Analysis of Multiple Pesticide Residues in Raw Materials Used in Dietary Supplements by GC/ECD and NPD

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(1)KOREAN J. FOOD SCI. TECHNOL. Vol. 36, No. 6, pp. 863~871 (2004). ©The Korean Society of Food Science and Technology. GC/ECDf NPD¢ Ï ;8Ë® º öò %. 9ª º~³£ ª+ ;.'ÁJç+* z¶L ®'·. Analysis of Multiple Pesticide Residues in Raw Materials Used in Dietary Supplements by GC/ECD and NPD Sun-Young Park and Sangsuk Oh* Department of Food and Nutritional Sciences, Ewha Womans University Analyses of residual pesticides in raw materials used for dietary supplements were performed using multiingredients simultaneous analysis method. Pesticides such as BHC, chlorpyrifos, and quintozene were detected in 12 domestic and 7 imported samples, suggesting need for monitoring pesticides in domestic and imported raw materials and establishing residual limit of each pesticide. Key words: dietary supplements, pesticide, food raw material, GC-ECD, GC-NPD. *. . ~ n*Wö & V&ÁÏ~ V.¶òf ®öòB V &ÁÏ J;>Ú ®æ pf öòö & ¦Æ ¶ò º ~³£j ªC~¶ ~& .. *&~ f ·' ³ºæ" ® b z, .{, ÷, jò W÷~ B÷ ² Ã &ö V¢ '« W÷ .O" ;Fæ¢ Ï'b ;æ Ë' ® ²jWË væ ® . ¾ f z®Ú VËW ì¾ "'b ¦Ã>æê jî B®~ ãÖ ²j¶¢ *_* ¢' Ïÿ ¢ ~² b ãB' ¶º b ¦·Ïb b¢ ¢~º Òf& B ~ ® (2). 2002j ®~£®n*ÓöB~ ;VË ® ~ *Wª ÎîVçj * Ï Òëö V, RF~ ãÖ ÆÃ^, ÊÆÖf b¦Bê, &J&bº JÒ ~ ¦·Ï Ãçj ~& (3). ^B6 j Ö~ V * Onb " ^ê 'f b ÖÒ¾¢öBê &æzö V ;ö ² &Ò~V *~ “;VË®ö & »”j B;~&æò ®öòö & ¦·Ï~ Bö " Wªj « > ®º Úêº jç ; . ®n*j :ûb VËWj ;~º ;VË®» B ;>º 6öB ²j¶ b& B~ ®Ú ;VË® öòö & '' ¦Æ& jº ;æò, ;VË® öò~ º~³£~ n*W ¦Æ¢ * V& Ï ;B ® Ïö Bò J;>Ú ® . V¢B öBº ;VË®öòö &~ º~³£. Òò 5 O» ò òº â, sâ, rö, &J&b, , V C 16« 139®Ï(Table 1), ãÿ£_Ë(BÞ)" îÞ(¦Â), V ] 6 ¢ Û 2004j 2ú¦V 3ú Òö «~& . ò 7 >ò >âf 4Û2oC ïË &~ ÒÏ~&b, òº ËçöB 20Û4oC~ Nö &~ ÒÏ ªêV ªê~ ªC~& . ª+&ç ³£ Ò&çb F; ³£f C 36«b GC-ECDf GCNPD ªC &Ë ³£j J~ £~ º~³£ îÏV & J;>Ú ®º FV"²B(Table 2)f Úªjê Ëbî ³£b º;>º dieldrin, endosulfan-sulfate, heptachlor, malathion, methoxychlor, Ò ¦Ânê& ¸f ³£j " ~ F;~& . £ 5 8\ ³£~ &® 36«f Dr. Ehrenstorfer(99% purity, Germany) öB «~ ÒÏ ~&, ºÂÏ j^Ê 5 Ö(Wako pure Chemical Industries, Ltd., Japan)f º~ ³£Ïj ÒÏ~ & . $ "z¾Þ(Duksan pure chemical Co., Ltd., Korea) 5 Z>Ö¾Þ(Junsei Chemical Co., Ltd., Japan)f ß/. *Corresponding author: Sangsuk Oh, Department of Food and Nutritional Sciences, Ewha Womans University, Seoul 120-750, Korea Tel: 82-2-3277-3558 Fax: 82-2-3277-2862 E-mail: [email protected] 863.

