The Korean Society of Pesticide Science

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The Korean Journal of Pesticide Science - Vol. 20 , No. 2
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The Korean Journal of Pesticide Science - Vol. 20, No. 2, pp. 104-127
Abbreviation: Korean Journal of Pesticide Science
ISSN: 1226-6183 (Print) 2287-2051 (Online)
Print publication date Jun 2016
Received 25 Mar 2016 Revised 27 May 2016 Accepted 17 Jun 2016
DOI: https://doi.org/10.7585/kjps.2016.20.2.104

LC-MS/MS와 GC-MS/MS를 이용한 사과와 쌀 시료에서 320종 농약의 다성분 분석
김종환 ; 김영진 ; 권영상 ; 서종수*
안전성평가연구소 환경독성연구센터

Development of Multi-residue Analysis of 320 Pesticides in Apple and Rice Using LC-MS/MS and GC-MS/MS
Jong-Hwan Kim ; Yeong-Jin Kim ; Young-Sang Kwon ; Jong-Su Seo*
Environmental Toxicology Research Center, Korea Institute of Toxicology, Jinju 52834, Korea
Correspondence to : *jsseo@kitox.re.kr

Funding Information ▼
초록

본 연구는 사과와 쌀에서 320성분 농약에 대한 다성분 동시분석법을 확립하고자 수행되었다. 시료의 추출은 QuEChERS법을 사용하였고, 추출 후 잔류물은 LC-MS/MS와 GC-MS/MS로 기기분석 하였다. 시험 농약은 LC-MS/MS 251성분, GC-MS/MS 110성분을 선발하였으며, 41성분은 공통적으로 적용되었다. 분석법의 정량한계는 LC-MS/MS에서 0.01~20 μg/kg, GC-MS/MS에서 0.1~100 μg/kg으로 산출되었다. 사과와 쌀에서 회수율 70~120%, 상대 표준편차 20% 이내의 조건을 충족한 성분은 LC-MS/MS로 분석한 농약 중 각각 242성분(96%)과 237성분(94%)로 나타났으며, GC-MS/MS로 분석한 농약 중에는 각각 103성분(94%)과 83성분(76%)로 나타났다. 본 연구를 통해 QuEChERS 전처리와 LC-MS/MS 및 GC-MS/MS를 이용한 분석법은 농산물(사과 및 쌀) 중 잔류농약 다성분 동시 분석에 효과적으로 적용될 것으로 기대된다.

Abstract

A new analytical method has been developed to determine 320 pesticides in apple and rice. The extraction of pesticides was carried out based on QuEChERS sample extraction, and determination was performed using LC-MS/MS and GC-MS/MS. 320 pesticides were selected for experiments. 251 and 110 pesticides among them were analysed by LC-MS/MS and GC-MS/MS, respectively. 41 pesticides of them were analyzed by both GC-MS/MS and LC-MS/MS. Among pesticides analysed by LC, 242 pesticides (96% of total number) in apple and 237 pesticides (94% of total number) in rice showed recoveries in the range of 70~120% with RSD ≤ 20%. In case of pesticides analyzed by GC-MS/MS, 103 pesticides (94% of total number) in apple and 83 pesticides (76% of total number) in rice were successfully validated. These results indicated that LC-MS/MS and GC-MS/MS analysis with the QuEChERS sample preparation can be partly applied to multi-residue pesticides in agricultural products.

Keywords: GC-MS/MS, LC-MS/MS, Multiresidue analysis, Pesticide, QuEChERS
키워드: 농약, 다성분동시분석
서 론

농약은 현대 농업에 있어 작부체계 및 재배방법 개선, 품질과 저장성의 향상 및 노동력 절감, 생산량 증대 등을 위한 중요하고도 필수적인 농업자재이다(Fenik 등, 2011; Lee 등, 2013). 그러나 농작물에 살포된 농약은 사용목적을 달성한 후 환경에서 분해되어 잔류하지 않는 것이 가장 이상적이지만 농약은 대부분 유기합성물질로서 자체의 물리화학적 특성에 따라 농작물 및 토양 등 재배환경 중에 잔류하게 된다(Do 등, 2010; Lee 등, 2008). 잔류농약은 농산물을 섭취하는 단계에서 인체에 흡수, 축적되어 안전성 문제를 발생시킬 가능성이 있으므로 효율적인 농산물 안전관리를 위해서는 잔류농약에 대한 지속적인 연구와 모니터링이 필요하다.

현재 세계 각국에서는 농산물 안전성 확보를 위하여 자국에서 생산된 농산물 뿐만 아니라 수입산 농산물에 대해서도 유해물질 규제와 검역기준을 대폭 강화하고 있으며, 농산물을 통해 섭취될 수 있는 잔류농약에 대한 안전성을 확보하기 위하여 국가마다 농산물에 대한 농약안전사용기준과 농약의 최대잔류허용기준(Maximum Residue Limits, MRLs)을 설정하여 관리하고 있다(Bhanti 등, 2007). 또한, 농식품의 안전성에 대한 소비자의 높은 관심에 따라 농식품 내의 유해물질을 신속 정확하게 분석하는 기술이 중요시 되고 있다. 그 중에서도 대표적인 유해 물질인 잔류농약 분석은 다양한 매트릭스 내에 존재하는 극미량의 성분을 분석하기 위해 농약 이외의 복잡한 불순물을 선택적으로 제거해야하는 정제방법이 복잡할 뿐만 아니라 분석결과의 공적, 법적 사용을 위하여 높은 신뢰성이 요구되기 때문에 많은 시간과 비용, 분석자의 숙련된 기술이 요구된다(Lee 등, 2012).

최근 농식품 중의 잔류농약 분석을 위해 전처리방법을 간소화 시키면서 고감도 질량분석기를 이용하여 신속하게 분석하는 방법이 필수적이기에 대부분 다종다성분 분석법이 적용되고 있다(Guana 등, 2010; Ju 등, 2011; Kwon 등, 2011; Zhang 등; 2011). QuEChERS (Quick, Easy, Cheap, Effective, Rugged and Safe) 전처리법은 미농무성 농업연구소(Agricultural Research Service)에서 개발되어 AOAC 및 European Committee에서 농약다성분 분석법으로 인정받았으며(Anastassiades 등, 2003; Lehotay 등, 2010), 기존 농약 잔류분석법과 달리 분석방법이 간단하고 개발이 쉬운 장점을 가지고 있어 다양한 시료를 대상으로 농약의 다성분분석 뿐만 아니라 농약의 대사물질을 동시 분석하는데도 적용이 가능하다(Cajka 등, 2008; Ju 등, 2011; Koesukwiwat 등, 2010; Seo 등, 2013). 또한, 최근 국외 잔류 농약 분석에 관한 연구는 GC/MS/MS와 LC/MS/MS를 동시에 적용한 농약 다성분 분석연구가 수행되어지고 있다(Chamkasem 등, 2013; Lehotay 등, 2005; Pang 등, 2006).

따라서 본 연구에서는 최근 사용 빈도가 높은 국내 등록 농약에 대한 잔류분석법을 확립하기 위하여 LC-MS/MS와 GC-MS/MS를 이용하여 다종농약 다성분 동시분석법 적용시험을 수행하였다.

재료 및 방법
농약표준용액 및 시약

분석에 사용한 표준품은 HPC Standards GmbH (Cunnersdorf, Germany), AccuStandard (New Haven, CT, USA), LGC Standard (Teddington Middlesex, UK), Wako Pure Chemical (Osaka, Japan)로부터 구입하였으며 각각의 농약표준품은 acetone, acetonitrile으로 1,000 mg/L의 용액을 LC-MS/MS 및 GC-MS/MS 분석용 혼합표준용액(5 mg/L) 조제하여 4oC 냉장보관 하여 사용하였다.

분석에 사용된 용매인 formic acid (98%)는 Junsei Chemical(Tokyo, Japan), ammonium formate (99.995%)는 Sigma-Aldrich (Steinheim, Germany) 제품을 구입 하였다. 시료 추출 및 정제를 위해 사용한 acetonitrile, acetone, methanol은 Burdick&Jackson (Muskegon, MI, USA)로부터 구입하여 사용하였고, QuEChERS법 추출을 위해 QuEChERS Extract Kit (magnesium sulfate; 98.5~101.5%, sodium chloride; ≥ 99.5%, sodium citrate; 99.9%, disodium citrate sesquihydrate; 99%)와 정제를 위해 사용된 QuEChERS dispersive SPE 2 mL (primary secondary amine (PSA), octadecysilane end-capped, magnesium sulfate; 98.5~101.5%)은 Agilent(Boblingen, Germany)로부터 구입하여 사용하였다.

전처리방법

시험에 사용된 사과와 쌀은 친환경인증을 받은 무농약 시료로 분쇄기를 이용하여 균질화한 후 회수율 시험 및 blank 시료로 사용하였고 쌀시료의 경우 분쇄한 시료 5 g을 칭량하여 증류수 10 mL 넣고 1시간 습윤화 시켜 분석시료로 사용하였으며, 칭량된 각 시료에 acetonitrile 10 mL을 넣고 1분간 진탕하였다. 사과와 쌀 추출액에 4 g의 anhydrous magnesium sulfate, 1 g의 sodium chloride, 1 g의 sodium citrate, 0.5 g의 disodium citrate sesquihydrate 를 첨가 후 ceramic homogenizers를 이용하여 1분간 강하게 진탕 하였으며, 진탕한 시료는 원심분리기를 이용하여 4,500 rpm에서 5분간 원심분리를 하였다. Acetonitrile층과 water층을 분리 후, GC-MS/MS 분석을 위해서는 시료의 상징액 1 mL을 25 mg PSA, 150 mg magnesium sulfate (MgSO4), 25 mg C18EC (octadecysilane, end-capped)가 충진되어 있는 dispersive SPE tube에 넣고 1분간 진탕 후 12,000 rpm으로 2분간 원심분리하여 시액으로 사용하였고, LC-MS/MS 분석을 위해서는 상징액을 0.2 μm syringe filter (Whatman, PTFE)로 여과하여 시액으로 사용하였다(Fig. 1).

농약성분의 정량분석을 위한 검량선은 각각의 표준품을 acetonitrile에 녹여 1,000 mg/L의 stock solution을 조제한 후 무처리 시료 추출액과 혼합하여 10, 25, 100, 150, 200 및 250 μg/L 농도로 matrix matched calibration을 작성하였다. 각 농약성분에 대한 회수율 시험은 50 및 200 μg/kg 수준에서 결과를 확인하였다.


Fig. 1. 
Flow chart diagram of QuEChERS preparation for pesticides analysis.

기기분석 조건

LC-MS/MS는 Agilent Technologies사의 6460 Triple Quad LC/MS 기기를 사용하였고, 데이터 처리는 MassHunter Quantitative Analysis 소프트웨어를 사용하였다. GC-MS/MS는 Bruker사의 SCION TQ 기기를 사용하였고, 데이터 처리는 MS Work Station 8을 사용하였다. 분석 조건은 Table 1과 2에 나타내었다. LC-MS/MS 분석대상 농약 251종과 GC-MS/MS 분석대상 농약 110종에 대한 MRM 조건은 각각 Table 3과 4에 나타내었다.

Table 1. 
Analytical conditions of LC-MS/MS
Instrument : Agilent 6460 Triple Quad LC/MS with Agilent 1260 series HPLC
Column : Agilent Poroshell 120 EC-C18, 2.1 × 100 mm, I.d., 2.7 μm
Mobile phase A : 5 mM ammonium formate & 0.1% formic acid in water
Mobile phase B : 5 mM ammonium formate & 0.1% formic acid in methanol
Gradient program Time (min) A (%) B (%) Flow (mL/min)
Initial 85 15 0.3
1 85 15 0.3
1.5 40 60 0.3
10 10 90 0.3
15 10 90 0.3
20 2 98 0.3
20.1 85 15 0.3
25 85 15 0.3
Injection volume : 1 μL
Column temperature : 40oC
Sample Tray Temp. : 10oC
Ionization mode : ESI positive
Gas temperature : 325oC
Gas Flow : 6 mL/min
Nebulizer gas pressure : 35 psi
Ionspray voltage : +4000 V
Scan type : Dynamic MRM mode

Table 2. 
Analytical conditions of GC-MS/MS
Instrument : Bruker SCION TQ
Column : BR-5ms, 30 m × 0.25 mm i.d., 0.25 μm
Flow rate : Helium (99.999%) at 1.5 mL/min
Injection vol., mode : 1 μL, split ratio 50:1, 260℃
Column oven Temperature (oC) Rate (oC/min) Hold (min) Total (min)
90 3 3
120 20 0 4.5
300 8 3 30
Source temperature : 200oC
Transfer line : 280oC
Manifold : 40oC
Ionization : Electron ionization (EI), 70 eV
Scan mode : MRM (Multiple Reaction Monitoring) mode

회수율, 검출한계 및 정량한계의 측정

본 연구에서 잔류농약 분석법의 효율과 신뢰성을 검정하기 위하여 회수율 시험을 진행하였다. 회수율 시험은 무처리 사과와 쌀 시료에 첨가농도가 50 μg/kg, 200 μg/kg이 되도록 표준용액을 첨가한 다음 상기 전처리방법에 따라 회수율 시험을 3반복 수행하였다. 검출한계(limits of detection, LOD)와 정량한계(limits of quantification, LOQ)는 각 농도별 표준용액을 시료에 spiking하여 분석하여 얻은 크로마토그램을 기초로 하여 LOD는 S/N ratio가 3 이상, LOQ는 S/N ratio 10 이상을 기준으로 측정하였다.

