HS SPME GC MS 289 HS SPME GC MS 1,2 2 3 2,3 2 1 2 (11, 110161 ; 21, 100050 ; 31, 100069) :, 31 (23, 8 ), 6 10, 01002012gΠL,85 %110 %,3 %12 % : ;;,; ;,; Headspace Solid2Phase Microextraction Combined with Gas Chromatography Mass Spectrometry for Determination of Organochlorine and Pyrethroid Pesticides in Milk ZHU Jie, YANG Xin, FENGJin2fang, SHI Zhi2xiong, ZHAO Yun2feng, ZHOU Yan2ming, WU Yong2ning (College of Food Science, Shenyang Agriculture University, Liaoning Shenyang 110161, China) Abstract: Objective A rapid method was developed for multi2residues determination of organochlorine and pyrethroids pesticides. Method Headspace solid2phase microextraction (HS2SPME) was used as sample pretreatment method for extraction and concentration. Gas chromatography with mass spectrometry detection ( GC2MSD) was used to analyze 31 pesticides (included 23 organochlorine pesticides and 8 pyrethroids) in milk. Two stable isotope compounds, 6 labeled hexachlorobenzene and 10 labeled mirex, were used as internal standards for the quantification. Results The method showed good recoveries (range from 85 % to 110 %) and repeatability ( RSD < 12 %) for all compounds, with detection limits ranging from 01002 to 012 gπl. Conclusion As the analytical procedure does not include any concentration or cleanup steps, it is easy and fast to perform, making it applicable for analysis in pesticides monitoring programmes in milk. Key word : Pyreghrins ; Pesticides ; Hydrocarbons, Chlorinated ; Mass Fragmentography ; Chemistry, Analytical ; Milk 20 60, [2 ] : (2001BA804A19 2001BA804A45) : :, [3 ] [4,5 ],, [6,7 ],, [1 ], ( Solid phase, microextraction, SPME) 1989 Pawliszyn,,,,,,, [8,9 ] SPME, [10,11 ],,SPME, ( GC MSD) (SIM) 23 8, 10 6 2,
290 CHINESE JOURNAL OF FOOD HYGIENE 2007 19 4,,,,, 1 111 QP2010 plus () : Rxi 5MS (30 m 0125 mm 0125m,Restex ) ; SPME,Supelco (Bellefonte, PA, USA),( PA,85m) ;15 ml,,varian ;,Corning ; (Vortex 2 GENIE, Scientific Industries) ( EASY pure R UVΠUF) > 991999 % () 112 11211 23 ( p, p DDE p, p DDD o, p DDT p, p DDT > 99 %) Sigma (St1Louis, MO, USA) ; 8 ( > 98 %) Dr1 Ehrenstorfer ( Augsburg, Germany) 11212 10 ( 10 mirex ; 100 mgπl 6 ( 6 HCB ; 100 mgπl), ( Cambridge Isotope Laboratories, USA) 11213 (Fisher ) ( ) 113 11311,,10 ml,, 20 11312,,, 4 : 2 mgπl, p, p DDE p, p DDDo, p DDT p, p DDT 1 mgπl, 015 mgπl, 4 mgπl 11313 10 mirex 6 HCB ( 100 mgπl ) 016 ml, 10100 ml, 610 mgπl, 4 114,4, 1 h 115 15 ml, 5 ml 5 l 113 g NaCl,, ( ), 20 s,4, 20 min,90 50 min,,260 5 min,,gc MS 116 11611 260 ;, 110 mlπmin,3 mlπmin ;,1 min (1 min 6) ; : 50, 1 min, 30 Πmin 150,5 Πmin 185, 4 min, 10 Πmin 280, 6 min, 30183 min 11612 ( EI), 70 ev ; :220 ; :220 ; : + 013 kv ; : 1115 min( scan mode),50450 u, 2 211 [12 ],: (PA,85m),113 g, 90 50 min,260 5 min 212 31 2, (SCAN), NIST05, 90 1 31 2 (TIC) 1, TIC
