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1 J. Fd Hyg. Safety 20(3), (2005) GC-NPD w Simetryn Buprofezin ½ Á½ Á ³Á½ Á Áw Á š y q Simultaneous Determination of Simetryn and Buprofezin by Gas Chromatography with Nitrogen Phosphorus Detector Eunjeung Kim, Sungdan Kim, Jaekyoo Lee, Soojin Kim, Sangmi Lee, Sunhee Han, and Heegon Kang 4FPVM.FUSPQMJUBO$JUZ*OTUJUVUFPG)FBMUI&OWJSPONFOU4FPVM,PSFB (BOHCVL"HSJDVMUVSBM1SPEVDUT*OTQFDUJPO5FBN 3FDFJWFE.BSDI"DDFQUFE"VHVTU ABSTRACT This method was described for the simultaneous determination of simetryn and buprofezin in rice, vegetables, and fruits by gas chromatography(gc) with nitrogen phosphorus detector. The GC method of simetryn and buprofezin was shown to give a linear detection ranges between 0.019~9.306mg/kg, 0.023~11.27mg/kg, respectively. For evaluation of GC method, simetryn spiked into rice, vegetables and fruits at the level of 4.653mg/ kg was determined. The recoveries of simetryn by GC method were ranged from 57.9 to 115.9%. For evaluation of GC method, buprofezin spiked into rice, vegetables and fruits at the level of 2.817mg/kg was determined. The recoveries of buprofezin by GC method were ranged from 56.5 to 121.5%. Key words: simultaneous determination, simetryn, buprofezin, GC ü w r x t 2014 ƒ t y w y ƒ ƒ š q y y j w» ƒ ƒ š. ¾ ƒœ l w ƒ. ü š. ü š w» w w ³» y w ƒ w. x š simetryn [N,N'-diethyl- 6-(methylthio)-1,3,5-triazine- 2,4-diamine, MW:213.3]( 1) triazine ü ww Ÿw w, w w ƒ f (400mg/l, 20 o C) 1) mw y ƒ 2-3) simetryn w 4-7) ƒ. Author to whom correspondence should be addressed. ù simetryn w liquid chromatography mass spectrometry 8) gas chromatography with nitrogen phosphorus detecter w š 9). Buprofezin[2-[1,1-dimethylethyl)imino]tetrahydro-3-(1- methylethyl)-5-phenyl-4h-1,3,5-thiadiazin-4-one, MW:305.4] ( 1) thiadiazine m m leafhoppers whitefly z 10). w screenwš w z w 11) w w š 12-13). Simetryn buprofezin x w» tœ 14) w. wš rw simetryn 159

2 160 &VOKFVOH,JNFUBM Fig. 1. Chemical structures of simetryn(a) and buprofezin(b). buprofezin w» w š ( ), 7 ( e,,, qv e, š,, m m) 3 (,, j ) w GC-NPD GC-MSD w wš ƒ sƒwš w. q š š 1 ( ), 7 ( e,,, qv e, š,, m m) 3 (,, j ) w w, simetryn t t Dr. Ehrenstorfer(Germany) t w š buprofezin ( ) (Japan) t w. acetonitrile Honeywell(USA) t w š, NaCl TEDIA(USA), p w. Sharkskin (E&K filter, U.S.A), filter 13mm 0.2µm nylon syringe filter(whatman, U.S.A) w. š» food mixer(w ),» Robot Coupe Blixer 5 Plus (France) w,» omni mixer(international Waterbury, U.S.A) w. gas chromatography w w detector mass selective detector nitrogen phosphorus detector w š software chemstation w. x Simetryn buprofezin w» w Fig kg w 20g Fig. 2. Schematic diagram of simetryn and buprofezin znalysis. w 20ml š 2 z 100ml acetonitrile yww omni mixer 2 ³ y w 2 w 50g w 100ml acetonitrile yww omni mixer 2 ³ y w. y sharkskin filter w w. 10~15g NaCl k w z acetonitriled wš acetonitriled 10ml w w acetone 1ml w k z w x w. x GC-NPD GC-MSD d w Table 1, 2. z d Simetryn t mg/l w 0~9.306mg/l t w buprofezin t mg/l w 0~11.27mg/l t Table 1. Instrumental condition of GC-NPD for simetryn and buprofezin analysis Column Oven temperature Injection temperature Detector temperature Gas flow DB-1701(30.0 m 320 µm 0.25 µm) 110 o C(1 min) 15 o C/min 200 o C(8 min) 10 o C/min 260 o C(7 min) 210 o C 300 o C N 2 (1.4 ml/min)