Table 3. 
Parameters for 251 pesticide residue analysis by LC-MS/MS
No. Pesticides Retention time (min) Parent ion Quantitative ion (m/z) Collision energy (V) Qualitative ion (m/z) Collision energy (V) Fragmentor Voltage (V)
1 Abamectin B1 12.3 890.5 145.0 30 113.2 50 140
2 Acephate 1.0 184.0 143.0 5 95.0 20 90
3 Acetamiprid 4.1 223.1 126.0 20 56.2 20 100
4 Acibenzolar-S-methyl 6.2 211.0 136.1 28 91.2 16 120
5 Alachlor 7.2 270.1 238.1 10 162.1 15 80
6 Aldicarb 4.5 116.1 89.0 5 70.1 5 80
7 Ametoctradin 8.7 276.1 176.1 30 149.0 30 170
8 Amisulbrom 9.2 466.0 227.0 18 107.8 18 100
9 Amitraz 11.2 294.0 163.0 9 121.9 30 90
10 Azimsulfuron 5.4 424.9 181.9 10 155.9 34 110
11 Azinphos-methyl 5.8 318.0 132.1 8 77.0 40 80
12 Azoxystrobon 6.0 404.2 372.2 11 344.2 20 100
13 Bendiocarb 4.8 224.1 167.1 5 109.0 10 80
14 Benfuracarb 9.42 411.0 251.9 8 194.9 20 100
15 Benfuresat 14.9 391.2 149.1 16 65.2 84 104
16 Bensulfuron-methyl 5.8 410.9 148.9 15 181.9 20 120
17 Benthiavalicarb-Isopropyl 6.6 382.2 180.1 29 116.1 20 120
18 Benzobicyclon 6.5 446.9 256.9 24 228.9 40 160
19 Benzoximate 8.4 364.1 199.0 10 105.1 31 100
20 Bifenazate 6.8 301.2 198.0 4 170.0 16 75
21 Bitertanol 8.4 338.2 70.1 10 99.1 10 100
22 Boscalid 6.3 343.1 307.1 20 140.0 20 100
23 Bromacil 4.8 261.0 204.9 4 131.9 44 80
24 Buprofezin 9.7 306.2 116.1 14 201.1 14 100
25 Cadusafos 8.7 271.1 159.0 10 97.0 49 90
26 Cafenstrol 6.7 351.2 100.1 3 72.1 28 50
27 Carbarl (NAC) 5.0 202.1 145.0 4 127.0 20 60
28 Carbendazim 3.7 192.1 160.1 20 132.1 30 110
29 Carbofuran 4.8 222.2 165.0 14 123.0 16 100
30 Carboxin 5.0 236.1 142.9 8 87.0 20 85
31 Carfentrazone-ethyl 7.7 412.1 345.9 20 365.9 12 150
32 Carpropamid 7.9 334.1 139.0 20 103.0 40 100
33 Chlorantraniliprole 5.8 484.0 285.9 13 452.8 15 100
34 Chlorfluazron 11.3 540.0 382.9 20 347.0 50 120
35 Chlorpyrifos 10.2 350.0 97.1 25 197.9 25 60
36 Chlorsulfuron 4.9 358.0 141.0 16 167.0 12 105
37 Chromafenozide 6.9 395.2 175.1 20 147.0 55 100
38 Clethodim 6.6 360.1 164.1 16 136.1 24 97
39 Clofentezine 8.3 303.0 138.0 20 102.0 55 100
40 Clomazone 5.9 240.1 124.9 16 89.0 52 105
41 Clothianidin 3.9 250.0 132.0 20 169.0 20 100
42 Cyazofamid 7.2 325.1 108.0 11 261.2 11 100
43 Cyclosulfamuron 6.8 422.1 260.9 12 217.9 24 110
44 Cyflufenamid 8.4 413.2 203.1 38 241.2 13 120
45 Cyhalofop-butyl 9.0 358.2 256.0 28 120.0 8 90
46 Cymoxanil 4.2 199.1 128.0 4 111.0 12 61
47 Cyproconazole 6.6 292.1 70.1 16 125.0 30 100
48 Cyprodinil 7.4 226.2 77.1 50 93.1 50 120
49 Cyromazine 0.9 167.1 85.0 16 125.1 16 100
50 DDVP (Dichlovos) 4.8 221.0 109.0 19 126.9 19 120
51 Dinotefuran 2.3 203.1 129.2 4 114.2 8 81
52 Diafenthiuron 11.0 385.2 329.1 16 278.1 32 140
53 Diazinon 8.0 305.1 169.1 20 153.1 20 160
54 Dichlofluanid 6.8 350.0 224.1 10 123.1 35 100
55 Diethofencarb 6.1 268.2 180.1 13 226.1 13 80
56 Difenoconazole 8.8 406.1 251.0 20 337.1 19 100
57 Diflubenzuron 7.4 311.1 158.2 8 141.1 36 90
58 Dimepiperate 8.9 264.1 119.0 10 146.0 5 100
59 Dimethametryn 7.2 256.0 186.0 18 91.0 26 130
60 Dimethenamid 6.3 276.1 244.1 16 168.2 16 80
61 Dimethoate 4.1 230.0 199.0 5 171.0 10 80
62 Dimethomorph (1) 6.2 388.2 301.1 20 165.0 25 120
Dimethomorph (2) 6.5 388.2 301.1 20 165.0 25 120
63 Dimethylvinphos 6.8 331.0 127.0 15 170.1 47 90
64 Demeton-S-methyl 4.9 231.1 89.1 2 61.1 30 50
65 Diniconazole 8.6 326.1 70.1 25 159.0 30 120
66 Diphenamid 5.7 240.2 134.1 20 167.0 20 100
67 Dithiopyr 9.1 402.1 271.9 30 353.9 24 135
68 Diuron 5.6 233.1 72.1 25 160.0 25 100
69 Dymron 6.6. 269.0 151.0 16 119.0 25 90
70 Edifenphos 7.8 311.1 109.0 35 111.0 25 80
71 EPN 8.8 324.1 157.1 20 295.9 12 50
72 Esprocarb 9.7 266.2 91.1 20 65.1 79 110
73 Ethaboxam 5.2 321.1 183.1 35 200.1 35 160
74 Ethiofencarb 5.2 226.1 107.1 15 164.2 7 50
75 Ethofenprox 12.7 394.3 177.2 21 135.1 33 100
76 Ethoprophos 7.1 243.1 97.0 30 131.0 20 100
77 Ethoxyquin 6.0 218.0 159.9 32 173.9 18 130
78 Ethoxysulfuron 6.6 398.9 260.9 10 217.8 22 120
79 Etoxazole 10.7 360.2 141.0 35 63.1 129 150
80 Etrimfos 7.8 293.1 125.0 24 265.1 25 120
81 Famoxadone 8.1 397.1 353.0 8 261.2 8 120
82 Fenamidone 6.2 312.2 92.1 25 65.1 40 100
83 Fenamiphos 7.4 304.2 217.0 20 202.0 40 110
84 Fenarimol 7.0 331.1 268.0 25 81.0 30 120
85 Fenazaquin 11.4 307.2 161.2 25 147.1 25 100
86 Fenbuconazole 7.3 337.1 70.0 20 125.0 20 120
87 Fenhexamid 7.1 302.1 97.2 20 55.2 40 134
88 Fenobucarb (BPMC) 6.1 208.1 95.1 15 152.1 9 40
89 Fenothiocarb 7.5 254.2 72.1 14 160.1 12 100
90 Fenoxanil (1) 7.4 329.1 302.1 4 86.3 20 80
Fenoxanil (2) 7.5 329.1 302.1 4 86.3 20 80
91 Fenoxaprop-ethyl 9.4 362.1 288.1 12 121.1 28 138
92 Fenoxycarb 7.5 302.0 116.0 7 256.0 7 90
93 Fenpyroximate 11.0 422.2 366.2 24 135.0 35 100
94 Fenthion (MPP) 7.8 279.0 169.1 12 247.0 8 115
95 Fentrazamide 7.9 350.0 83.0 20 154.0 8 80
96 Ferimzone 5.9 255.2 124.1 30 132.1 30 120
97 Flomicamid 3.6 230.0 203.0 14 148.0 30 100
98 luaxrypyrim 8.8 427.2 145.1 25 205.1 5 100
99 Flubendiamide 7.7 408.0 273.8 17 255.8 22 100
100 Flucetosulfuron 6.0 488.1 156.0 16 273.0 24 125
101 Fludioxonil 6.3 266.2 229.1 10 158.1 47 100
102 Flufenacet 7.1 364.1 152.0 16 194.0 4 85
103 Flufenoxuron 10.8 489.1 158.1 17 141.2 35 150
104 Flumioxazin 5.8 355.1 299.1 32 327.0 32 135
105 Fluopiolide 6.5 383.0 172.9 25 108.9 91 100
106 Fluopyram 6.9 397.1 173.0 20 207.9 32 125
107 Fluquinconazole 6.9 376.0 307.0 30 108.1 69 100
108 Flusilazole 7.4 316.1 247.1 15 165.0 20 120
109 Flutolanil 6.5 324.2 262.1 15 242.1 25 120
110 Forchlorfenuron 5.6 248.1 129.1 18 155.1 19 100
111 Fosthiazate 5.2 284.1 104.0 20 228.0 9 70
112 Furathiocarb 9.6 383.2 195.1 10 252.0 10 100
113 Gibberrellic acid 4.1 364.2 239.3 14 221.2 20 90
114 Halosulfuron-methyl 6.8 434.9 182.1 10 139.1 50 120
115 Haloxyfop 7.7 362.0 316.1 12 91.2 36 120
116 Hexaconazole 8.2 314.1 70.1 20 159.1 20 120
117 Hexaflumuron 9.1 461.0 158.0 20 141.0 48 134
118 Hexazinone 4.9 253.2 171.0 12 71.1 36 100
119 Hexythiazox 10.3 353.2 168.0 22 228.2 15 100
120 Imazalil 5.3 297.1 159.0 30 69.1 30 100
121 Imazosulfuron 6.3 413.1 152.9 8 156.0 16 110
122 Imibenconazole 10.0 411.0 124.9 27 170.8 25 100
123 Imicyafos 4.6 305.1 201.0 16 235.0 14 120
124 Imidacloprid 3.9 256.1 175.1 20 209.1 20 100
125 Inabenfide 6.2 339.1 321.0 12 80.0 32 125
126 Iprobenfos 7.6 289.2 91.1 17 205.1 6 50
127 Iprovalicarb 6.8 321.3 119.1 20 203.1 5 80
128 Isoprocarb (MIPC) 5.4 194.2 95.1 10 137.1 10 70
129 Isoprothiolane 6.5 291.1 189.0 15 231.1 12 70
130 Isopyrazam 8.8 360.2 244.0 20 320.1 16 130
131 Kresoxim-methyl 7.7 314.0 222.0 10 267.0 5 80
132 Linuron 6.1 249.0 159.9 16 182.0 8 100
133 Lufenuron 10.2 511.0 157.8 10 140.9 30 100
134 Malathion 6.5 331.0 127.0 5 99.0 10 80
135 Mandipripamid 6.4 412.2 328.2 12 125.0 40 100
136 Mefenacet 6.7 299.1 148.1 15 120.2 25 100
137 Mepanipyrim 6.9 224.2 77.1 45 106.1 40 100
138 Mepronil 6.6 270.2 119.0 20 91.0 45 100
139 Metalaxyl 5.5 280.2 160.1 22 220.2 14 100
140 Metamifop 9.5 441.1 288.0 22 180.1 22 150
141 Metazosulfuron 6.1 476.1 182.1 20 295.1 10 110