HS SPME GC MS 291 (11,21,2 1 6,31,41,51,61,71,81,91,101,111,121,131,141,151,161,171 p, p DDE,181,191, 201 p, p DDD,211o, p DDT, 221, 231 p, p DDT, 241, 251, 261, 271, 281, 28 1 10,291,301,311 ) 1 31 2, SIM,,31 2 1 1 ( ( %) (t R Πmin) %) Q1 Q2 ( ( %) (t R Πmin) %) Q1 Q2 1 HCH alpha ( ) 111720 181(100) 183(94) 185(75) 2 HCB( ) 121003 284(100) 286(78) 288(45) 2 6 HCB( 6 ) 111993 290(100) 292(62) 294(24) 3 HCH beta ( ) 121630 219(100) 217(77) 221(50) 4 Linedane () 121907 219(100) 217(78) 221(48) 5 PCNB( ) 131112 237(100) 235(63) 239(60) 6 HCH delta ( ) 131870 181(100) 183(98) 185(34) 7 Chlorothalonil ( ) 141105 266(100) 264(77) 268(49) 8 HEPT() 161302 272(100) 270(55) 274(80) 9 S 421 ( ) 161699 130(100) 132(94) 134(31) 10 Aldrin( ) 171728 263(100) 261(66) 265(67) 11 Dicofol ( ) 181090 139(100) 141(62) 250(23) 12 HCE() 191270 353(100) 351(53) 355(84) 13 Allenthrin() 191386 123(100) 91(35) 136(24) 191504 123(100) 91(30) 136(21) 14 trans Chlordane() 191860 373(100) 371(45) 375(89) 15 cis Chlordane () 201307 373(100) 371(45) 375(89) 16 trans Nonachlor () 201453 409(100) 407(98) 411(61) 17 p, p DDE( ) 201919 318(100) 316(78) 320(48) 18 Dieldrin( ) 201942 263 (100) 261(63) 265 (73) 19 Endrin() 211509 263 (100) 261(61) 265 (67) 20 p, p DDD( ) 211972 235 (100) 237(65) 239 (23) 21 o, p DDT( ) 221062 235 (100) 237(64) 239 (23) 22 cis Nonachlor () 221077 409 (100) 407(98) 411 (61) 23 p, p DDT( ) 221851 235 (100) 237(64) 239 (24) 24 Teramethrin( ) 231838 164 (100) 81(23) 123 (26) 231981 164 (100) 81(23) 123 (50) 25 Bifenthrin() 231993 181 (100) 166(35) 182 (16) 26 Fenpropathrin() 241127 181 (100) 125(83) 265 (48) 27 Phenothrin() 241462 183 (81) 123(100) 81 (32) 241533 183 (68) 123(100) 81 (42) 28 Mirex( ) 251005 272 (100) 270(55) 274 (79) 28 10 Mirex( 10 ) 241994 277 (100) 275(60) 279 (76) 29 Lambda Cyhalothrin ( ) 251091 181 (100) 141(63) 197 (81) 30 cis Permethrin( ) 251988 183 (100) 163(20) 165 (18) 31 trans Permethrin ( 261155 183 (100) 163(28) 165 (27) )
292 CHINESE JOURNAL OF FOOD HYGIENE 2007 19 4 213,5 ml 1 2 5 10 20 50 l31, 5 l 10 mirex 5 l,28 0199,3 0198, SΠN = 3 (LOD), LOD 13 C 6 HCB,p, p 012gΠL,01002gΠL 2 DDD 6, 214, 10 2 5, 2 l40 l( LOD ( gπl) ( gπl) 2 ( n = 5) R ( n = 6) ( n = 6) ( gπl) ( %) ( gx RSD) ( gπl) ( %) ( gx RSD) 1 0102 01420 y = 277153 x + 1476199 019994 018 90 8. 2 16 92 6. 7 2 01006 01210 y = 799189 x + 5800103 019983 014 95 5. 1 8 92 4. 5 3 0102 01420 y = 188199 x + 4308146 019924 018 89 6. 6 16 94 6. 1 4 0102 01420 y = 233157 x 2254169 019989 018 90 5. 1 16 93 6. 0 5 0105 01420 y = 76115 x 262155 019994 018 103 7. 1 16 106 5. 8 6 0114 01840 y = 149115 x 6098119 019819 116 86 11. 3 32 86 10. 1 7 0120 01840 y = 80100 x + 1522115 019870 116 85 11. 9 32 90 10. 7 8 0106 01420 y = 148168 x 3272173 019946 018 105 9. 7 16 93 8. 6 9 0108 01420 y = 158136 x 4976103 019943 018 95 7. 3 16 104 5. 7 10 0105 01420 y = 141160 x 927179 019986 018 91 8. 2 16 93 7. 0 11 0109 01420 y = 38148 x + 1068170 019955 018 104 9. 6 16 101 6. 1 12 0108 01420 y = 22108 x 510102 019933 018 90 7. 4 16 88 7. 9 13 0105 01420 y = 334118 x 23200173 019905 018 93 6. 1 16 90 4. 