CDFA-MRSM... 1... 2 CDFA MRSM SOP... 3... 3... 3... 3... 30... 52 Retention Time Locking... 52... 61 1
CDFA MRSM CDFA MRSM [California Department of Food and Agriculture CDFA ] [Center for Analytical Chemistry CAC ] [Multiresidue screen method MRSM ] 200 40 # FR-40 # MRLs 40 # 250 700 4500 1902 DPR 1991 CDFA DPR CDFA 1926 30 Anaheim Fresno Sacramento 12 CDFA MRSM MDL 0.005~0.2ppm 200 8 12 200 1 CDFA CAC CDFA MRSM Mill DB-1 DB-17 C 8 C 18 CDFA MRSM 1997 60 1
CDFA MRSM GC HPLC MRSM GC Agilent6890 GC Agilent6890 HPLC( HP-1 DB-1 30m 0.25mm 0.25 m HP-50+ DB-17 30m 0.25mm 0.25 m HP-1 DB-1 30m 0.53mm 1.5 m HP-17 DB-17 30m 0.53mm 1.0 m ) C8 4.6mm 250mm 5 Agilent1100 C18 4.6mm 250mm 5 Pickering5200 GC-MS Agilent5973 ECD ECD FPD FPD FLD HP-5MS 30m 0.25mm 0.25 m MSD ( 1-7) 1. 2. 3. 4. 5. 6. 2
7. CDFA MRSM SOP MRLs CDFA MRSM OP CH N CARB 1 2 3 4 5 6 7 8 9 10 11 1 Hobart Chopper model 8181 1L, ) OMNI MIXER HOMOGENIZER 17106 N EVAP Nitrogen Evaporation System Models 112 ECD FPD FLD 2 3
ACS 120 1 NaOH 0.5N pickering (cat.no CB130) 2 OPA diluent pickering (cat.no CB910 O-Phthaladehyde(OPA) pickering (cat.no 0120) Thiofluor pickering (cat.no 3700-2000) 100ml 5.0ml 1.0ml 60 9 3-4 15ml 300ml -18 15 100ml 10.0ml Florisil 1g Agilent AccuBOND II Part No. 188-2460 Supelco Supelclean Envi-Florislil Reorder No.57053) Aminopropyl 500mg Agilent AccuBOND II Part No.188-1050 Supelco Supelclean LC-NH2 Reorder No.57014 0.2 m 25mm 0.45 m 13 2ml Agilent Part No.5182-0554 5018-0864 Agilent Part No.5183-4529 16ml5183-4530 40ml GC 1.0m Agilent 0.25mm Part No.19091-60610 0.53mm Part No.19095-60610 HPLC C-18 Pickering 4.6mm 4.5cm Part No.18ECG002 ECD FPD 100% DB-1 HP-1 30m 0.25mm 0.25 m Agilent HP-1 Part No.19091Z-433 J&W DB-1 Part No.122-1032 50% DB-17 HP-50+ 30m 0.25mm 0.25 m Agilent HP-50+ Part No.19091L-433 J&W DB-17 Part No.122-1732 100% (DB-1 HP-1) 30m 0.53mm 1.50 m Agilent HP-1 Part No.19095Z-323 J&W DB-1 Part No.125-1032 50% (DB-17 HP-50+) 4
30m 0.53mm 1.0 m Agilent HP-50+ Part No.19095L-023 J&W DB-17 Part No.125-1732 MSD HP-5MS 30m 0.25mm 0.25 m Agilent HP-5MS Part No.190191S-433 HPLC C 8 4.6mm 25cm 5 m Pickering Part No.1846250 C 18 4.6mm 25cm 5 m Pickering Part No.1846150 3 MRSM : 1. 2. 3 3. / GC-FPD FL 1g NH 2 0.5g GC-MS GC-ECD LC-FLD 5
3.1 a OP CH CARB 5 454 40#(40-Code of Federal Requlations) 180.1 ( ) ( ) 6
b c 8. 3.2 3.2.1 50.0g 25.0g 9. 10. 3.2.2. 100ml 50ml 3.2.3 2 11. 12. 3.2.4 100ml 10-15g 5-7.5gNaCl 13. 7 14.