142 Metconazole 8.3 320.2 70.1 25 125.1 50 100
143 Methabenzthiazuron 5.4 222.1 165.1 17 150.1 35 100
144 Methidathion 5.7 303.0 85.0 15 145.0 10 70
145 Methiocarb 6.2 226.1 169.1 5 121.1 10 80
146 Methomyl 3.6 163.1 88.1 5 106.1 5 50
147 Methoxyfenozide 6.5 369.2 149.1 13 133.1 15 100
148 Metobromuron 5.4 259.0 170.0 18 148.2 18 100
149 Metolachlor 7.3 284.2 252.2 15 176.1 25 100
150 Metolcarb 4.6 166.1 109.1 10 94.1 25 50
151 Metrafenone 8.5 40.91 209.0 8 226.9 16 105
152 Metribuzin 4.9 215.1 187.2 28 60.0 53 100
153 Mevinphos-1 4.1 225.1 127.1 10 193.1 0 50
Mevinphos-2 4.3 225.1 127.1 10 193.1 0 50
154 Milbemectin A3 12.0 511.3 95.0 30 105.0 60 100
Milbemectin A4 12.6 525.4 55.2 80 91.0 114 120
155 Molinate 6.7 188.1 55.1 25 126.1 10 120
156 Monocrotophos 3.7 224.1 127.0 10 193.0 0 100
157 Myclobutanil 6.7 289.2 70.1 27 125.0 27 100
158 Napropamide 7.1 272.2 171.1 18 129.1 18 100
159 Nicosulfuron 4.7 411.1 182.0 16 106.0 36 120
160 Novaluron 9.3 493.0 158.2 16 141.2 52 90
161 Nuarimol 6.1 315.1 81.0 30 251.9 25 120
162 Ofurace 4.8 282.1 160.2 18 254.2 13 100
163 Omethoate 2.0 214.0 125.0 20 183.0 5 80
164 Oxadiazon 9.9 345.1 220.0 18 177.0 19 135
165 Oxadixyl 4.5 279.1 219.0 32 177.0 4 75
166 Oxamyl 3.2 237.1 72.1 10 90.1 10 80
167 Oxaziclomefon 9.4 376.1 190.1 11 133 27 100
168 Paclobutrazole 6.5 294.1 70.1 20 125.0 48 100
169 Penconazole 7.8 284.1 70.1 20 159.0 39 80
170 Pencycuron 8.6 329.0 125.0 24 89.0 60 100
171 Pendimethalin 10.3 282.1 212.1 13 194.1 17 70
172 Penoxsulam 5.0 484.1 195.0 28 164.0 36 160
173 Penthiopyrad 7.8 360.1 275.9 8 177.0 36 110
174 Pentoxazone 9.5 354.2 286.0 15 186.0 15 135
175 Phenthoate 7.6 321.1 79.0 55 135.0 20 100
176 Phorate 8.3 261.0 75.0 4 199.1 0 60
177 Phosalone 8.4 368.1 181.9 10 75.1 100 100
178 Phosphamidone 4.5 300.1 127.0 20 174.1 17 120
179 Phoxim 8.2 299.1 77.0 36 129.0 4 70
180 Picoxystrobin 7.5 368.1 145.0 16 205.1 4 75
181 Piperophos 8.8 354.1 171.0 20 255.1 12 90
182 Pirimicarb 4.8 239.2 72.1 20 182.2 18 100
183 Pirimiphos-methyl 8.3 306.2 108.1 22 164.1 32 100
184 Probenazole 6.9 224.0 77.3 88 51.2 40 62
185 Prochloraz 8.2 376.1 308.0 13 70.0 22 50
186 Profenofos 9.4 373.0 302.9 15 127.9 50 90
187 Prometryn 6.5 242.2 158.1 27 200.1 27 100
188 Propamocarb 2.2 189.2 102.1 15 73.9 20 100
189 Propanil 6.2 218.0 162.0 15 127.0 20 120
190 Propaquizafop 9.8 444.1 100.0 12 56.1 36 115
191 Propiconazole 8.0 342.1 159.0 20 69.0 20 120
192 Propoxur 4.8 210.2 111.1 10 93.1 25 50
193 Pymetrozine 1.9 218.1 105.2 20 79.0 30 110
194 Pyraclofos 8.3 361.1 138.1 40 111.0 50 100
195 Pyraclostrobin 8.2 388.1 194.1 10 163.1 20 120
196 Pyrazolate 8.5 439.0 91.2 36 173.1 16 118
197 Pyrazophos 8.4 374.1 222.1 20 194.1 30 120
198 Pyribenzoxim 9.8 413.2 119.0 35 289.1 30 100
199 Pyributicarb 10.1 331.2 108.0 30 181.1 19 70
200 Pyridaben 11.6 365.2 147.1 18 309.2 13 100
201 Pyridaphenthion 6.7 341.1 189.1 24 205.1 24 100
202 Pyrifluquinazon 6.7 465.1 423.0 20 107.0 32 145
203 Pyriftalid 5.9 319.1 139.0 28 179.0 32 155
204 Pyrimethanil 6.0 200.1 77.1 50 181.1 43 100
205 Pyrimidifen 9.6 378.1 184.1 27 150.0 45 150
206 Pyriminobac-methyl (E) 6.4 362.2 330.2 10 284.1 30 100
Pyriminobac-methyl (Z) 5.9 362.2 330.2 15 75 110 100
207 Pyrimisulfan 5.6 420.1 369.9 16 254.8 24 100
208 Pyriproxyfen 10.1 322.1 96.0 16 185.0 16 100
209 Pyroquilon 4.7 174.1 117.0 41 130.0 41 100
210 Quinalphos 7.6 299.1 96.9 32 163.0 24 110
211 Quinmerac 4.1 222.0 203.9 8 141.0 36 95
212 Quinoclamine 4.7 208.1 77.0 37 105.0 35 100
213 Quizalofop-ethyl 9.4 373.1 298.9 16 162.9 36 145
214 Saflufenacil 5.9 501.1 348.9 24 197.9 48 140
215 Sethoxydim 9.7 328.2 282.2 4 178.1 16 116
216 Silafluofen 14.8 426.1 287.2 0 168.1 34 90
217 Simeconazole 7.1 294.1 73.0 25 134.9 25 100
218 Simetryn 5.1 214.1 68.1 35 124.0 29 100
219 Spinetoram (j) 9.2 748.5 142.0 28 98.0 60 180
Spinetoram (L) 9.9 760.5 142.0 28 98.0 60 180
220 Spirodiclofen 11.1 411.2 71.0 10 313.1 10 120
221 Spiromesifen 10.6 371.1 273.1 15 255.0 19 40
222 Sulfoxaflor 4.2 278.1 174.2 4 154.2 28 50
223 Tebuconazole 7.9 308.2 70.0 20 125.0 30 120
224 Tebufenozide 7.5 297.0 133.0 10 104.9 18 100
225 Tebufenpyrad 9.7 334.1 117.0 37 145.0 37 150
226 Tebupirimfos 9.8 319.0 153.1 30 277.0 18 100
227 Teflubenzuron 9.9 381.2 141.1 30 158.0 12 100
228 Terbuthylazine 6.3 230.1 174.1 15 104.0 35 120
229 Terbutryn 6.6 242.1 186.1 15 71.0 20 120
230 Tetraconazole 7.1 371.9 159.0 28 70.0 28 120
231 Thenylchlor 7.0 324.1 127.0 4 97.0 48 70
232 Thiabendazole 3.9 202.0 131.1 40 175.0 30 120
233 Thiacloprid 4.2 253.0 126.0 20 186.0 10 90
234 Thiamethoxam 3.7 292.0 211.0 10 181.1 20 80
235 Thiazopyr 7.8 397.2 377.1 20 355.1 28 170
236 Thidiazuron 4.8 221.0 102.0 12 127.8 12 107
237 Thifensulfuron-methyl 4.6 388.0 167.0 10 204.9 25 110
238 Thiobencarb 8.5 258.1 125.0 13 89.1 67 50
239 Thiodicarb 5.0 355.1 88.0 15 108.0 10 80
240 Thiophanate-methyl 4.7 343.1 151.0 16 93.1 50 96
241 Triadinil 6.8 268.0 100.7 20 101.2 20 50
242 Toclofos-methyl 8.3 301.0 125.0 15 175.0 24 110
243 Tolylfluanid 9.8 371.1 73.1 20 355 12 120
244 Triadimefon 6.6 294.1 69.0 15 197.0 20 120
245 Triazophos 6.8 314.1 162.1 17 119.0 35 100
246 Tricyclazole 4.4 190.1 136.0 42 163.1 42 120
247 Trifloxystrobin 9.0 409.2 186.1 14 206.1 14 100
248 Triflumizole 9.0 346.1 73.1 11 278.1 11 100
249 Triflumuron 8.3 359.1 155.9 16 138.9 40 90
250 Uniconazole 7.3 292.2 70.1 22 125.0 30 110
251 Vamidothion 4.0 288.1 146.0 4 118.0 20 85
220 Spirodiclofen 11.1 411.2 71.0 10 313.1 10 120
221 Spiromesifen 10.6 371.1 273.1 15 255.0 19 40
222 Sulfoxaflor 4.2 278.1 174.2 4 154.2 28 50
223 Tebuconazole 7.9 308.2 70.0 20 125.0 30 120
224 Tebufenozide 7.5 297.0 133.0 10 104.9 18 100
225 Tebufenpyrad 9.7 334.1 117.0 37 145.0 37 150
226 Tebupirimfos 9.8 319.0 153.1 30 277.0 18 100
227 Teflubenzuron 9.9 381.2 141.1 30 158.0 12 100
228 Terbuthylazine 6.3 230.1 174.1 15 104.0 35 120
229 Terbutryn 6.6 242.1 186.1 15 71.0 20 120
230 Tetraconazole 7.1 371.9 159.0 28 70.0 28 120
231 Thenylchlor 7.0 324.1 127.0 4 97.0 48 70
232 Thiabendazole 3.9 202.0 131.1 40 175.0 30 120
233 Thiacloprid 4.2 253.0 126.0 20 186.0 10 90
234 Thiamethoxam 3.7 292.0 211.0 10 181.1 20 80
235 Thiazopyr 7.8 397.2 377.1 20 355.1 28 170
236 Thidiazuron 4.8 221.0 102.0 12 127.8 12 107
237 Thifensulfuron-methyl 4.6 388.0 167.0 10 204.9 25 110
238 Thiobencarb 8.5 258.1 125.0 13 89.1 67 50
239 Thiodicarb 5.0 355.1 88.0 15 108.0 10 80
240 Thiophanate-methyl 4.7 343.1 151.0 16 93.1 50 96
241 Triadinil 6.8 268.0 100.7 20 101.2 20 50
242 Toclofos-methyl 8.3 301.0 125.0 15 175.0 24 110
243 Tolylfluanid 9.8 371.1 73.1 20 355 12 120
244 Triadimefon 6.6 294.1 69.0 15 197.0 20 120
245 Triazophos 6.8 314.1 162.1 17 119.0 35 100
246 Tricyclazole 4.4 190.1 136.0 42 163.1 42 120
247 Trifloxystrobin 9.0 409.2 186.1 14 206.1 14 100
248 Triflumizole 9.0 346.1 73.1 11 278.1 11 100
249 Triflumuron 8.3 359.1 155.9 16 138.9 40 90
250 Uniconazole 7.3 292.2 70.1 22 125.0 30 110
251 Vamidothion 4.0 288.1 146.0 4 118.0 20 85