(2) ®"²æ B 36 ² B 6 ^ (2004). 864. Table 1. List of raw materials of dietary supplements for pesticides analysis Samples. Scientific name. White ginseng Ginseng steamed red Ganoderma Coriolus versicolors Shiitake mushroom Aloe Acanthopanacis cortex Lycii fructuses Liriopis Tuber Atractylodis Rhizoma Alba Corni fructus Foxglove Mugwort Schizandrae fructuses Cnidii rhizoma Astagali radix. Panax schinseng Nees Panax ginseng Ganoderma lucidum Karst Coriolus versicolor Quel/Polystictus versicolor Fr. Lentinus edodes (Berk.) sing. Cortinellus edodes Aloe ferox Miller(Liliaceae) Acanthopanax senticosus. Lycium chinense Mill Ophiopogonis japonicus Ker-Gawler Atractylodes japonica Koidz. Cornus officinalis Sieb. et Zucc Rehmannia glutinosa var. Purpurea Artemisia princeps Schizandra chinensis Baillon = Schisandra chinensis Cnidium officinale Makino Astragalus membranaceus Bunge. Total. No. of samples 21 4 10 10 7 2 9 9 9 7 8 8 7 10 9 9 139. Table 2. Maximum residue limits in herbal medicines Pesticides BHC (α, β, γ, and δ-BHC) DDT (DDD and DDE) Aldrin Dieldrin Endrin. Maximum residue limits (ppb) 200 100 10. £j ÒÏ~& . ;BÏ florisil ÞÒæº 130oCöB 2* Wz Î ê VöB ê ÒÏ~& . 88 5 Ë~ GC-ECDº HP 5890 series II(Hewlett-packard 5890 series II, USA)¢ ÒÏ~&, GC-NPDº Agilent Technologies 6890 (Varian Technologies Ltd., USA)j ÒÏ~&b, GC-MSº Varian CP-3800 Gas Chromatograph with Varian Saturn 2000 GC/MS(Varian Technologies Ltd., USA)¢ ÒÏ~& . ö 5 Ï~ `* ''~ &®f j^Êö 1 mL 1,000 µg(1,000 ppm) j F~ê &öj ò , ¢ GC-ECD~ ªCÏ b&Ï group 1, 2f GC-NPD~ ªC &Ë b & Ï group 3b ~& . ¢ '' 1 mL 100 µg(100 ppm) b C~ 4Û2oC ïË & ~ & ÒÏ *ö &Ï j 1 mL 0.1-50 µg (0.1-50 ppm)b C~ ÒÏ~& . þÏ~ `* ®* 7~ Wª ÿ ªC»(7), P.A.M.(8) j ^ ~ ªC~& . ºÂ: òº '. V ^.~, ªêV¢ ÒÏ~ ª ê ê, ò £ 30 gj ~ 70% j^Ê 100 mL¢ I, 10ª* z Ú Df r ò¢ æ¢ Ï~ "z¾. Fig. 1. Scheme for sample extraction.. Þ 10-15 gj If 150 mL~ FÒ÷ö " ê 1ª* z. Ú Dº . Ï ºÂj 1* ÿn 4Û2oC ïË &~ ;~~ j^Ê" b [j ªÒÎ . ³»: çû(j^Ê) 20 mL¢ ~ 40oC ~~ >» ç öB 6{ ~ö Ï & ²ï Îj rræ ÃB ³» . 20% j^Ê F Ö 4 mL¢ IÚ ã~ º~bj j*® ..