3.2.5 80ml-100ml 40ml-50ml 3.2.6 1 3.2.7 10 15. 3.3 3.3.1 a 10ml 3 3 100ml b 80 2ml 2ml 2ml 1% / v/v OP CH CARB 16. 3.3.2 a 2ml 15ml 3.0ml 5.0ml b c GC-FPD d 0.2 m 5ml GC 3.3.3 a Florisil 1g 5ml 10% / v/v 5ml b 2ml Florisil 15ml 17. c 5ml 10% / v/v d 3.3.3.C e15ml 55 8
5.0ml f 5.0ml g h GC-ECD 3.3.4 N- a aminopropyl 4ml 1% / v/v b 2ml 1% / V/V 15ml 18. c 2ml 1% / V/V d 3.3.4.C e 15ml 55 <0.1ml 19. f 2.5ml g 20. h 0.2 m 5ml HPLC 4 4.1 13 4.2 4.2.1 DB-1 DB-17 FPD P Agilent 6890 4.2.2 1 l 4.2.3 220 250 150 2min 8 9
/min 250 12min 10ml/min DB-1 12ml/min DB-17 12ml/min 13min 2ml/min 15ml/min 5min 75ml/min 100ml/min 4.3 4.3.1 DB-1 DB-17 ECD Agilent 6890 4.3.2 1 l 4.3.3 200 320 150 2min 6 /min 270 8min 23min 1ml/min 2.3ml/min 60ml/min 4.3.4 4.3.1 ELCD 2 l 200 250 160 1min 10 /min 250 15min 20ml/min 65ml/min DB-5 10m 0.53mm 2.65 m DB-17 30m 0.53mm 0.25 m. 4.4 N- 4.4.1 HPLC Agilent 1100 Pickering Post Column System 4.4.2 20 l 4.4.3 a CDFA 42 1ml/min ex330nm em465nm min % 0 20 80 2 20 80 16 90 10 18 90 10 18.1 20 80 b % min ml/min % 0.00 0.5ml/min 0.00 B 15% 2.00 B 25% 10
8.00 B 25% 9.00 0.8ml/min 9.00 B 40% 10.00 B 45% 19.00 B 80% 25.00 0.8ml/min 25.00 B 80% 26.00 0.5ml/min 26.00 B 15% 4.4.4 1-0.5N NaoH 0.3ml/min 2-OPA 0.3ml/min 100 5 RT GC RT 0.005 RT 0.01 HPLC RT 0.15 6 6.1 6.1.1 ( ) ( ) ng = a b >125% <75% C 1 l, 20 l 6.1.2 = (ng) 6.2 6.2.1 50.0g( ) 100ml( ) 1000mg 1g 10ml( ) 5ml( ) 1ml 1000 l 1 l =1mg 11
25.0g( ) 50ml( ) 1000mg 1g 10ml( ) 5ml( ) 1ml 1000 l 1 l =1mg 6.2.2 50.0g( ) 100ml( ) 1000mg 1g 10ml( ) 2.5ml( ) 1ml 1000 l 20 l =40mg 25.0g( ) 50ml( ) 1000mg 1g 10ml( ) 2.5ml( ) 1ml 1000 l 20 l =40mg 6.3 ng/mg ppm 6.3.1 X(ppm)= (ng) (mg) X(ppm)=[ ( ) ( ) (ng)]/1(mg) = ( ) ( ) X(ppm)= ( ) 6.3.2 X(ppm)= (ng) = ( ) 40mg ( ) 0.025 12
6.4 70-120% 1 2 3 7 (ppm) (50g 1.0ml ) Profenofos 1.27 Methidathion 1.09 Trifluralin 0.25 Oxyflurofen 0.11 Propoxur 1.05 Oxamyl 0.93 Chlorpyrifos 0.05 Methidathion 0.05 Vinclozolin 0.10 Heptachlor 0.10 Oxamyl 0.25 Propoxur 0.25 Phosalone 2.18 Methyl Parathion 0.30 Dicloran 0.20 Carbofuran 0.54 Aldicarb Sulfoxide 0.59 Aldicarb Sulfone 0.73 7.1 SOP 7.1.1 DB-1/DB-17 FPD HP-5 NPD FPD S 7.1.2 DB-1/DB-17 ECD HP-5 13