Table 4. 
Parameters for 110 pesticide residue analysis by GC-MS/MS
No. Pesticides Retention time (min) Parent ion Quantitative ion (m/z) Collision energy (V) Qualitative ion (m/z) Collision energy (V)
1 Acrinathrin-1 24.862 290 93 20 95 20
Acrinathrin-2 25.060 290 93 20 95 20
2 Alachlor 17.976 188 160 15 131 15
3 Aldrin 19.005 263 193 30 228 30
4 Anilofos 24.726 226 157 10 184 10
5 BHC (alpha) 15.254 181 145 25 109 25
BHC (beta) 15.983 181 145 25 109 25
BHC (delta) 16.960 181 145 25 109 25
BHC (gamma) 16.188 181 145 25 109 25
6 Bifenox 24.759 341 189 15 281 15
7 Bifenthrin 24.380 181 166 15 167 15
8 Bromobutide 17.749 119 91 30 65 15
9 Bromoproylate 24.411 341 185 10 183 10
10 Butachlor 20.770 176 147 15 134 15
11 Captan 20.189 149 105 10 79 10
12 Cabofuran 6.586 164 149 10 103 25
13 Carbophenothion 22.974 342 157 10 296 5
14 Chinomethionat 20.566 234 206 15 148 10
15 Chlordane (cis) 20.864 375 266 15 301 15
Chlordane (trans) 20.547 375 266 15 301 15
16 Chlorfenapyr 21.806 247 227 30 200 30
17 Chlorfenvinphos (cis) 20.044 267 159 15 203 15
Chlorfenvinphos (trans) 19.795 267 159 15 203 15
18 Chlorfluazuron 17.553 321 304 20 286 15
19 Chlorobenzilate 22.184 251 111 30 139 30
20 Chlorothalonil 16.639 266 231 15 133 35
21 Chlorpropham 14.682 213 127 10 171 10
22 Chlorpyrifos-methyl 17.764 286 93 20 271 10
23 Cyflufenamid 18.389 412 223 15 294 10
24 Cyfluthrin-1 27.220 206 151 25 177 25
Cyfluthrin-2 27.350 206 151 25 177 25
Cyfluthrin-3 27.420 206 151 25 177 25
Cyfluthrin-4 27.480 206 151 25 177 25
25 Cyhalothrin-1 25.370 197 141 5 161 5
Cyhalothrin-2 25.590 197 141 5 161 5
26 Cypermethrin-1 27.620 181 127 30 152 25
Cypermethrin-2 27.750 181 127 30 152 25
Cypermethrin-3 27.820 181 127 30 152 25
Cypermethrin-4 27.870 181 127 30 152 25
27 Cyprodinil 19.806 224 208 25 224 10
28 o,p-DDT 22.390 235 165 15 199 15
p,p-DDD 22.389 235 165 15 199 15
p,p-DDE 22.184 246 176 20 211 20
p,p-DDT 23.262 235 165 15 200 10
29 Deltamethrin 26.128 253 93 20 172 10
30 Dichlofluanid 15.352 224 77 15 123 10
31 Diclofop-methyl 23.605 253 162 15 190 15
32 Dicloran 15.628 206 148 20 176 20
33 Dicofol 19.327 139 75 25 111 25
34 Dieldrin 21.506 263 193 30 228 20
35 Dimethoate 15.639 125 79 20 93 20
36 Dimethylvinphos 19.021 295 109 15 295 15
37 Diphenylamine 14.162 169 115 40 139 40
38 Disulfoton 16.814 142 81 15 109 10
39 Endosulfan (alpha) 20.862 241 206 15 170 25
Endosulfan (beta) 22.243 241 206 15 170 25
Endosulfan-sulfate 22.394 272 237 15 143 25
40 Endrin 21.981 263 193 30 228 15
41 EPN 24.373 157 77 20 110 15
42 Ethalfuralin 14.579 276 202 10 248 5
43 Ethion 23.141 272 237 20 119 25
44 Etridiazole 8.690 211 183 10 140 20
45 Fenamidone 24.611 238 103 30 238 30
46 Fenamiphos 21.042 303 154 25 288 10
47 Fenitrothion 18.561 277 109 20 260 10
48 Fenothiocarb 20.777 160 72 15 160 5
49 Fenpropathrin 24.591 265 181 20 210 10
50 Fenvalerate-1 28.700 225 119 15 147 15
Fenvalerate-2 28.950 225 119 15 147 15
51 Ferimzone (E,Z) 20.431 239 107 10 82 10
52 Fipronil 19.924 367 213 30 255 20
53 Flucyrhrinate-1 27.819 199 157 15 107 15
Flucyrhrinate-2 28.070 199 157 15 107 15
54 Fludioxonil 21.204 248 154 10 182 10
55 Fluopyram 16.681 396 223 10 173 10
56 Folpet 20.332 260 130 10 232 10
57 Fthalide 19.362 272 215 25 243 25
58 Halfenprox 27.688 263 235 15 115 20
59 Heptachlor 18.106 272 235 15 237 15
Heptachlor-epoxide 19.970 353 263 15 282 15
60 Imazalil 21.195 215 145 25 173 25
61 Indanofan 24.704 174 131 20 159 20
62 Indoxacarb 29.425 218 134 20 203 20
63 Iprodione 24.171 314 245 15 271 10
64 Isofenphos 20.005 213 121 15 185 10
65 Lufenuron 10.586 353 203 5 174 25
66 Mecarbam 20.105 131 86 15 74 15
67 Methidation 20.499 145 85 5 58 15
68 Methoxychlor 1 20.115 227 169 25 212 15
Methoxychlor 2 21.076 227 169 25 212 15
Methoxychlor 24.534 227 169 25 212 15
69 Metobromuron 17.404 170 143 25 91 50
70 Metolachlor 18.920 162 134 10 133 10
71 Metribuzin 17.767 198 82 15 110 10
72 Mevinphos 10.723 192 127 10 164 10
73 Novaluron 7.367 168 140 15 112 20
74 Oxyfluorfen 21.572 361 252 20 300 20
75 Parathion 19.161 291 109 15 137 10
76 Parathion-methyl 17.917 263 109 10 246 5
77 Pendimethalin 19.784 252 162 10 191 10
78 Penthiopyrad 18.889 302 152 5 302 5
79 Permethrin-1 26.560 183 153 10 168 10
Permethrin-2 26.715 183 153 10 168 10
80 Phorate 15.177 260 75 5 231 5
81 Picoxystrobin 17.510 335 173 10 303 10
82 Pirimiphos-ethyl 19.538 333 163 10 180 10
83 Probenazole-1 12.961 130 77 20 103 20
Probenazole-2 15.530 130 77 20 103 20
84 Procymidone 20.263 283 96 10 67 25
85 Prometryn 18.256 241 184 10 226 10
86 Propiconazole-1 23.090 259 69 10 191 10
Propiconazole-2 23.240 259 69 10 191 10
87 Prothiofos 21.204 267 221 20 239 20
88 Pyridalyl 28.055 204 148 20 176 20
89 Pyridaphenthion 24.137 340 199 10 109 20
90 Quinoclamine 18.794 207 172 10 144 20
91 Quintozene 16.053 237 143 20 117 20
Methyl Pentachlorophenyl sulfide 18.638 296 263 20 246 20
Pentachloroanilline 17.362 265 193 20 229 10
92 Silafluofen 28.178 179 151 10 286 20
93 Simazine 15.889 201 173 5 186 5
94 Simeconazole 17.962 211 121 10 195 10
95 Simetryn 18.067 213 170 10 185 10
96 Spiromesifen 23.980 272 209 15 254 10
97 Tebupirimfos 17.205 261 137 15 153 15
98 Tefluthrin 17.010 177 127 10 157 10
99 Terbufos 16.362 231 175 15 157 20
100 Terbutryn 18.549 185 170 10 111 20
101 Tetradifon 24.999 159 131 10 111 25
102 Thiazopyr 18.882 327 263 30 277 30
103 Thifluzamide 21.466 194 125 25 166 15
104 Tolclofos-methyl 17.943 265 250 15 93 20
105 Tolyfluanid 19.994 238 137 15 110 25
106 Tralomethrin 29.595 253 172 10 199 25
107 Triadimenol 20.270 168 70 10 112 10
108 Trifluralin 14.854 306 264 10 160 25
109 Vinclozolin 17.873 212 145 20 172 20
110 Zoxamide 23.912 187 159 20 123 20