3 4JNVMUBOFPVT%FUFSNJOBUJPOPG4JNFUSZOBOE#VQSPGF[JOCZ(BT$ISPNBUPHSBQIZà 161 Table 2. Instrumental condition of GC-MSD for simetryn and buprofezin analysis Instrument Column Oven temperature Injection temperature Carrier gas MSD Ionization method Ion source temperature Transfer line temperature scan range 5973 GC-MSD HP-5MS(30.0m 250µm 0.25µm) 100 C(2min) o 10 C/min o 280 o C(15min) 230 o C He(Splitless, 1.0ml/min) EI 230 o C 150 o C m/z w w. ƒ z x t x š ( ), ( e,, ), (qv e, š,, m m) (,, j ) ƒƒ simetryn 4.653mg/kg, buprofezin 2.817mg/kg ƒ t ƒ w z w w z d w. š Simetryn y t GC-NPD w š(fig. 3) GC-MSD y (Fig. 4). GC-NPD w 0.019~9.306mg/kg ùkü (R:0.99) w 0.019mg/kg. ù tœ simetryn w x» 0.05mg/kg ³ 14) w ƒ w ùkû. Buprofezin y t GC-NPD w š(fig. 3), GC/MSD y (Fig. 5) GC-NPD 0.023~ 11.27mg/kg ùkü (R:0.99) w 0.023mg/kg. Valverde 15) buprofezin GC-NPD w buprofezin w 0.02mg/kg šw ew. w ù tœ buprofezin» e 1.0mg/kg,» eƒ 0.1mg/kg ³ 14) û buprofezin. Simetryn w z GC-NPD š 1 ( ), 7 ( e,,, qv e, š,, m m) 3 (,, j ) 4.653mg/kg simetryn t ƒw z w Table w z 57.9% 115.9% ùkû. j simetryn z 57.9, 68.8% xw 11 û ùkû e simetryn z 112.5, 115.9% ƒ ùkû. Mashiro 8) LC-MS d w simetryn z 83% š šwš GC-NPD d w ƒ ùkû. w Kazuhiro(9)ƒ šw x,, simetryn z 72.5, 78.5, 80.3% ùkû. simetryn z 83.9~115.9% ùkû. Fig. 3. GC-MSD chromatograms of simetryn standard solution and buprofezin standard solution.

4 162 &VOKFVOH,JNFUBM Fig. 4. Mass spectrum of simetryn. Fig. 5. Mass spectrum of buprofezin. Buprofezin w z GC-NPD š 1 ( ), 7 ( e,,, q v e, š,, m m) 3 (,, j ) 2.817mg/kg buprofezin t ƒw z w Table w z 56.5% 121.5% ùkû. e z 115.8, 121.5% ƒ ùkû,»k z 92.6~106.5% yw ùkþ. Valverde 15) š GC-NPD w

5 4JNVMUBOFPVT%FUFSNJOBUJPOPG4JNFUSZOBOE#VQSPGF[JOCZ(BT$ISPNBUPHSBQIZà 163 Table 4. Recoveries of simetryn in spiked samples by GC-NPD Recoveries(%, meanûs.d. n=5) Rice Û 6.3 Spinach Û 10.9 Leaf mustard 84.8 Û 5.1 Korean cabbage 92.1 Û 4.2 Paprika 83.9 Û 3.1 Green pepper 94.7 Û 5.5 Cucumber 98.4 Û 0.7 Tomato 89.3 Û 11.3 Persimon 95.9 Û 2.1 Apple 57.9 Û 0.5 Kiwi 68.8 Û 16.7 buprofezin z w 0.02mg/kg 99.1% š w, GC-MSD SIM mode w z 77.9% š šw 16). buprofezin s³z 89~100% š š 15) wš ew w. Ibrahim 17) m buprofezin z d w z 90.5~92.75% š w. Table 5. Recoveries of buprofezin in spiked samples by GC- NPD Recovery rate (%, meanûs.d. n=5) Rice Û 12.9 Spinach Û 10.3 Leaf mustard 95.8 Û 1.9 Korean cabbage 95.9 Û 5.6 Paprika 99.8 Û 3.5 Green pepper Û 0.9 Cucumber Û 5.9 Tomato 92.6 Û 11.5 Persimon Û 1.4 Apple 56.5 Û 2.4 Kiwi 65.1 Û 15.8 j buprofezin z 56.5, 65.1% ùkû simetryn xw û z ùkþ. š 112.5% z ùkü, Hideo 18) alkali flame ionization detector w GC 85% šw ùkû. š 1 ( ), 7 ( e,,, qv e, š,, m m) 3 (,, j ) simetryn buprofezin GC-NPD GC-MSD w. 1. Simetryn GC- NPD w w 0.019mg/kg buprofezin GC-NPD w w 0.023mg/kg d. 2. š 1, 7, 3 11 t ƒw z x ww š simetryn 112.5%, buprofezin 115.8% yw ùkü z simetryn 83.9~115.9%, buprofezin 92.6~121.5%, z simetryn 57.9~95.9%, buprofezin 56.5~102% ùkü. 3. š ƒ w» w w y w. tœ simetryn buprofezin ù mw ƒ w y w, z ƒ ƒ w». š x 1. Tomlin : The pesticide manual, 10th Ed. British Crop Protection Council, (1995). 2. Marion, G., Dieter, M., Bernd, M.G., Thomas, W., Aiqian, Z., Xie, Q., Cheng, S., Jingwen, C., Bernhard, P., Ernst, L. and Antonius, K.: Triazines in the aquatic systems of the Eastern Chinese Rivers Liao-He and Yangtse. Chemosphere, 47, (2002). 3. Seiichi, N. and Toshio, I.: Pesticide residues in water and an aquatic plant, nelumbo nucifera, in a river mouth at lake kasumigaura, Japan. Chemoshere, 33(7), (1996). 4. Frias, S., Sanchez, M.J. and Rodriguez, M.A.: Determination of triazine compounds in ground water samples by micellar

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