ELCD 7.1.3 C 18 C 8 NPD 7.1.4 / CH OP Chlorpyrifos Carb Carbaryl 7.2 GC/MS 0.5-1.0ng/ l / 3 7.2.1 1 20ml 0.5ml 2 2.0ml 3 5ml 25% / Florisil lg 5ml 4 5 5ml 25% / 6 0.5ml 7 7.2.4 PTFE 7.2.2 / 1 50g 150gNa 2 SO 4 150ml 2 2min 3 4 60ml 5 0.5ml 6 PTFE 7.2.3 1 3.3.3.a b c d Florisil 0.5ml 2 PTFE 7.2.4 PTFE 1 1 PTFE 0.45 m 4mm 1ml 2 3 14
8 8.1 (ppm) (ppm) (%) (MDL)(ppm) 15
8.2 (ppm) (MRL S ) LOD 16
9 9.1 9.1.1 A OP-9 ( g/ml) ( g/ml) Acephate 0.20 2.0 Chlorphyrifos-methyl 0.05 0.5 DEF 0.05 0.5 Ethion 0.05 0.5 Methamidophos 0.10 1.0 Omethoate 0.20 2.0 Parathion 0.05 0.5 Parathion-methyl 0.05 0.5 Tetrachlorvinphos 0.10 1.0 B OP-10 ( g/ml) ( g/ml) Azinphos-methyl 0.20 1.0 Chlorpyrifos 0.05 0.5 DDVP DDVP 0.10 1.0 Diazinon 0.10 1.0 Dimethoate 0.05 0.5 ( ) -Mevinphos 0.072 0.7 ( ) -Mevinphos 0.028 0.3 Malathion 0.10 1.0 Methidathion 0.05 0.5 Phosmet 0.20 2.0 Profenofos 0.10 1.0 9.1.2 A CH-6 ( g/ml) ( g/ml) Chlorothalonil 0.10 1.0 Chlorthal-dimethyl 0.10 1.0 Cypermethrin 0.40 2.0 Endosulfan 0.10 1.0 Endosulfan 0.10 1.0 Endosulfan 0.10 1.0 Hexachlorobenzene 0.05 0.5 Trifluralin 0.10 1.0 17
B CH-10 ( g/ml) ( g/ml) Captan 0.40 1.0 Chloropyrifos 0.10 1.0 CIPC 1.00 2.0 P.P-DDE P.P-DDE 0.10 1.0 Dichlobenil 0.05 0.5 Dicloran 0.05 0.5 Iprodione 0.40 1.0 PCNB 0.05 1.0 cis-permethrin 0.20 1.0 trans-permethrin 0.20 1.0 Vinclozolin 0.10 1.0 9.1.3 CDRB-10 ( g/ml) ( g/ml) Aldicarb 0.50 5.0 Aldicarb Sulfoxide 0.50 5.0 Aldicarb Sulfone 0.50 5.0 Carbaryl 0.50 5.0 Carbofuran 0.50 5.0 3- Carbouran,3-OH 0.50 5.0 Isoprocarb 0.50 5.0 Methiocarb 0.50 5.0 Methomyl 0.50 5.0 Promecarb 0.50 5.0 18
9.2 4.1 1 l Agilent 6890FPD OP-9 HP-1 30m 0.53mm 1.0 m RT, Area Height (ppm)(rt * ) 0.10 (2.26) 0.20 (6.37) 0.20 (6.37) 0.05 (10.50) 0.05 (10.61) 0.05 (11.81) 0.10 (13.44) 0.05 (14.20) 0.05 (15.26) RT (min) A/H RT (min) A/H RT (min) A/H RT (min) A/H RT (min) A/H RT * RT 19
9.3 9.3.1 RT RT 0.005 RT 0.01 0.15 9.3.2 75%-125% 10 10.1 10.1.1 SR # 10.1.2 SR # 1 10.1.3-5~-15 10.1.4 SR # 10.1.5 10.2 1000 g/ml 1000 g/ml 10.2.1 10.2.2 10.2.3 10.2.4 30 10.2.5 mg/ml 10.2.6 10.2.7 SS # SR # A B C 2 10.2.8 SM # 3 10.2.9 20