(3) GC/ECDf NPD¢ Ï ;VË® "º öò 7 Wª º~³£ ªC. 865. Table 3. Operating conditions of GC-ECD GC-ECD operating conditions Column Detector Injector temp. Detector temp. Oven temp.. Injection vol. Carrier gas Mode. Ultra-2 (50 m lengthÜ0.32 mm I.D.Ü0.17 m film-thickness), SPB-608 (30 m lengthÜ0.25 mm I.D.Ü0.25 m film-thickness) Electron capture detector 270oC 300oC Initial temp.: 130oC, initial time: 2 min Level Rate (oC/min) Final temp. (oC) 1 10 185 2 10 215 3 10 300 1 µL N2 (1.2 mL/min) Split (50 : 1). Final time (min) 8 5 5. Table 4. Operating conditions of GC-NPD GC-NPD operating conditions Column Detector Injector temp. Detector temp. Oven temp.. Injection vol. Carrier gas Mode. Varian CP782124 24CB (30 m lengthÜ0.25 mm I.D.Ü0.25 m film-thickness), Varian CP 81L 5CB (30 m lengthÜ0.25 mm I.D.Ü0.25 m film-thickness) Nitrogen phosphorus detector 250oC 280oC Initial temp.: 140oC, initial time: 3 min Level Rate (oC/min) Final temp. (oC) 1 20 180 2 3 200 3 30 280 1 µL N2 (1.5 mL/min) Split (5 : 1). Final time (min) 2 2 5. Table 5. Operating conditions of GC-MS GC-MS operating conditions Column Transfer line Injector temp. Oven temp.. Injection vol. Carrier gas Mode Ionization mode Mass range Solvent delay time. CP-Sil 8 CB LOW BLEED/MS (10 m lengthÜ0.53 mm I.D.Ü0.25 m film-thickness) 220oC 280oC Initial temp.: 60oC, initial time: 1.5 min Level Rate (oC/min) Final temp. (oC) Final time (min) 1 18 280oC 1 1 µL He (1.2 mL/min) Split (10 : 1) Electron impact (EI+) m/z 70 - m/z 650 5 min. ;B: Ò florisil ÞÒæö Ö 5 mL¢ . 2-3OÞ ; ê~ ³ê FÂ~ ªÒ, ÞÒæö 20% j^ÊF Ö 5 mL¢ ?f O»b FÂ~ ªÖ . ê þÏ 2 mL¢ . 1-2OÞ ;ê~ ³ê ÏÂ* þ&ö Aº. . ÞÒæö Ï & <Ú®º çöB 20% j^Ê F Ö 5 mL¢ ÏÂ~ ÿ¢ þ&ö Îf ÏÂf 40 ~~ >» çöB 6{ ~ö Ï & ²ï Îj rræ ÃB ³»~, j^Ê 4 mL¢ &~ þÏb ~& (Fig. 1).. GC ª+` ;B þÏf Table 3, Table 4, 5 Table 5f ?f b ªC~& . ²>N þ ³£ ¦Â>æ pf ò( ^ÿ) £ 30 gö &ç³£ b &Ïj 1,000 ppb >&b B bj 5 mL Î&~ ÿ¢ ºÂ ;BO»b 3² > ¾Ò~ ªC~& ..

(4) ®"²æ B 36 ² B 6 ^ (2004). 866. Fig. 4. Chromatograms of 10 different pesticide standards (GCNPD).. Fig. 2. Chromatograms of 17 different pesticide standards (GCECD).. ÿªC &Ë~& . W B v