결과 및 고찰
검출한계 및 정량한계

분석을 위한 검출한계(limit of detection, LOD) 및 정량한계(limit of quantitation, LOQ)를 측정하기 위해 제조한 표준품 혼합용액을 0.005~100 μg/L로 희석하여 각각 3반복으로 분석하였다. 각 농약의 LOD는 LC-MS/MS 분석에서 0.005~18 μg/kg, GC-MS/MS에서 0.08~80 μg/kg 수준이었으며, LOQ는 LC-MS/MS분석에서 0.01~20 μg/kg, GC-MS/MS의 경우 0.1~100 μg/kg 범위로 나타나 시료 중에 함유된 ppb 수준의 미량 농약성분의 검출이 가능할 것으로 판단되었다(Table 5, 6).

Table 5. 
Average recovery and RSD of 251 pesticides spiked in apple and rice at two different concentrations with LC-MS/MS (n=3)
No. Compound LOD (μg/kg) LOQ (μg/kg) Recovery, % (RSD, %) Apple Recovery, % (RSD, %) Rice
50 μg/kg 200 μg/kg 50 μg/kg 200 μg/kg
1 Abamectin B1 3 5 91.3(5.9) 101.3(2.8) 59.7(9.7) 92.1(5.4)
2 Acephate 0.1 0.5 93.1(5.6) 93.4(0.8) 84.3(2.3) 94.5(1.2)
3 Acetamiprid 0.01 0.05 114.9(2.7) 99.3(1.1) 78.0(3.7) 108.0(0.5)
4 Acibenzolar-S-methyl 3 5 101.7(13.4) 94.7(5.4) 81.2(6.8) 111.5(5.6)
5 Alachlor* 5 10 110.4(1.7) 92.3(0.7) 83.3(13.8) 100.2(8.3)
6 Aldicarb 0.01 0.05 105.8(1.2) 99.3(0.9) 94.0(5.9) 105.1(3.6)
7 Ametoctrdin 0.03 0.05 100.1(1.1) 98.5(0.9) 89.2(6.1) 101.7(3.2)
8 Amisulbrom 1 2 87.2(9.9) 99.6(0.4) 92.4(4.8) 99.9(2.9)
9 Amitraz 0.03 0.05 2.56(11.8) 1.36(8.9) 72.3(2.4) 64.5(10.0)
10 Azimsulfuron 0.03 0.05 109.6(4.8) 102.3(3.3) 89.5(9.1) 93.4(9.4)
11 Azinphos-methyl 0.1 0.5 104.1(3.1) 95.7(3.0) 93.0(3.5) 100.6(2.6)
12 Azoxystrobin 0.05 0.1 101.6(2.9) 97.8(0.8) 83.3(1.4) 101.7(1.1)
13 Bendiocarb 0.05 0.5 112.6(3.7) 99.6(1.8) 83.7(3.6.) 110.2(0.8)
14 Benfuracarb 0.03 0.05 - - - 1.7(58.5)
15 Benfuresate 0.005 0.01 115.7(1.7) 94.1(4.3) 442.8(39.0) 165.4(18.5)
16 Bensulfuron-methyl 0.01 0.05 109.3(2.8) 107.5(0.4) 83.9(2.5) 94.7(9.4)
17 Benthiavalicarb-Isopropyl 0.05 0.1 105.6(3.3) 95.6(1.4) 86.4(5.1) 104.7(2.5)
18 Benzobicyclon 0.03 0.05 96.0(8.7) 85.5(2.1) 82.3(3.2) 92.8(8.7)
19 Benzoximate 0.05 0.1 102.7(0.8) 101.8(1.1) 91.3(1.9) 104.2(0.3)
20 Bifenazate 0.005 0.01 35.0(2.7) 33.6(1.8) 69.8(3.0) 80.1(2.5)
21 Bitertanol 0.5 1 97.5(3.1) 95.4(1.0) 104.5(4.9) 96.1(2.9)
22 Boscalid 0.1 0.5 106.1(6.0) 102.0(0.2) 84.9(8.9) 108.9(1.6)
23 Bromacil 0.005 0.01 103.3(3.9) 106.4(1.0) 86.6(2.0) 118.1(1.8)
24 Buprofezin 0.01 0.05 100.8(5.6) 96.8(2.6) 83.8(2.0) 101.2(1.5)
25 Cadusafos 0.05 0.1 102.3(2.8) 92.7(1.8) 92.6(1.7) 101.3(1.9)
26 Cafenstrole 0.03 0.05 110.2(5.1) 100.1(2.4) 81.1(4.1) 110.5(2.0)
27 Carbaryl(NAC) 0.05 0.1 105.6(3.2) 97.9(1.6) 86.9(2.5) 113.3(1.7)
28 Carbendazim 0.01 0.05 93.8(2.2) 90.6(0.4) 77.0(0.4) 92.3(0.3)
29 Carbofuran* 0.05 0.1 104.0(5.7) 93.9(0.8) 83.7(1.8) 97.0(0.9)
30 Carboxin 0.03 0.05 91.0(1.7) 90.2(0.8) 86.4(1.8) 110.7(1.0)
31 Carfentrazone-ethyl 0.008 0.01 160.3(3.2) 102.6(1.0) 91.5(3.4) 104.1(1.0)
32 Carpropamide 0.01 0.05 103.6(2.0) 100.7(1.2) 77.4(6.4) 107.8(0.9)
33 Chlorantraniliprole 0.5 1 99.1(5.2) 98.0(1.5) 91.7(5.2) 100.4(1.2)
34 Chlorfluazuron* 0.05 0.5 78.8(2.2) 76.0(1.4) 73.7(2.8) 81.2(6.6)
35 Chlorpyrifos 1 2 93.4(1.1) 92.1(4.6) 91.3(1.8) 98.6(1.2)
36 Chlorsulfuron 0.1 0.5 107.6(3.7) 117.4(1.9) 89.1(1.6) 91.1(1.4)
37 Chromafenozide 0.05 0.1 105.9(3.1) 100.7(0.9) 92.1(3.3) 106.4(1.2)
38 Clethodim 0.05 0.5 101.5(0.9) 102.8(1.3) 79.6(2.5) 85.3(4.1)
39 Clofentezine 0.5 1 105.1(5.1) 107.3(1.2) 97.2(6.2) 115.1(2.1)
40 Clomazone 0.03 0.05 100.7(4.2) 94.9(0.6) 85.0(3.3) 105.8(1.0)
41 Clothianidin 0.1 1 80.7(4.0) 85.6(3.1) 86.4(3.8) 100.8(3.8)
42 Cyazofamid 0.05 0.1 113.5(0.4) 109.9(0.9) 100.1(1.8) 117.0(0.5)
43 Cyclosulfamuron 0.01 0.05 98.3(4.8) 88.8(1.9) 87.0(0.6) 95.3(4.5)
44 Cyflufenamid* 0.1 0.5 104.6(1.7) 99.9(0.1) 76.1(10.0) 108.9(0.9)
45 Cyhalofop-butyl 5 25 91.7(7.9) 91.2(10.2) 90.4(2.8) 98.3(2.3)
46 Cymoxanil* 0.05 0.1 101.5(3.0) 96.2(1.7) 82.6(3.0) 106.2(1.2)
47 Cyproconazole 0.5 1 99.3(1.3) 94.1(1.8) 90.1(0.1) 107.9(2.7)
48 Cyprodinil 5 7 93.9(0.7) 94.7(2.2) 83.3(3.3) 100.8(0.6)
49 Cyromazine 0.01 0.05 40.3(5.2) 44.3(1.7) 39.3(7.0) 39.3(5.9)
50 DDVP (Dichlovos) 1 5 98.2(1.0) 92.6(4.4 108.7(12.8) 112.0(5.2)
51 Dinotefuran 0.1 0.5 106.7(4.2) 99.6(1.9) 84.5(1.8) 97.1(1.0)
52 Diafenthiuron 0.01 0.05 - 5.87 14.0(20.6) 37.1(5.4)
53 Diazinon 0.05 0.1 101.2(2.4) 96.4(1.1) 98.9(3.7) 102.9(2.0)
54 Dichlofluanid* 0.1 0.5 108.6(2.1) 115.6(2.3) - -
55 Diethofencarb 0.2 0.5 89.5(13.2) 92.0(8.5) 77.9(1.1) 93.2(2.4)
56 Difenoconazole 0.5 1 103.7(1.7) 100.8(1.7) 87.2(6.1) 106.7(1.6)
57 Diflubenzuron 0.5 1 102.9(2.5) 98.2(0.9) 93.2(0.6) 97.6(1.8)
58 Dimepiperate 1 5 99.7(1.2) 96.5(1.1) 86.8(2.9) 102.9(1.9)
59 Dimethametryn 0.01 0.05 99.7(2.0) 97.3(1.0) 94.1(4.2) 102.1(3.8)
60 Dimethenamid 0.05 0.5 100.6(4.1) 96.4(0.3) 90.2(3.0) 108.0(2.1)
61 Dimethoate* 0.01 0.05 104.8(1.8) 102.5(0.7) 84.6(1.1) 106.6(0.8)
62 Dimethomorph 0.5 1 91.4(4.2) 94.6(1.4) 96.1(2.8) 101.5(1.3)
63 Dimethylvinphos* 0.5 1 78.2(6.7) 93.3(0.2) 103.6(6.6) 114.2(3.9)
64 Demeton-S-Methyl 0.01 0.05 101.1(5.1) 93.4(2.0) 90.1(3.8) 103.7(1.4)
65 Diniconazole 0.5 1 100.2(2.6) 97.5(3.4) 97.5(1.2) 103.3(2.9)
66 Diphenamid 0.05 0.1 100.1(4.2) 95.6(1.6) 86.1(3.2) 102.3(2.2)
67 Dithiopyr 1 2 94.1(4.0) 98.1(2.3) 81.0(15.0) 98.4(2.2)
68 Diuron 0.05 0.5 102.3(2.8) 96.6(1.3) 83.3(2.5) 104.1(1.3)
69 Dymron 0.01 0.05 107.3(2.6) 98.3(2.0) 89.5(5.9) 110.2(2.9)
70 Edifenphos 0.1 0.5 105.7(2.8) 100.8(0.8) 90.2(4.1) 112.5(1.2)
71 EPN* 0.7 1 95.9(14.9) 99.4(7.1) 75.2(3.5) 103.9(7.6)
72 Esprocarb 0.05 0.1 97.3(1.9) 92.3(0.4) 84.7(3.0) 102.8(1.1)
73 Ethaboxam 0.5 1 104.1(1.0) 96.9(1.0) 86.9(9.7) 99.9(1.2)
74 Ethiofencarb 0.05 0.3 95.8(3.2) 92.6(1.7) 87.2(1.2) 104.2(2.1)
75 Ethofenprox 0.1 0.5 96.7(0.7) 97.9(7.5) 81.6(1.0) 101.1(0.4)
76 Ethoprophos 0.1 0.5 100.6(4.2) 92.6(1.6) 87.0(0.6) 99.9(1.8)
77 Ethoxyquin 0.3 0.5 33.4(3.2) 34.3(2.1) 65.9(2.2) 86.4(4.0)
78 Ethoxysulfuron 0.005 0.01 101.1(7.8) 86.1(1.5) 82.8(2.8) 93.5(9.7)
79 Etoxazole 0.01 0.05 110.0(10.2) 102.6(4.3) 85.6(1.1) 95.5(2.7)
80 Etrimfos 0.1 0.5 99.1(1.6) 95.9(1.4) 99.4(3.6) 104.2(2.8)
81 Famoxadone 0.3 0.5 96.3(1.7) 95.8(3.5) 102.3(9.7) 101.7(1.9)
82 Fenamidone* 0.05 0.2 100.0(4.3) 97.3(1.3) 86.4(6.3) 98.0(3.4)
83 Fenamiphos* 0.05 0.1 102.5(3.6) 96.4(1.0) 81.0(2.8) 106.8(1.0)
84 Fenarimol 4 5 103.6(8.4) 95.6(3.6) 86.5(9.3) 101.7(4.9)
85 Fenazaquin 0.1 0.5 95.7(18.7) 96.7(4.4) 85.6(2.2) 95.5(1.5)
86 Fenbuconazole 0.5 1 103.5(1.4) 94.3(3.0) 93.4(2.9) 101.4(1.1)
87 Fenhexamid 0.1 0.3 - - 82.9(9.6) 103.5(4.6)
88 Fenobucarb (BPMC) 0.1 1 88.7(8.0) 87.8(6.3) 78.5(5.4) 91.4(4.0)
89 Fenothiocarb* 0.01 0.05 105.3(0.3) 96.1(2.1) 79.1(0.8) 106.6(2.6)
90 Fenoxanil 1 5 108.4(2.9) 95.7(0.6) 83.1(3.3) 102.5(3.0)
91 Fenoxaprop-Ethyl 0.03 0.05 103.7(4.5) 96.8(2.0) 83.7(2.4) 105.4(1.6)
92 Fenoxycarb 0.03 0.05 103.8(3.1) 97.5(0.7) 88.0(5.2) 105.4(1.1)
93 Fenpyroximate 0.7 1 97.5(2.7) 91.6(4.4) 91.6(2.1) 99.6(1.4)
94 Fenthion(MPP) 0.1 0.5 97.6(3.5) 91.4(2.0) 86.3(8.7) 103.1(4.6)
95 Fentrazamide 0.03 0.05 99.0(4.2) 96.4(2.4) 103.3(2.6) 105.4(3.8)
96 Ferimzone* 0.05 0.1 93.1(3.7) 89.4(3.2) 75.3(0.3) 87.2(1.3)
97 Flonicamid 0.1 0.5 103.2(3.7) 93.5(0.5) 93.8(3.5) 100.7(1.3)
98 Fluacrypyrim 0.05 0.1 101.9(0.3) 96.0(1.5) 84.2(3.9) 101.3(0.8)
99 Flubendiamide 0.5 1 104.9(2.9) 95.6(0.3) 94.3(3.9) 100.5(1.3)
100 Flucetosulfuron 0.04 0.05 107.3(2.4) 100.8(2.4) 102.3(5.6) 117.6(2.2)
101 Fludioxonil* 0.5 1 104.9(7.9) 96.4(0.9) 106.4(1.5) 110.5(1.2)
102 Flufenacet 0.1 0.5 103.8(3.7) 95.8(1.4) 86.9(4.0) 107.8(1.7)
103 Flufenoxuron 0.05 0.1 96.8(0.5) 89.8(10.6) 87.1(2.5) 97.6(0.1)
104 Flumioxazin 4 5 98.5(8.4) 95.7(6.6) 76.7(7.3) 105.5(3.4)
105 Fluopicolide 0.05 0.1 108.9(3.2) 94.1(1.4) 84.7(8.0) 111.8(1.9)
106 Fluopyram* 0.01 0.05 112.8(1.0) 96.6(0.9) 82.3(6.7) 110.0(2.1)
107 Fluquinconazole 0.05 0.1 99.3(5.8) 94.5(2.9) 86.2(7.4) 107.1(3.5)
108 Flusilazole 0.5 1 107.7(0.9) 95.1(1.5) 82.8(0.3) 109.7(3.5)
109 Flutolanil 0.01 0.05 102.5(4.8) 94.3(4.1) 79.7(0.4) 108.9(3.7)
110 Forchlorfenuron 0.1 0.5 98.6(2.4) 92.6(1.1) 84.2(2.4) 97.5(2.4)
111 Fosthiazate 0.01 0.05 104.6(1.7) 95.7(1.0) 90.1(1.9) 102.7(1.6)
112 Furathiocarb 0.05 0.1 101.7(1.4) 95.6(0.2) 84.7(3.7) 100.4(0.7)
113 Gibberellic acid 10 15 110.6(10.5) 100.9(6.6) 81.1(7.0) 88.4(3.9)
114 Halosulfuron-methyl 0.05 0.1 99.9(5.4) 89.2(1.9) 86.9(1.6) 93.9(8.0)
115 Haloxyfop 0.3 0.5 105.6(1.1) 91.6(1.0) 84.5(12.7) 96.6(2.8)
116 Hexaconazole 0.1 0.5 100.6(1.8) 92.5(0.8) 88.4(5.6) 100.0(0.7)
117 Hexaflumuron 5 10 89.0(14.7) 93.7(4.0) 100.1(11.6) 96.2(1.6)
118 Hexazinone 0.005 0.01 105.0(1.8) 96.0(1.0) 86.2(4.3) 103.0(2.6)
119 Hexythiazox 0.05 0.1 100.3(1.6) 92.6(3.3) 86.6(1.7) 96.5(1.6)
120 Imazalil* 0.05 0.1 99.9(0.8) 94.2(1.1) 88.1(1.5) 100.1(3.1)
121 Imazosulfuron 0.08 0.1 107.2(3.1) 101.1(3.0) 97.4(9.5) 114.9(1.1)
122 Imibenconazole 0.7 1 98.1(11.4) 102.1(6.1) 110.3(5.0) 109.9(0.5)
123 Imicyafos 0.008 0.01 110.9(3.2) 101.6(0.8) 90.4(3.3) 103.0(2.1)
124 Imidacloprid 0.5 1 77.5(5.4) 81.8(1.6) 91.2(1.7) 100.9(0.7)