2 14 01002 01110 y = 243165 x 2279185 019964 012 94 6. 5 4 102 4. 2 15 01002 01110 y = 296115 x 3074199 019911 012 104 8. 4 4 101 7. 3 16 01003 01110 y = 127179 x 1411159 019913 012 108 8. 8 4 105 6. 1 17 0101 01210 y = 81145 x 6462122 019975 014 88 11. 2 8 90 8. 0 18 0104 01420 y = 41175 x 876103 019916 018 91 9. 1 16 96 6. 1 19 0107 01420 y = 9189 x 281125 019877 018 86 11. 6 16 104 10. 1 20 0102 01210 y = 69191 x 792113 019935 014 92 7. 2 8 95 6. 1 21 0102 01210 y = 71172 x 2325173 019917 014 81 9. 4 8 92 7. 7 22 01003 01110 y = 77122 x 836103 019905 012 107 8. 7 4 103 6. 9 23 0104 01210 y = 27102 x 716154 019947 014 89 7. 3 8 95 5. 6 24 0109 01840 y = 84159 x 1361193 019920 116 90 10. 1 32 88 8. 2 25 0110 01840 y = 93182 x 520110 019903 116 86 7. 4 32 91 6. 2 26 0113 01840 y = 29146 x + 303141 019912 116 91 8. 5 32 89 7. 4 27 0111 01840 y = 83104 x + 245180 019962 116 94 7. 7 32 95 6. 6 28 01005 01110 y = 123110 x 800191 019914 012 104 5. 3 4 96 3. 4 29 0118 01840 y = 25103 x + 229111 019926 116 90 10. 2 32 86 8. 4 30 0110 01840 y = 102185 x + 431170 019932 116 88 9. 1 32 93 7. 6 31 0110 01840 y = 103194 x + 1040130 019943 116 90 8. 4 32 91 7. 1
HS SPME GC MS 293 2,2) 5 l ( 016gΠL),,, 2, 70 %120 % 3 31 HS SPME,,,,,,,,, [1 ]. [M]. :,2003 : 59262. [2 ]. [M]. :,2002 :212177. [3 ] APLADA2SARLIS P, LIAPIS K S, MILISDIS G E, et al. Study of procymidone and propargite residue levels resulting from application to greenhouse tomatoes[j ]. Environ Contam Toxicol,1994,52 :135. [4 ] GRETCH F M, ROSEN J D. Automated sample clean2up for pesticide multiresidue analysis[j ]. Assoc Off Anal Chem,1987,67 :7732775. [5 ],,,. [J ].,2004,22 (5) :5512554. [6 ],,,. 44 [J ].,2005,33 (2) :290. [7 ] JONG2KI HONG, HYE2YOUNG KIM, DO2GYUN KIM, et al. Rapid determination of chlorinated pesticides in fish by freezing2lipid filtration, solid2phase extraction and gas chromatography2mass spectrometry[j ].J Chromatogr A,2004,1038 :27235. [8 ] PAWLISZYN J. Sample preparation : Quo Vadis [ J ]. Anal Chem, 2003,75 :2543. [9 ] BELARDI R G, PAWLISZYN J. The application of chemically modified fused silica fibers in the extraction of organics from water matrix samples and their rapid transfer to capillary columns[j ]. Water Pollut Res J Can, 1989,24 :179. [10 ] TOMKINSA B A, BARNARD A R. Determination of organochlorine pesticides in ground water using solid2phase microextraction followed by dual2column gas chromatography with electron2capture detection [J ].J Chromatogr A, 2002,964 :21233. [11 ] NATALIA CAMPILLO, ROSA PENALVER, NEREA AGUINAGA, et al. Solid2phase microextraction and gas chromatography with atomic emission detection for multiresidue determination of pesticides in honey[j ]. Anal Chim Acta, 2006,562 :9215. [12 ],,,.. [:2007 03 08 ] :R15 ;TQ4501263 ;TS25211 :A :1004 8456 (2007) 04 0289 05 2007 (WHL) 5 17, 10 8,,,,,,, 2002,,;,20 % ; 1992 37 44,35 %,30 %, 2002,18 1818 %, 116,1991 31 %2002,2218 %,711 %, 2 6000,1992,39 %, 97 %, 1816 %,116