.0 | 3.6 |
| 96 | Propachlor | 16.41 | 9.6 | 8.6 | 9.1 | 9.9 | 9.2 | 9.3 | 5.4 |
| 97 | Prothiofos | 15.99 | 8.4 | 9.0 | 9.1 | 9.3 | 7.4 | 8.6 | 8.7 |
| 98 | Pyrifenox 1 | 12.89 | 10.9 | 10.2 | 10.1 | 9.8 | 9.1 | 10.0 | 6.5 |
| 99 | Pyrimethanil | 13.94 | 9.6 | 10.1 | 9.8 | 9.9 | 9.1 | 9.7 | 3.9 |
| 100 | Simetryn | 13.06 | 10.8 | 10.0 | 11.3 | 10.8 | 10.3 | 10.6 | 4.9 |
| 101 | Terbacil | 14.82 | 12.4 | 12.6 | 13.3 | 12.5 | 13.1 | 12.8 | 3.0 |
| 102 | Tetraconazole | 18.31 | 12.0 | 12.6 | 11.3 | 12.3 | 10.8 | 11.8 | 6.3 |
| 103 | Thenylchlor | 16.58 | 7.7 | 8.3 | 8.8 | 8.4 | 8.2 | 8.3 | 4.9 |
| 104 | Tribufos | 16.66 | 8.8 | 8.4 | 8.7 | 9.0 | 9.1 | 8.8 | 2.9 |
| 105 | Tricyclazole | 15.72 | 7.5 | 6.9 | 9.4 | 9.0 | 8.4 | 8.2 | 12.3 |
| 106 | Zoxamide (decomposed) | 13.40 | 10.2 | 9.8 | 10.5 | 9.5 | 10.2 | 10.0 | 3.7 |
| 107 | Benoxacor | 14.44 | 8.1 | 7.9 | 8.5 | 7.9 | 7.4 | 8.0 | 4.8 |
| 108 | Bromacil | 13.70 | 9.3 | 7.3 | 10.1 | 8.6 | 8.7 | 8.8 | 11.4 |
| 109 | Bromobutide | 16.17 | 11.2 | 15.3 | 14.0 | 12.5 | 12.6 | 13.1 | 11.9 |
| 110 | Butamifos | 13.56 | 10.1 | 10.0 | 11.0 | 10.5 | 10.1 | 10.3 | 4.1 |
| 111 | Dichlofenthion | 15.12 | 10.1 | 10.0 | 10.2 | 10.5 | 9.8 | 10.1 | 2.6 |
| 112 | Diphenamid | 16.42 | 12.3 | 11.6 | 11.9 | 12.1 | 11.6 | 11.9 | 2.7 |
| 113 | Hexaconazole | 14.00 | 10.3 | 10.3 | 10.5 | 10.3 | 10.4 | 10.4 | 1.0 |
| 114 | Mefenoxam | 16.33 | 9.3 | 10.2 | 10.0 | 9.3 | 9.8 | 9.7 | 4.3 |
| 115 | Napropamide | 17.40 | 10.1 | 9.6 | 9.4 | 10.3 | 10.1 | 9.9 | 3.7 |
| 116 | Oxadixyl | 16.07 | 10.5 | 10.3 | 10.5 | 10.5 | 10.2 | 10.4 | 1.3 |
| 117 | Paclobutrazol | 19.31 | 11.5 | 10.7 | 10.9 | 10.6 | 11.3 | 11.0 | 3.5 |
| 118 | Phenothrin 1 | 19.42 | 11.3 | 12.7 | 12.6 | 11.9 | 12.9 | 12.2 | 5.5 |
| 119 | Phenothrin 2 | 18.98 | 10.2 | 10.4 | 10.7 | 10.7 | 10.5 | 10.5 | 2.0 |
| 120 | Piperophos | 12.94 | 9.1 | 9.2 | 9.5 | 10.2 | 9.2 | 9.4 | 4.9 |
| 121 | Prohydrojasmon 1 | 13.23 | 8.6 | 8.2 | 8.9 | 9.3 | 8.9 | 8.8 | 4.8 |
| 122 | Prohydrojasmon 2 | 12.42 | 12.7 | 9.9 | 10.5 | 8.5 | 9.2 | 10.2 | 15.7 |
| 123 | Propazine | 18.63 | 10.1 | 10.2 | 10.2 | 10.0 | 9.7 | 10.0 | 2.0 |