125 Inabenfide 0.8 1 96.8(2.2) 92.4(2.9) 103.6(2.2) 97.7(5.3)
126 Iprobenfos 0.01 0.05 100.4(1.2) 93.8(0.8) 88.6(1.2) 100.3(0.9)
127 Iprovalicarb 0.05 0.1 95.5(3.3) 93.9(1.0) 91.4(4.4) 101.5(1.4)
128 Isoprocarb (MIPC) 0.1 1 100.6(1.0) 91.8(0.9) 87.0(4.0) 100.9(2.7)
129 Isoprothiolane 0.05 0.1 103.4(0.9) 94.9(1.6) 77.0(2.8) 105.5(3.2)
130 Isopyrazam 0.03 0.05 105.8(1.1) 96.6(0.7) 83.1(6.6) 106.1(1.6)
131 Kresoxim-methyl 0.5 1 101.8(3.9) 96.0(1.8) 99.3(5.5) 105.1(1.4)
132 Linuron 0.01 0.05 82.9(14.3) 87.6(12.2) 76.5(2.4) 91.7(6.5)
133 Lufenuron* 0.1 0.5 93.7(16.8) 91.7(9.9) 84.8(10.5) 95.7(1.9)
134 Malathion 0.5 1 106.3(3.1) 94.5(2.3) 80.3(6.5) 110.0(0.8)
135 Mandipropamid 0.05 0.1 100.9(0.4) 94.0(1.5) 73.0(0.9) 100.3(1.1)
136 Mefenacet 0.05 0.1 102.5(1.6) 95.3(1.3) 87.9(2.9) 102.0(1.7)
137 Mepanipyrim 1 2 101.2(2.3) 94.2(1.2) 80.3(9.7) 101.8(3.0)
138 Mepronil 0.05 0.08 108.8(1.8) 92.5(1.3) 78.5(6.4) 111.2(2.9)
139 Metalaxyl 0.05 0.1 104.0(2.0) 94.7(0.9) 88.4(1.1) 101.5(0.8)
140 Metamifop 0.05 0.1 102.3(4.4) 98.6(2.3) 88.3(2.6) 106.2(0.1)
141 Metazosulfuron 0.08 0.1 109.4(8.1) 113.8(2.2) 92.5(1.2) 89.1(4.5)
142 Metconazole 0.1 0.5 103.8(1.0) 94.4(0.6) 88.8(4.1) 101.4(2.4)
143 Methabenzthiazuron 0.05 0.1 98.9(2.2) 92.4(0.2) 83.5(5.6) 99.5(1.6)
144 Methidathion* 0.1 0.5 103.5(1.2) 95.4(2.2) 83.6(2.4) 102.9(1.5)
145 Methiocarb 0.1 0.5 99.3(2.4) 92.2(0.7) 87.9(1.5) 104.7(1.8)
146 Methomyl 0.05 0.1 100.6(2.0) 91.9(0.2) 106.6(3.7) 114.7(0.6)
147 Methoxyfenozide 0.1 0.5 109.9(1.6) 95.0(0.1) 86.6(1.9) 112.9(0.9)
148 Metobromuron* 0.1 0.5 98.5(3.2) 93.5(0.9) 90.3(5.5) 98.7(1.6)
149 Metolachlor* 1 2 100.5(2.1) 92.0(0.7) 86.9(1.2) 100.4(2.4)
150 Metolcarb 0.1 1 104.1(1.2) 94.9(1.2) 88.4(2.5) 101.2(5.1)
151 Metrafenone 0.03 0.05 100.6(0.9) 97.7(0.5) 90.9(2.0) 100.2(0.6)
152 Metribuzin* 1 5 110.9(0.8) 97.1(2.9) 76.0(3.7) 115.2(3.4)
153 Mevinphos (E,Z)* 0.1 0.5 106.7(1.5) 95.4(0.5) 84.8(2.8) 97.9(1.1)
154 Milbemectin A3 0.3 0.5 95.4(3.2) 93.4(4.3) 86.4(5.9) 98.0(3.3)
Milbemectin A4 0.5 1 92.2(4.0) 96.2(2.0) 79.3(3.6) 95.7(2.2)
155 Molinate 5 10 101.7(0.5) 95.9(8.9) 85.4(5.1) 95.0(6.4)
156 Monocrotophos 0.1 0.5 103.6(1.6) 97.4(0.4) 85.8(1.3) 101.1(1.9)
157 Myclobutanil 1 2 103.7(1.8) 93.2(0.9) 89.2(6.8) 109.2(1.8)
158 Napropamide 0.05 0.1 103.0(1.0) 95.0(1.4) 90.1(4.9) 103.3(1.8)
159 Nicosulfuron 0.005 0.01 84.4(1.7) 82.4(1.6) 83.7(2.4) 91.5(2.8)
160 Novaluron* 0.5 1 84.7(13.1) 91.4(4.8) 92.9(5.6) 98.4(2.9)
161 Nuarimol 2 5 325.3(0.4) 159.8(1.0) 502.4(4.2) 183.0(3.6)
162 Ofurace 0.05 0.5 108.5(3.1) 93.8(1.7) 83.4(5.4) 107.6(1.9)
163 Omethoate 0.1 0.5 91.1(2.8) 90.8(1.6) 87.8(1.4) 95.9(1.2)
164 Oxadiazon 0.1 0.5 95.8(3.9) 92.1(2.9) 92.0(2.0) 93.8(1.1)
165 Oxadixyl 0.008 0.01 109.3(2.6) 99.8(0.2) 81.0(3.9) 104.3(2.6)
166 Oxamyl 0.01 0.05 102.3(1.5) 94.1(0.3) 92.7(1.1) 100.3(1.1)
167 Oxaziclomefon 0.05 0.1 99.3(7.6) 95.7(1.6) 88.5(3.1) 101.6(0.6)
168 Paclobutrazol 0.5 1 101.3(5.1) 93.7(0.5) 95.9(7.3) 110.0(2.7)
169 Penconazole 0.1 0.5 100.2(0.7) 93.9(1.1) 88.1(3.6) 103.2(2.7)
170 Pencycuron 0.05 0.1 96.8(3.3) 94.5(1.8) 106.7(3.8) 109.2(2.6)
171 Pendimethalin* 1 2 89.3(3.8) 89.9(4.8) 100.7(7.0) 96.0(2.9)
172 Penoxsulam 0.03 0.05 101.2(3.3) 93.4(1.7) 100.7(5.2) 102.3(2.7)
173 Penthiopyrad* 0.008 0.01 104.5(2.0) 94.7(0.8) 85.8(2.6) 110.1(0.8)
174 Pentoxazone 1 5 102.6(6.6) 99.6(5.1) 98.8(12.5) 109.8(6.3)
175 Phenthoate 0.1 0.5 95.8(2.1) 93.9(1.8) 89.2(3.3) 100.4(3.4)
176 Phorate 0.05 1 96.6(5.9) 91.8(4.0) 95.1(6.3) 108.2(4.6)
177 Phosalone 0.1 0.5 99.3(1.1) 95.7(0.7) 81.2(2.4) 106.7(0.1)
178 Phosphamidone 0.05 0.1 105.2(1.4) 97.0(0.7) 94.4(1.7) 100.8(2.3)
179 Phoxim 0.03 0.05 95.2(1.6) 93.7(1.4) 91.7(1.8) 102.1(0.9)
180 Picoxystrobin* 0.01 0.05 100.7(1.8) 94.9(1.3) 94.8(2.2) 89.6(0.9)
181 Piperophos 0.05 0.1 99.8(0.2) 92.2(1.0) 85.6(1.7) 99.8(1.7)
182 Pirimicarb 0.01 0.05 100.2(1.4) 93.4(0.5) 90.6(1.9) 102.4(2.7)
183 Pirimiphos-methyl 0.1 0.5 99.3(1.9) 94.2(1.4) 92.8(3.1) 102.2(1.4)
184 Probenazole* 5 15 100.6(2.5) 94.2(1.1) 81.0(6.7) 100.9(3.1)
185 Prochloraz 0.5 1 95.8(0.3) 92.8(0.7) 93.6(5.2) 99.6(1.9)
186 Profenofos 0.1 0.5 101.1(1.5) 95.1(0.8) 86.3(1.5) 101.6(1.8)
187 Prometryn* 0.1 0.5 97.1(1.8) 90.7(0.6) 89.2(2.6) 102.2(0.9)
188 Propamocarb 0.005 0.01 86.1(6.4) 85.6(1.5) 82.2(2.5) 92.2(1.1)
189 Propanil 1 5 94.5(3.4) 91.8(1.4) 89.3(4.0) 104.8(2.5)
190 Propaquizafop 0.03 0.05 99.2(2.2) 97.6(1.2) 87.6(2.9) 81.5(1.4)
191 Propiconazole* 0.7 1 97.1(0.4) 91.8(1.0) 93.9(1.4) 106.4(1.1)
192 Propoxur 0.05 0.1 105.3(2.5) 92.6(1.3) 87.5(3.1) 104.9(1.4)
193 Pymetrozine 0.03 0.05 53.0(0.6) 52.8(1.1) 62.8(0.7) 73.5(3.0)
194 Pyraclofos 0.5 1 96.2(2.2) 91.8(0.5) 94.6(0.9) 97.6(2.5)
195 Pyraclostrobin 0.05 0.2 97.7(1.5) 95.0(0.8) 93.8(1.9) 102.7(1.9)
196 Pyrazolate 0.05 0.1 101.6(1.1) 97.3(0.2) 81.4(3.7) 105.2(0.4)
197 Pyrazophos 0.1 0.5 96.3(1.9) 94.1(0.3) 99.8(3.2) 98.2(0.8)
198 Pyribenzoxim 1 2 98.0(2.3) 94.7(2.0) 86.1(4.7) 104.0(1.8)
199 Pyributicarb 0.05 0.1 93.7(12.1) 94.5(1.9) 88.9(0.8) 101.8(0.1)
200 Pyridaben 0.05 0.1 97.9(3.0) 92.5(9.3) 57.4(1.2) 72.2(2.1)
201 Pyridaphenthion* 0.1 0.5 102.4(1.1) 95.1(1.3) 90.0(4.6) 103.5(2.1)
202 Pyrifluquinazon 0.005 0.01 95.6(2.4) 97.6(1.4) 87.0(1.1) 107.1(4.2)
203 Pyriftalid 0.5 1 103.2(4.2) 96.4(0.9) 88.4(3.3) 105.4(2.7)
204 Pyrimethanil 1 5 97.6(5.6) 97.1(1.4) 109.7(9.3) 95.9(4.8)
205 Pyrimidifen 0.05 0.1 100.3(1.4) 96.9(0.2) 98.6(4.9) 104.7(0.9)
206 Pyriminobac-methyl (Z) 0.1 0.5 100.3(2.5) 93.2(0.7) 87.9(1.7) 101.9(1.2)
Pyriminobac-methyl (E) 0.1 0.5 99.9(2.3) 92.7(0.6) 90.9(4.1) 102.0(2.8)
207 Pyrimisulfan 0.008 0.01 99.5(1.7) 93.5(1.0) 96.9(1.7) 100.6(1.5)
208 Pyriproxyfen 0.05 0.1 92.3(15.1) 94.4(3.5) 93.7(2.3) 102.9(0.7)
209 Pyroquilon 0.05 0.1 97.6(1.2) 92.0(0.4) 81.3(3.4) 103.9(2.6)
210 Quinalphos 0.03 0.05 100.5(0.3) 94.4(0.5) 92.5(4.2) 103.9(0.4)
211 Quinmerac 0.005 0.01 105.6(7.6) 94.7(0.8) 71.5(0.5) 88.7(2.2)
212 Quinoclamine* 1 5 95.0(6.1) 94.9(2.4) 88.2(7.4) 103.4(5.0)
213 Quizalofop-ethyl 0.01 0.05 100.4(2.8) 95.2(1.5) 88.8(2.5) 106.9(1.6)
214 Saflufenacil 0.03 0.05 99.7(6.6) 94.4(3.1) 99.7(6.6) 100.2(5.6)
215 Sethoxydim 0.03 0.05 91.4(1.1) 93.4(0.5) 95.6(2.9) 95.3(1.3)
216 Silafluofen* 0.03 0.05 91.6(1.3) 97.9(0.3) 99.4(0.6) 101.3(0.6)
217 Simeconazole* 1 3 98.5(6.4) 93.1(1.3) 86.6(7.2) 107.6(4.9)
218 Simetryn* 0.05 0.1 98.1(1.7) 91.0(0.2) 90.8(3.0) 101.3(1.0)
219 Spinetoram (j) 0.03 0.05 91.6(2.5) 90.3(0.8) 100.3(0.3) 101.1(3.1)
Spinetoram (L) 0.03 0.05 91.0(1.0) 91.6(2.3) 101.1(1.2) 98.4(4.9)
220 Spirodiclofen 0.05 0.1 94.9(9.3) 93.1(6.9) 83.3(2.8) 100.6(1.9)
221 Spiromesifen* 0.7 1 97.8(14.1) 91.0(6.2) 92.3(4.2) 98.4(0.5)
222 Sulfoxaflor 0.005 0.01 81.3(0.7) 88.6(1.8) 81.0(3.6) 90.3(1.6)
223 Tebuconazole 0.1 0.5 101.3(2.2) 94.4(1.0) 92.6(3.6) 101.2(1.7)
224 Tebufenozide 0.1 0.5 101.5(2.5) 95.6(2.2) 92.9(6.4) 108.7(1.7)
225 Tebufenpyrad 0.1 0.5 97.0(12.4) 101.8(5.4) 90.1(3.1) 86.3(1.9)
226 Tebupirimfos* 0.05 0.1 93.2(3.9) 92.5(0.7) 104.7(2.5) 102.4(0.9)
227 Teflubenzuron 4 5 91.7(6.6) 99.5(2.9) 86.7(6.8) 98.3(2.2)
228 Terbuthylazine 0.5 1 105.4(0.7) 94.4(1.1) 89.2(2.5) 112.4(2.4)
229 Terbutryn* 0.05 0.1 97.7(0.5) 92.6(0.3) 89.6(2.9) 101.7(2.5)
230 Tetraconazole 0.1 1 97.8(5.1) 93.9(1.7) 113.0(4.1) 112.3(2.3)
231 Thenylchlor 0.03 0.05 104.5(2.8) 94.5(1.3) 90.9(1.4) 103.8(1.9)
232 Thiabendazole 0.5 1 95.3(1.8) 92.9(1.2) 86.1(3.3) 93.3(0.9)
233 Thiacloprid 0.03 0.05 100.6(3.4) 94.9(0.4) 89.2(2.5) 100.7(2.0)
234 Thiamethoxam 0.1 0.5 99.8(1.8) 92.4(1.1) 83.2(1.2) 107.3(1.3)
235 Thiazopyr* 0.5 1 100.4(3.2) 93.4(1.8) 88.4(2.6) 105.9(0.8)
236 Thidiazuron 0.1 0.5 111.0(2.6) 96.8(1.2) 81.6(8.8) 107.0(2.8)
237 Thifensulfuron-methyl 0.01 0.05 106.2(4.2) 99.4(1.8) 113.4(4.0) 113.8(2.3)
238 Thiobencarb 0.1 0.5 97.9(1.5) 90.9(1.4) 93.3(5.2) 102.9(1.0)
239 Thiodicarb 0.05 0.2 105.5(2.8) 97.5(1.2) 45.2(2.9) 79.6(0.9)
240 Thiophanate-methyl 18 20 111.6(6.5) 106.5(0.5) 99.4(0.8) 116.5(0.5)
241 Triadinil 3 5 98.4(15.0) 93.3(7.6) 105.6(10.4) 115.7(1.6)
242 Tolclofos-methyl* 5 10 88.2(6.6) 90.4(4.8) 97.0(15.1) 101.6(2.4)
243 Tolylfluanid* 4 5 259.6(55.8) 66.7(45.2) 314.2(10.9) 184.7(19.2)
244 Triadimefon 0.5 1 105.7(2.6) 93.3(1.4) 87.3(4.9) 108.4(2.2)
245 Triazophos 0.01 0.05 103.1(1.6) 94.5(0.4) 88.8(1.0) 104.5(1.8)
246 Tricyclazole 0.01 0.05 107.4(4.0) 100.4(0.5) 88.7(5.2) 102.4(1.5)
247 Trifloxystrobin 0.05 0.1 99.5(1.7) 93.5(1.0) 86.7(2.4) 102.0(0.8)
248 Triflumizole 0.05 0.1 112.1(3.0) 104.9(2.1) 103.5(1.9) 107.0(0.7)
249 Triflumuron 0.05 0.5 100.4(4.7) 92.9(1.3) 87.4(3.1) 107.0(0.7)
250 Uniconazole 0.8 1 97.4(1.7) 92.3(2.1) 95.3(2.3) 100.0(3.0)
251 Vamidothion 0.005 0.01 105.2(1.4) 96.2(0.7) 90.1(1.3) 101.0(1.7)
*41 pesticides were analyzed by both GC-MS/MS and LC-MS/MS.