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(9) "öB Wª ~ ÏÒ>º BBf ^Zª *(retention time) ² >æ Wª ÿ;~ Öê¢ ¸¢ > ® (9). ³£~ ¦ï. 5 ¦Âê &bî~ ³ê¢ '' 100, 1000, 5000, 10000, 50000 ppb ~ ¦ïF(calibration curve)j ·W Ö" r~ ç&ê >(r2)f VV~ ¦Âê(instrument detection limit, IDL)º GCNPDf GC-ECD¢ ª~ V~& (Table 6). ECDöB~ ç&ê>º 0.9973-1.0000î, NPDöBº 0.9915-0.9999 ³êf VVf~ &êº ·^ Ö"¢ áîb, ¦Âêº ECD~ ãÖ 3-50 ppbî, NPDöBº 3-10 ppb ® *(7)öB ¾æÞ ³Öb º~³£ V&Ïf &Ú 5010,000 ppb º*æ ¦Â&Ëº* 6>î .. Fig. 3. Chromatograms of 9 different pesticide standards (GCECD).. Ûê¾Ò ¶ò~ ªCf SPSS Windows 11.0 *Îj Ï~ W ªN, ï, &ÞN¢ ~& . Î ªCòº 3² > G;~&b, ªCê7 ¶ B ò~ ªC 8f B~&, $ þöB ªC~& ïb¦V ² ½ÚÂ 8f V' ¦;j ~& .. Ö 5 V ³£~ chromatogram GC-ECDö ~ ªC &Ë group 1 &³£ tecnazene, α-BHC, β-BHC, quintozene, δ-BHC, heptachlor, aldrin, o,p'-DDE, p,p'-DDE, endrin, o,p'-DDT + p,p'-DDD, endosulfansulfate, p,p'-DDT, bifenox, cyhalothrin, deltamethrin" group 2 &³£ γ-BHC, chlorothalonil, α-endosulfan, dieldrin, o,p'DDD, bromopropylate, methoxychlor, tetradifon, fenarimolf ÿ ªC &Ë~&, GC-NPDö ~ ªC &Ë group 3 terbufos, disulfoton, dimethoate, chlorpyrifos-methyl, chlorpyrifos, malathion, methidathion, myclobutanil, ethion, EPN $. ³£~ ²>N ²>Nf 3² > ¾Ò~ ªC ï~ ¾æÚî. (Table 7). Ö" tecnazene" α-BHC, aldrin, bromopropylate & jv' Ô~æò, *Ú' ²>N º*º 72.1-100.3% ¾ æ¾ jv' ·^~& . ¦Â* ³£ Ú FÛ 7 ® öò 7 F; bW öò 16« 139 ®Ïö & ³£ º~ïj ECD ªC &Ë ³£ 26«, NPD ªC &Ë ³£ 10«ö &~ ªC~& (Table 8). ªCò 139®Ï 7 19®ÏöB ³£ ¦Â>î . â( â, >â, ªö, ³»)f 21®Ï 7 6®ÏöB ¦Â>î, ¦ ÂB ³£f chlorpyrifos, quintozene, BHC& . sâ~ ãÖ 4 ®Ï 7 1®Ï ¦Â>îb, ¦ÂB ³£f quintozene, BHC & . ÚæªUf 10®Ï 7 3®Ï ¦Â>îb, ¦ÂB ³ £f chlorpyrifos&, V¶º 9®Ï 7 3®Ïb, ¦ÂB ³ £f chlorpyrifosf α-endosulfanî . 7®Ï 7 1®Ï" J¶ 10®Ï 7 2®ÏöB ¦ÂB ³£f chlorpyrifos& . Â§f 9®Ï 7 3®ÏöB chlorpyrifos, aldrin, α-endosulfan, tecnazene ¦Â>î . ÚÖ öòf >« öò~ ¦Â ®Ï>¢ jv~, ÚÖ öò~ ãÖ 61®Ï 7 12®ÏöB ³£ ¦Â>îb, >« öò~ ãÖ 78®Ï 7 7®ÏöB ³£ ¦Â>î . ÚÖ öò~ ''~ ®Ïö & ¦Â ®Ï >¢ , â~ ãÖ.