| 124 | Pyributicarb | 15.51 | 12.1 | 11.5 | 11.7 | 11.9 | 11.8 | 11.8 | 1.9 |
| 125 | Pyrifenox 2 | 15.63 | 10.4 | 9.9 | 9.8 | 10.1 | 9.6 | 10.0 | 3.1 |
| 126 | Quinalphos | 19.16 | 10.5 | 10.0 | 10.7 | 10.6 | 10.0 | 10.3 | 3.4 |
| 127 | Tebufenpyrad | 24.05 | 9.0 | 9.8 | 10.0 | 9.8 | 9.3 | 9.6 | 4.1 |
| 128 | Tolfenpyrad | 14.78 | 9.3 | 9.6 | 9.4 | 9.7 | 9.3 | 9.5 | 1.7 |
| 129 | Aldrin | 16.26 | 7.6 | 7.6 | 7.4 | 8.0 | 7.5 | 7.6 | 3.2 |
| 130 | cis-Chlordane | 14.97 | 8.4 | 7.1 | 9.1 | 9.2 | 7.9 | 8.3 | 10.3 |
| 131 | Dicofol | 16.78 | 11.9 | 10.8 | 11.5 | 11.3 | 11.1 | 11.3 | 3.6 |
| 132 | Dieldrin | 17.19 | 10.6 | 9.4 | 10.7 | 11.0 | 9.7 | 10.3 | 6.8 |
| 133 | Endrin | 14.07 | 11.3 | 11.4 | 9.8 | 9.2 | 11.2 | 10.6 | 9.7 |
| 134 | Heptachlor | 16.02 | 7.3 | 6.9 | 8.0 | 8.3 | 7.1 | 7.5 | 7.9 |
| 135 | trans-Chlordane | 14.40 | 9.2 | 10.1 | 9.9 | 9.7 | 9.8 | 9.7 | 3.5 |
| 136 | 1-Naphthylacetamide | 15.87 | 11.6 | 10.1 | 10.7 | 10.1 | 10.7 | 10.6 | 5.7 |
| 137 | Bromophos ethyl | 16.80 | 8.8 | 7.7 | 9.5 | 8.9 | 8.7 | 8.7 | 7.6 |
| 138 | Carboxin | 15.98 | 11.4 | 10.9 | 11.3 | 11.5 | 11.1 | 11.2 | 2.3 |
| 139 | Chlorbenside | 16.42 | 9.2 | 9.6 | 9.4 | 9.1 | 9.3 | 9.3 | 2.0 |
| 140 | Chlorofenson | 24.99 | 7.8 | 7.4 | 8.4 | 8.3 | 8.2 | 8.0 | 5.1 |
| 141 | clomazone | 12.47 | 8.8 | 8.9 | 8.8 | 8.9 | 8.6 | 8.8 | 1.2 |
| 142 | Disulfoton | 12.98 | 8.7 | 8.6 | 9.3 | 10.2 | 8.7 | 9.1 | 7.3 |
| 143 | Epoxiconazole | 18.61 | 10.6 | 10.4 | 10.8 | 10.7 | 10.6 | 10.6 | 1.6 |
| 144 | Ethofumesate | 14.37 | 9.8 | 10.1 | 10.1 | 10.2 | 10.4 | 10.1 | 2.3 |
| 145 | Fenamidone | 19.17 | 10.3 | 10.4 | 10.3 | 10.2 | 9.7 | 10.2 | 2.7 |
| 146 | Flutriafol | 16.28 | 10.5 | 11.1 | 10.6 | 10.6 | 10.3 | 10.6 | 2.9 |
| 147 | Isazophos | 12.96 | 9.0 | 9.1 | 9.7 | 10.2 | 9.2 | 9.4 | 5.2 |
| 148 | Phorate | 11.79 | 7.0 | 7.8 | 7.6 | 8.3 | 7.8 | 7.7 | 5.8 |
| 149 | Picolinafen | 18.97 | 11.1 | 11.0 | 11.1 | 11.4 | 10.8 | 11.1 | 2.2 |
| 150 | Propaphos | 15.89 | 11.0 | 10.8 | 11.4 | 10.5 | 10.7 | 10.9 | 3.0 |
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