농약성분별 회수율

회수율 실험은 친환경인증을 받은 사과와 쌀 시료에 최종농도가 50 μg/kg, 200 μg/kg 되도록 표준품 혼합용액을 시료에 첨가하여 QuEChERS 전처리 방법으로 추출한 시험용액을 LC-MS/MS와 GC-MS/MS에 적용하여 회수율을 검증하였다. 분석대상 농약에 대한 분석법 확립 결과 표준곡선의 직선성은 0.05~0.2 mg/L 범위에서 R2> 0.99이었으며 회수율에 대한 결과는 Table 5과 6에 나타내었다.

Table 6. 
Average recovery and RSD of 110 pesticides spiked in apple and rice at two different concentrations with GC-MS/MS (n=3)
No. Compound LOD (μg/kg) LOQ (μg/kg) Recovery, % (RSD, %) Apple Recovery, % (RSD, %) Rice
50 μg/kg 200 μg/kg 50 μg/kg 200 μg/kg
1 Acrinathrin 20 30 85.9(4.9) 90.1(5.9) 72.2(1.7) 54.5(2.8)
2 Alachlor* 1 5 79.3(7.3) 92.0(5.0) 100.3(6.0) 91.2(12.5)
3 Aldrin 3 5 77.9(5.1) 91.3(7.3) 93.8(5.0) 92.6(8.6)
4 Anilofos 1 5 83.5(4.4) 95.2(4.7) 78.9(1.6) 35.9(2.8)
5 BHC 1 5 76.9(8.3) 92.3(4.6) 94.4(8.9) 88.9(12.0)
6 Bifenox 0.08 0.1 89.4(2.1) 92.5(5.1) 91.2(1.3) 81.3(1.0)
7 Bifenthrin 1 5 95.0(5.4) 102.6(5.8) 72.2(1.5) 54.5(0.9)
8 Bromobutide 1 3 80.7(7.4) 95.6(5.8) 102.9(4.7) 94.0(11.1)
9 Bromopropylate 0.08 0.1 86.0(6.3) 97.6(5.2) 88.3(2.4) 87.2(0.9)
10 Butachlor 1 2 85.8(5.6) 99.8(5.2) 101.9(3.1) 92.3(6.7)
11 Captan 20 30 37.6(1.7) 27.0(4.8) 65.0(6.6) 37.3(14.2)
12 Carbofuran* 0.3 0.8 101.5(14.7) 105.7(6.8) 101.5(13.4) 112.9(5.2)
13 Carbophenothion 5 10 86.0(5.6) 98.4(5.6) 88.5(2.1) 79.5(0.5)
14 Chinomethionat 30 50 34.6(3.5) 22.7(5.7) 44.5(1.5) 30.1(1.5)
15 Chlordane 0.3 0.5 85.0(7.1) 93.2(5.1) 94.2(5.9) 89.8(7.4)
16 Chlorfenapyr 5 10 98.1(7.3) 101.1(6.0) 98.0(1.7) 89.2(3.8)
17 Chlorfenvinphos 1 5 79.4(7.1) 96.7(5.3) 95.7(3.8) 86.9(5.9)
18 Chlorfluazuron* 3 5 104.8(9.1) 111.1(6.4) 126.1(4.2) 130.5(9.7)
19 Chlorobenzilate 1 5 86.3(6.6) 99.9(5.2) 89.8(0.4) 83.6(2.4)
20 Chlorothalonil 5 10 80.5(2.7) 86.0(6.4) 90.7(10.2) 87.2(12.8)
21 Chlorpropham 1 5 74.0(9.6) 91.9(2.4) 96.7(10.1) 91.1(13.4)
22 Chlorpyrifos-methyl 1 5 75.7(8.6) 91.2(5.3) 96.8(6.9) 85.5(11.8)
23 Cyflufenamid* 8 10 81.3(7.8) 93.8(1.6) 62.7(1.4) 49.5(1.6)
24 Cyfluthrin 30 50 84.1(4.1) 88.3(5.6) 77.3(1.2) 64.3(2.9)
25 Cyhalothrin (lambda) 3 5 88.6(5.3) 92.3(6.5) 76.8(0.3) 68.5(1.4)
26 Cypermethrin 10 30 84.1(2.5) 88.6(6.0) 82.0(1.0) 66.2(1.8)
27 Cyprodinil 5 8 84.5(7.9) 95.9(6.7) 99.1(3.8) 93.7(9.6)
28 DDT 0.1 0.3 90.0(6.1) 98.4(5.9) 91.8(1.8) 83.7(4.0)
29 Deltamethrin 10 30 76.1(4.4) 83.0(5.1) 70.7(3.6) 44.3(8.1)
30 Dichlofluanid* 1 3 24.0(0.1) 37.2(1.0) 55.1(0.2) 19.5(5.8)
31 Diclofop-methyl 10 30 93.8(9.5) 100.1(6.2) 88.8(1.1) 87.0(0.8)
32 Dicloran 8 10 86.0(1.1) 92.2(6.1) 94.3(5.8) 86.0(13.7)
33 Dicofol 10 30 89.5(6.9) 105.2(5.4) 96.5(4.1) 92.6(10.5)
34 Dieldrin 1 3 88.6(6.1) 93.8(5.3) 90.1(6.5) 88.8(6.0)
35 Demethoate* 20 30 79.8(3.4) 94.1(5.3) 85.2(4.6) 76.8(10.6)
36 Dimethylviphos* 5 8 74.0(7.5) 91.1(3.8) 86.0(3.8) 75.7(8.5)
37 Diphenylamine 3 5 73.8(8.5) 84.9(2.5) 92.5(10) 92.2(17.9)
38 Disulfoton 0.5 0.8 75.2(6.5) 92.0(3.8) 104.5(5.7) 96.4(13.2)
39 Endosulfan sulfate 25 50 84.8(7.2) 97.6(3.4) 81.3(4.4) 76.9(1.8)
Endosulfan-α 1 3 82.4(6.9) 94.4(6.3) 89.5(4.8) 89.0(9.8)
Endosulfan-β 0.8 1 90.9(5.0) 97.2(6.6) 92.6(2.9) 86.1(4.4)
40 Endrin 3 5 89.0(7.7) 95.5(7.8) 92.0(4.7) 83.3(5.9)
41 EPN* 1 5 89.0(4.0) 93.7(5.3) 86.1(1.6) 76.6(1.4)
42 Ethalfluralin 1 5 95.4(7.4) 102.3(1.1) 98.1(6.6) 88.9(13.4)
43 Ethion 20 30 101.1(1.7) 100.3(5.2) 90.9(1.5) 82.4(1.5)
44 Etridiazole 0.3 0.5 76.8(10.7) 96.4(4.0) 88.4(9.2) 92.2(19.6)
45 Fenamidone* 1 5 85.9(7.6) 99.2(7.1) 91.2(3.2) 84.7(2.2)
46 Fenamiphos* 5 10 82.3(5.8) 92.6(6.0) 91.3(1.7) 82.4(1.7)
47 Fenitrothion 5 10 78.6(6.8) 87.7(4.6) 96.3(7.0) 88.8(9.7)
48 Fenothiocarb* 1 5 83.6(5.7) 97.4(5.6) 101.5(4.3) 91.1(4.6)
49 Fenpropathrin 5 10 91.2(5.8) 102.7(5.0) 93.1(2.0) 80.9(1.2)
50 Fenvalerate 10 30 87.9(2.1) 92.1(5.0) 80.9(1.3) 64.2(2.5)
51 Ferimzone 80 100 97.6(2.8) 71.0(1.5) 105.1(2.7) 102.0(6.8)
52 Fipronil 1 3 93.1(6.2) 95.2(6.1) 103.5(2.3) 94.6(3.1)
53 Flucythrinate 8 10 85.0(2.2) 89.9(5.3) 80.6(1.5) 67.4(3.6)
54 Fludioxonil* 1 5 87.5(6.5) 99.5(5.7) 92.1(2.5) 85.9(1.2)
55 Fluopyram* 10 30 75.5(7.5) 90.4(0.5) 62.7(1.6) 49.0(7.3)
56 Folpet 5 10 66.8(1.5) 85.9(2.5) 72.7(7.0) 46.0(7.4)
57 Fthalide 5 10 86.2(7.1) 96.9(3.9) 97.1(3.0) 95.6(8.6)
58 Halfenprox 5 10 88.0(2.1) 93.2(5.3) 86.9(0.5) 81.3(1.5)
59 Heptachlor 1 5 73.6(7.9) 87.9(6.0) 93.4(5.9) 88.2(14.7)
Heptachlor-epoxide 1 5 79.9(8.9) 91.9(6.9) 96.9(6.2) 91.1(12.2)
60 Imazalil* 25 50 92.7(9.0) 101.9(8.5) 91.7(6.8) 86.0(2.3)
61 Indanofan 10 25 87.9(5.1) 102.6(6.6) 84.0(1.9) 81.8(3.1)
62 Indoxacarb 10 30 74.8(3.4) 84.2(4.5) 71.2(1.6) 58.4(5.3)
63 Iprodione 10 30 82.6(5.2) 92.7(2.4) 70.0(3.7) 46.4(6.0)
64 Isofenphos 1 5 79.8(5.2) 94.0(3.9) 101.8(2.5) 93.4(5.8)
65 Lufenuron* 1 5 38.4(7.1) 26.3(1.5) 31.3(5.3) 10.7(17)
66 Mecarbam 5 10 77.2(6.9) 95.5(3.6) 96.0(3.9) 89.2(5.6)
67 Methidathion* 5 8 78.6(5.9) 96.8(4.9) 97.5(2.6) 88.0(6.3)
68 Methoxychlor 0.3 0.5 93.9(4.2) 103.1(5.0) 92.0(1.3) 86.4(0.6)
69 Metobromuron* 50 80 75.9(9.1) 85.6(5.3) 90.6(4.5) 83.2(9.1)
70 Metolachlor* 1 5 86.0(5.8) 95.7(10.4) 103.4(3.8) 93.8(7.5)
71 Metribuzin* 1 5 74.2(6.3) 88.2(3.0) 97.7(5.9) 89.9(8.9)
72 Mevinphos* 5 10 70.7(11.6) 95.3(3.8) 86.1(14.1) 75.6(9.3)
73 Novaluron* 1 5 35.6(17.3) 47.2(1.5) 33.7(7.1) 16.5(9.7)
74 Oxyfluorfen 5 10 90.6(6.6) 105.1(3.5) 96.0(1.6) 86.8(2.8)
75 Parathion 3 5 79.4(5.7) 90.9(5.3) 100.1(3.7) 95.9(8.7)
76 Parathion-methyl 5 8 75.5(6.9) 85.8(3.8) 96.1(4.4) 87.4(12.2)
77 Pendimethalin* 1 5 80.8(4.6) 91.8(5.2) 98.9(2.0) 92.8(7.4)
78 Penthiopyrad* 10 30 82.8(9.3) 94.3(1.4) 54.6(2.0) 41.3(0.6)
79 Permethrin 10 25 89.6(5.3) 96.6(6.1) 84.0(2.8) 81.8(1.3)
80 Phorate* 5 10 70.3(7.5) 95.2(6.8) 106.3(4.6) 98.8(13.4)
81 Picoxystrobin* 1 5 106.1(3.6) 102.7(4.5) 63.0(1.5) 49.1(1.5)
82 Pirimiphos-ethyl 1 5 101.2(4.0) 104.7(2.5) - -
83 Probenazole* 5 10 81.8(13.0) 97.3(4.5) 35.1(9.4) 31.5(8.5)
84 Procymidone 10 25 90.4(4.9) 96.1(7.0) 102.4(3.7) 93.3(8.3)
85 Prometryn* 5 10 80.1(9.3) 96.8(5.4) 98.2(5.4) 92.1(8.9)
86 Propiconazole* 5 10 89.6(8.9) 99.7(5.5) 88.8(3.8) 79.9(2.2)
87 Prothiofos 5 10 83.3(5.0) 99.4(5.3) 99.2(1.7) 92.1(4.2)
88 Pyridalyl 5 10 85.4(2.7) 92.0(5.9) 87.0(1.9) 77.2(2.1)
89 Pyridaphenthion* 5 10 85.7(4.9) 95.8(2.3) 78.4(1.8) 69.8(3.5)
90 Quinoclamine* 5 10 74.1(4.2) 83.9(4.7) 86.7(1.6) 80.2(6.6)
91 Quintozene 50 80 94.5(8.4) 101.3(2.0) 91.9(6.0) 87.8(12.9)
Propiconazole* 5 10 89.6(8.9) 99.7(5.5) 88.8(3.8) 79.9(2.2)
Prothiofos 5 10 83.3(5.0) 99.4(5.3) 99.2(1.7) 92.1(4.2)
Pyridalyl 5 10 85.4(2.7) 92.0(5.9) 87.0(1.9) 77.2(2.1)
Pyridaphenthion* 5 10 85.7(4.9) 95.8(2.3) 78.4(1.8) 69.8(3.5)
Methyl-pentachlorophenyl sulfide 0.1 0.3 74.9(7.5) 86.7(9.1) 98.7(3.4) 83.1(12.2)
Pentachloroaniline 1 5 74.3(7.2) 84.8(6.4) 90.9(6.5) 86.1(13.3)
92 Silafluofen* 1 5 89.3(2.9) 96.0(5.4) 87.0(0.6) 80.9(2.0)
93 Simazine 5 10 71.2(8.1) 91.3(5.6) 98.2(9.2) 90.6(14.5)
94 Simeconazole* 1 25 74.7(7.4) 91.1(3.6) 96.3(7.0) 91.2(7.9)
95 Simetryn* 5 1 82.1(7.4) 99.1(4.4) 97.8(6.4) 93.0(12.2)
96 Spiromesifen* 1 5 83.0(5.5) 97.2(3.0) 82.5(2.9) 74.6(1.3)
97 Tebupirimfos* 1 5 75.0(8.4) 91.7(5.1) 99.4(5.0) 89.7(14.4)
98 Tefluthrin 0.08 0.1 84.3(8.3) 95.5(7.4) 104.5(8.5) 94.9(15.8)
99 Terbufos 1 5 70.9(8.4) 86.6(4.2) 101.3(7.2) 94.0(15.7)
100 Terbutryn* 5 10 78.3(6.4) 94.2(5.1) 96.1(5.7) 91.4(10.4)
101 Tetradifon 1 5 97.2(1.5) 101.9(5.7) 89.5(1.1) 85.3(0.8)
102 Thiazopyr* 5 10 86.7(7.2) 99.2(5.7) 105.3(6.7) 94.9(10.5)
103 Thifluzamide 1 5 87.6(6.6) 102.6(5.6) 98.1(0.6) 89.5(2.0)
104 Tolclofos-methyl* 1 5 78.3(7.6) 92.2(5.9) 100.4(6.5) 93.2(13.1)
105 Tolylfluanid* 5 10 44.9(6.1) 52.6(5.4) 54.7(1.5) 25.6(9.1)
106 Tralomethrin 1 5 76.1(4.0) 83.4(4.9) 70.0(3.0) 44.1(8.1)
107 Triadimenol 5 10 83.8(7.3) 95.3(5.8) 99.2(2.7) 91.7(4.1)
108 Trifluralin 1 5 95.3(2.4) 101.1(1.2) 99.5(6.7) 91.9(15.8)
109 Vinclozolin 1 5 84.8(7.7) 95.7(6.0) 102.4(8.1) 95.0(12.9)
110 Zoxamide 1 5 81.0(6.4) 90.0(3.6) 69.9(3.2) 43.5(4.3)
*41 pesticides were analyzed by both GC-MS/MS and LC-MS/MS.