(10) GC/ECDf NPD¢ Ï ;VË® "º öò 7 Wª º~³£ ªC. 867. Table 6. Correlation coefficients and IDL of pesticides Instruments. Groups. Correlation coefficients. IDL ppb. Ultra-2. SPB-608. Ultra-2. SPB-608. Group 1 (n = 17). Tecnazene α-BHC β-BHC, Quintozene δ-BHC Heptachlor Aldrin o,p'-DDE p,p'-DDE Endrin o,p'-DDT + p,p'-DDD Endosulfansulfate p,p'-DDT Bifenox Cyhalothrin Deltamethrin. 0.9996 0.9999 0.9973 0.9999 1.0000 0.9993 0.9999 0.9996 0.9996 0.9990 1.0000 0.9999 0.9990 0.9993 0.9995 1.0000. 0.9980 0.9997 0.9991 0.9998 0.9998 0.9993 0.9999 0.9977 0.9989 0.9999 0.9995, 0.9993 0.9991 0.9997 0.9986 0.9995 0.9999. 6 4 50 3 4 10 7 10 10 10 10 10 10 10 10 20. 6 6 10 6 10 10 7 10 10 10 10, 10 10 10 10 10 10. Group 2 (n = 9). γ-BHC Chlorothalonil α-endosulfan Dieldrin o,p'-DDD Bromopropylate Methoxychlor Tetradifon Fenarimol. 0.9999 0.9995 0.9998 0.9990 0.9998 0.9997 0.9994 0.9997 0.9996. 0.9999 0.9993 0.9992 0.9998 1.0000 0.9998 0.9996 0.9999 0.9998. 5 20 8 6 10 10 20 10 8. 6 20 10 10 10 10 20 10 8. Varian CP782124 24CB. Varian CP 81L 5CB. 0.9965 0.9966 0.9960 0.9998 0.9991 0.9999 0.9992 0.9999 0.9988 0.9997. 0.9956 0.9916 0.9950 0.9999 0.9961 0.9999 0.9919 0.9999 0.9947 0.9915. GC-ECD. GC-NPD. Pesticides. Group 3 (n = 10). Terbufos Disulfoton Dimethoate, Chlorpyrifos-methyl Chlorpyrifos Malathion Methidathion Myclobutanil Ethion EPN. 13®Ï 7 3®Ï, ÚæªUf 4®Ï 7 2®ÏöB ³£ ¦Â >î, V¶º 4®Ï 7 3®Ï, J¶º 5®Ï 7 2®Ï, Â§f 4®Ï 7 2®ÏöB ¦Â>î . >« öò ''~ ® Ïö & ¦Â ®Ï>¢ , âf 8®Ï 7 3®Ï, sâ f 4®Ï 7 1®Ï, ÚæªUf 6®Ï 7 1®Ï, f 5®Ï 7 1®Ï, Â§f 5®Ï 7 1®ÏöB ³£ ¦Â>î . Cho (10)f ÚÖ V¶öB chlorpyrifos& ¦Â>î, V¶ 4«öB chlorothalonil ¦Â>îb, ÚÖ Â§ 2«öBº pendimethalin ¦Â>î ~& . ß® £Ò ô ÒÏ>º V¶, Â§, Ò, _ 4«ö ÷7>Ú ®î ÚÏf öB V¶f Â§öB~ º~³£~ ¦ÂN ¸~~ ©" FÒ~& . $ ÚÖ öòf >« öò~ ''~ ®Ïö & ¦Â®Ï >f ¦ÂNj jv ~j r, >« £ 97®Ï 7 1®Ïò ³£ ¦Â>î. Varian CP782124 Varian CP 81L 24CB 5CB 9 7 9 8 10 7 7 7 8 9. 9 7 3 7 7 10 5 10 6 9. ÚÖ £öBº 154®Ï 7 8®ÏöB º~³£ ¦Â> Ú ÚÖ £öB º~³£ ¦ÂN ¸b, ÚæªU" â, sâ 5 ö & ¶òº jç ;ÚB b æ³' & jº~ . ¦Â ³£~ ï³ê 5 º* ÚÖ ®öò 7 º~³£~ ªCÖ" ¦ÂB ³£~ « ~º 3«b chlorpyrifos, α-endosulfan, aldrinî, >« ®öò 7 ¦ÂB ³£f 4«b quintozene, BHC, chlorpyrifos, tecnazeneb ¾æÒ (Table 9). ï ³ê º*º chlorpyrifos& 25-159 ppb&, α-endosulfanf 47-378 ppb, aldrinf 95 ppb, quintozenef 0.7-2 ppb, BHCº 0.9-189 ppb& . Ö"º ³£~ ·WöB " r, ÚÖ ®öòö B ¦ÂB º~³£~ «~º >« ®öòöB ¦ÂB º~.