0 4 1 2 10.2.10 10.2.11 10.3 10.3.1 50 10.3.2 10.3.3 10.3.4 10.3.5 3% 5% 10.3.6 10.3.7 10.3.8 5% 10.3.9 GC-MSD/IRD 10.3.10., 6 10.4 1000 g/ml 10ppm 1.0ppm 0.1ppm 10.4.1 1000 g/ml 10.4.2 4ml 10.4.3 4 5 a 10ng/ l 0.5ml 1mg/ml 50ml 60ml b 1ng/ l : 5ml 10ng/ l 50ml 21
c 0.1ng/ l : 0.5ml 10ng/ l 50ml 10.4.4 ng/ l 10.4.5 GC HPLC 10% 10.4.6 0 4 10.4.7 10.4.8 10.4.9 0.1ppm GC HPLC RT RRT 10.4.10 10.4.11 1000 g/ml 10.5 10.5.1 10.5.2 10.5.3 10.6 10.6.1 10.6.2 10.6.3 10.6.4 22
1 SR# CAS % mg 23
2 SS# + g g g % mg ml mg/ml 24
3 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 : : SM # : (#) ( g/ml) (ml) g/ml 25
4 : SS# mg/ml ml ml mg/ml SS#: g/ml 26
5 SS# mg/ml SS# mg/ml ml ml mg/ml g/ml SS# 27
6 SS# SS# 1 2 3 1 2 3 28
11 RT CDFA- CDFA- CDFA- acephate captan ( ) ( 10 ) ( ) 29
Retention Time Locking Agilent 6890N EPC 1. Agilent Instrument RTLock RTSearch, 1 1. RTL 2 52
RTLock New RTL Calibration.. Run1-Run5 Desired Ret Time 2 2. 3 53
4 RTLock Re Lock current method Calc new pressure Update current HP6890 Method 5 RTSearch Edit RT Table 54
Auto Retention Time Locking Agilent 6890N EPC Agilent 6890N 1. autolock.zip ALCK1HPL.TXT ALCK2HPL.TXT AUTOLOCK.DOC AUTORTCL.MAC ALCK1HPL.TXT ALCK2HPL.TXT AUTORTCL.MAC CORE C:\HPCHEM\CORE\ instrument on line MACRO AUTORTCL.MAC, GO [ENTER] 1 RTLock 1. 55
2. - A. A B *A.m *B.m test.m testa.m testb.m A B A testa.m 1 2 2. RTLock Auto RTL Calbration ( 3) 3. 56
OK 4 4. A 5 5. testa.m 20% 10% Abort Abort 6. 6 RTL_TEMP.M YES 7 7. 57
A 8 8. RTLock Edit RTL Calibration OK - 9 9. - A testa.m B testb.m A B testb.m 2 B 58
B. A B testa.m testb.m 9 A testa.m, RTLock Auto (Re)Lock current method 10 10. 11 11. 1 3 1 12 12. testa.m 1 13 59
13. testa.m 14. test.m 1 testa.m 1 test.m, 1 1 14 B testb.m A 2 B test.m 2 60
1 Pesticide Analytical Manual Volume l, Section 303: Method for Non-fatty Foods and reference therein. 2 J. Assoc.Off.Anal.Chem.(1985) Vol.68(2),29 3 Fresenius J Anal.Chem.(1991) 339,376-383 4 J. Assoc.Off.Anal.Chem.(1991) 74,554-565 5 Chromatographia (1987) 24,469-476 6 J. Agric.Food Chem (1991) 39(9),1658-1666. 7 California Department of Food and Agriculture Multiresidue Screen For Pesticides in Fruits and Vegetables 1998. 9 8 MRSM 2001.4 61