LC-MS/MS분석 대상 농약성분 251성분의 회수율은 사과시료의 경우 저농도(50 μg/kg)에서는 회수율이 70~120% 이내이고 표준편차 20% 이내인 농약은 242종이었고, 정성이 가능한 성분은 248종이었으며 benfuracarb, diafenthiuron, fenhexamid 농약 성분 3종은 검출 할 수 없었다. 고농도(200 μg/kg)에서는 회수율이 70~120% 이내이고 표준편차 20% 이내인 농약은 242종이었고, 정성이 가능한 성분은 249종이었으며, benfuracarb, fenhexamid 농약 성분 2종은 검출 할 수 없었다. 쌀시료의 경우 저농도에서는 회수율이 70~120% 이내이고 표준편차 20% 이내인 농약은 238종이었고, 정성이 가능한 성분은 249종이었으며 benfuracarb, dichlofluanid 농약 성분 2종은 검출 할 수 없었다. 고농도에서는 회수율이 70~120% 이내이고 표준편차 20% 이내인 농약은 243종이었고, 정성이 가능한 성분은 250종이었으며 dichlofluanid 농약 성분 1종은 검출 할 수 없었다(Table 5).

GC-MS/MS분석 대상 농약성분 110성분의 회수율은 사과시료의 경우 회수율이 70~120% 이내이고 표준편차 20% 이내인 농약은 저농도(50 μg/kg)와 고농도(200 μg/kg)에서 각각 103종과 104종이었으며, 모든 농약성분이 검출 되었다. 쌀시료의 경우 저농도와 고농도에서 회수율이 70~120% 이내이고 표준편차 20% 이내인 농약은 97종이었고, 정성이 가능한 성분은 109종이었으며 pirimiphos-ethyl 농약 성분 1종은 검출 할 수 없었다(Table 6).

각국 및 국제기구 등에서 연구수행에 활용된 분석방법에 대한 적합성은 회수율과 상대표준편차 등의 범위를 이용하여 판단하고 있으며, 국내는 회수율 70~120% 및 상대표준편차 20% 이하(Rural Development Administration, 2009), 유럽연합에서 제시한 회수율은 70~120%와 상대표준편차 20% 이하, 국제식품규격위원회는 회수율 60~120%와 상대표준편차 15~30% 이하로 규정하고 있다(Codex Alimentarius Commission, 2003). 본 연구결과에서 LC-MS/MS와 GCMS/MS를 이용한 다종농약 다성분 분석법에서 제시한 회수율은 최소 70% 이상과 상대 표준편차 20% 이하로 나타내어 국내 및 국제적 기준을 충족하였다. 따라서 본 연구에서 적용된 분석방법은 농산물 중 잔류되는 다성분 농약을 분석하는데 적용될 수 있을 것으로 판단되었다.

LC-MS/MS 분석 대상 농약 중에서 abamectin, chlorfluazuron은 기존에 수행된 선행 연구에서 LC-MS/MS 분석조건에서 정량이 불가능한 수준의 감도를 보여 분석불가 성분으로 분류된 바 있고(Kwon 등 2001), Hernando 등(2007)은 abamectine과 같은 macrocyclic lactone 화합물은 HPLCMS/MS의 drying gas 온도를 낮추면 감도를 높일 수 있다고 보고 하였다. Hernando 등(2007)의 연구 결과를 기기분석 조건에 반영 한 결과 사과시료에서 abamectin의 경우 90%, chlorfluazuron의 경우 75% 이상의 회수율을 보임으로써 잔류농약 다성분 분석 기준인 70~130% 이내를 만족하는 재현성이 우수한 결과를 얻을 수 있었다. 사과와 쌀시료에서 공통적으로 검출되지 않은 benfuracarb 농약은 기존의 농약잔류 연구결과에서 회수율이 잔류농약 다성분 분석 기준보다 낮은 경향을 보였다(Gwon 등, 2014; Yang 등, 2013). Benfuracarb는 중성 및 염기성 조건에서 음전하를 띄며, 음전하를 지니는 농약들은 QuEChERS 정제과정 중 PSA에 흡착되는 특성이 있어 회수율이 떨어지고 최종 시료 추출액이 pH 6이상의 조건에서는 검출이 되지 않는다는 연구 보고가 있다(Lehotay, 2003; Sannino 등, 2004). LC-MS/MS와 GC-MS/MS 분석대상 농약 dichlofluanid은 시료 추출과정 또는 시료 추출액의 pH의 증가에 의해 빠르게 분해되는 특징이 있고 질량분석기를 이용한 다성분 동시분석법에서 회수율이 낮은 성분으로 단성분 분석법으로 정량이 가능하다고 보고 된바 있다(Cho 등, 2013). 또한, GC-MS/MS 분석대상 농약인 pirimiphos-ethyl은 사과시료에서는 100% 이상의 회수율을 보였으나 쌀시료에서는 검출되지 않았다. 다른 matrix에 비해 시료 추출단계에서 쌀시료 습윤화 과정을 거치는 동안 pirimiphos-ethyl 성분이 acetonitrile 층으로 완벽하게 분리되지 않은 원인이 작용한 것으로 판단되어진다. 따라서 분석효율이 낮거나 미분석 대상 농약에 대해서는 시료 전처리법의 개선과 분석효율을 증대시키기 위한 추가적인 연구가 필요할 것으로 사료된다.

결 론

본 연구에서는 QuEChERS 시료 전처리법을 적용한 사과와 쌀 시료로부터 LC-MS/MS와 GC-MS/MS를 이용하여 잔류농약 동시다성분 분석의 가능성을 살펴보았다. LC-MS/MS 분석대상 농약성분 251종, GC-MS/MS 분석대상 농약성분 110종을 적용하여 320종 농약성분이 본 연구의 다성분 동시분석법 적용 시험을 통해 정성 및 정량이 동시에 가능함을 확인하였다. 분석대상 농약성분의 회수율은 70-120%의 적정 범위를 나타내었으나(Fig. 2), 이 범위를 벗어나는 회수율을 나타내는 성분들도 다수 존재하여 이를 개선하기 위해 분석효율이 낮은 농약성분들에 대해서는 추출방법 및 추가적인 시험법 적용과 개발이 필요하다고 판단되었으며, 본 연구에서 검토된 LC-MS/MS와 GC-MS/MS를 이용한 농약의 다성분 동시분석법은 앞으로 농산물의 농약잔류 모니터링 연구 분야에 적용될 수 있을 것으로 기대되었다.


Fig. 2. 
Distribution of recoveries in apple and rice using two different concentrations with LC-MS/MS and GC-MS/MS.

Acknowledgments

본 연구는 안전성평가연구소 기관 고유사업(KK-1510)에 의해 수행되었습니다.

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