(11) ®"²æ B 36 ² B 6 ^ (2004). 868. Table 7. Recovery rate and standard deviation of 36 pesticides Instruments. Groups. No.. Pesticides. Recovery rate, MeanÛS.D.(%), (n = 3). Group 1 (n = 17). 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17. Tecnazene α-BHC β-BHC Quintozene δ-BHC Heptachlor Aldrin o,p'-DDE p,p'-DDE Endrin o,p'-DDT p,p'-DDD Endosulfansulfate p,p'-DDT Bifenox Cyhalothrin Deltamethrin. 72.1Û1.5 85.2Û0.1 87.6Û1.9 79.0Û1.1 90.5Û2.1 89.8Û6.5 75.2Û3.7 95.3Û3.4 98.5Û2.5 99.8Û0.6 93.1Û1.5 90.1Û1.2 76.5Û2.0 100.3Û1.50 98.2Û5.2 90.5Û3.2 80.3Û2.5. Group 2 (n = 9). 18 19 20 21 22 23 24 25 26. γ-BHC Chlorothalonil α-endosulfan Dieldrin o,p'-DDD Bromopropylate Methoxychlor Tetradifon Fenarimol. 78.5Û1.2 77.9Û1.5 95.4Û1.5 95.9Û1.4 97.5Û4.2 72.3Û3.2 98.1Û0.5 95.2Û0.2 88.4Û4.2. Group 3 (n = 10). 27 28 29 30 31 32 33 34 35 36. Terbufos Disulfoton Dimethoate Chlorpyrifos-methyl Chlorpyrifos Malathion Methidathion Myclobutanil Ethion EPN. 82.3Û6.5 83.1Û0.3 93.0Û5.7 82.5Û1.4 85.7Û1.2 95.2Û1.1 80.2Û1.7 82.1Û6.2 93.9Û4.2 96.4Û1.2. GC-ECD. GC-NPD. ³£~ «~ 'rj r > ®î . ß® >« öò~ â (â, >â, ªö, ³»)öB ¦ÂB º~³£~ «~& · j r > ®îb, º " 7;¦öB ¶Ö â 5 ¢ öò âB®ö & ¶Ú¦ÒöB BHC& ¦Â> î ~º ;(16)f ¦ÂB ³£ ¢~~& . ³£ê ª* C 16« 139®Ï 7 ³£ê ª*j C 19®ÏöB ³£ ¦Â>îb, chlorpyrifos 13, BHC 3 5 αendosulfan 3, quintozene 2, aldrin, tecnazene '' 1 ¦Â>î (Fig. 5). f ?f Ö"º ¦' 6; Â #ã j²~ 7öB ¦Â>î~ chlorpyrifos~ nê& &Ë ¸ ² Ò>î ~º ÚÏ" FÒ~&(11), " 2003j B ¶ò(12)ö ~~ ³£º~V&j ." ³Öb~ 95% öB chlorpyrifos, procymidone, endosulfan ¢ ~º . ÚÏ"ê FÒ~& . chlorpyrifosº öB BBB "> ÏOBÏ FVê ÚÏB *Ò FVê ÚÏBº Ú ÏB Ë~ 1*¢ Næ~ ®º(13), FV "²ê ³£f æÏW Ö , z'b Ö n;>Ú ®Ú ~ã 7 öB ¾ ª >æ pº ßW r^ö 1970j& êö FV "²ê ÚÏB¢ &Ú~ ÒÏ~ ®Ú ÒÏnê& ¸f © b ÒòB . ¦Â* ³£ % chlorpyrifos~ chromatogram(GC-NPD) GC-NPDöB~ &³£ 10«j ¾æÞ ©b ò ªC * &³£~ chromatogramj áf Ö" ªÒ& ·^j r > ®î (Fig. 6). $ âj ªC~ áf chromatogramb &Ï~ ^Zª *(retention time) j ÛB jvª C Ö" âöB~ chlorpyrifosf ¢~~& (Fig. 7)..

(12) GC/ECDf NPD¢ Ï ;VË® "º öò 7 Wª º~³£ ªC. 869. Table 8. Number of detected samples in food raw materials tested Number of samples. Domestic. Imported. Samples. No. of Tested samples. No. of Detected samples. Detection rate (%). No. of Tested samples. No. of Detected samples. Detection rate (%). No. of Tested samples. No. of Detected samples. Detection rate (%). White ginseng Ginseng steamed red Ganoderma Coriolus versicolors, Shiitake mushroom Aloe Acanthopanacis cortex Lycii fructuses Liriopis Tuber Atractylodis RhizomaAlba Corni fructus Foxglove Mugwort Schizandrae fructuses Cnidii rhizoma Astagali radix. 21 4 10 10 7 2 9 9 9 7 8 8 7 10 9 9. 6 1 0 3 0 0 0 3 0 0 0 0 1 2 3 0. 28.6 25.0 0.0 30.0 0.0 0.0 0.0 33.3 0.0 0.0 0.0 0.0 14.3 20.0 33.3 0.0. 13 5 4 2 2 4 4 4 2 3 3 2 5 4 4. 3 0 2 0 0 0 3 0 0 0 0 0 2 2 0. 23.1 0.0 50.0 0.0 0.0 0.0 75.0 0.0 0.0 0.0 0.0 0.0 40.0 50.0 0.0. 8 4 5 6 5 5 5 5 5 5 5 5 5 5 5. 3 1 0 1 0 0 0 0 0 0 0 1 0 1 0. 37.5 25.0 0.0 16.7 0.0 0.0 0.0 0.0 0.0 0.0 0.0 20.0 0.0 20.0 0.0. Total. 139. 19. 13.7. 61. 12. 19.7. 78. 7. 9.0. Table 9. Pesticide residues detected in food raw materials Domestic Samples White ginseng. Detected pesticides. MeanÛS.D. (ppb), No. of No. of (n=3),(w/w) samples det.sa.. Detected pesticides. MeanÛS.D. (ppb), (n=3),(w/w). 13. 3. Chlorpyrifos. 62Û37. 8. 1 2. Quintozene BHC BHC. 2Û0 189Û5 11Û10. Ginseng steamed red. -. -. -. -. 4. 1 1. Quintozene BHC. 0.7Û1 0.9Û1. Ganoderma Coriolus versicolors Shiitake mushroom. 5 4 2. 0 2 0. Chlorpyrifos -. N.D.1) 53Û10 N.D.. 5 6 5. 0 1 0. Chlorpyrifos -. N.D. 32Û0 N.D.. Aloe. 2. 0. -. N.D.. -. -. -. -. Acanthopanacis cortex. 4. 0. -. N.D.. 5. 0. -. N.D.. Lycii fructuses. 4 5. 3 0 1. Chlorpyrifos α-Endosulfan. 40Û6 N.D. 47Û12. Liriopis tuber. 4. 0. -. N.D.. 5. 0. -. N.D.. Atractylodis rhizoma alba Corni fructus Foxglove Mugwort. 2 3 3 2. 0 0 0 0. -. N.D. N.D. N.D. N.D.. 5 5 5 5. 0 0 0 1. Chlorpyrifos. N.D. N.D. N.D. 25Û3. Schizandrae fructuses. 5. 2. Chlorpyrifos. 35Û1. 5. 0. -. N.D.. Cnidii rhizoma. 4. 1 1 2. Chlorpyrifos Aldrin α-Endosulfan. 159Û2 95Û54 378Û71. 5. 1. Tecnazene. 31Û11. Astagali radix. 4. 0. -. N.D.. 5. 0. -. N.D.. 61. 12. 78. 7. Total 1). No. of No. of samples det. sa.. Imported. N.D.: Not detected..

(13) ®"²æ B 36 ² B 6 ^ (2004). 870. Fig. 5. The number of pesticide residues detected in food raw material tested.. Fig. 8. Mass spectrum of chlorpyrifos standard. A: Chlorpyrifos in standard solution, B: Chlorpyrifos in NIST library.. Fig. 6. GC chromatograms of 10 different of pesticide standards (GC-NPD).. Fig. 7. GC chromatograms of chlorpyrifos detected from white ginseng (GC-NPD).. ¦Â* ³£ % chlorpyrifos~ chromatogram(GC-MS) GC-NPDöB ^Zª*(retention time)j ÛB ªC V òº GC-MS {~& . Chlorpyrifos~ &Ï" library öB~ ÆïN ~ ;ê¢ { ê m/z 314, m/z 258, m/z 197, m/z 97~ ÆïNj F~&(Fig. 8), &Ï" chlorpyrifos& ¦Â >îj ©b Òò>º ò¢ ªC Ö " &Ï" ?f m/z 314, m/z 258, m/z 197, m/z 97~ Æ ïNj {~ chlorpyrifos ¦ÂFZ¢ { > ®î. (Fig. 9).. º. £. º ;®S ê ¦·Ï B *" ;VË ® "öò 5 Ö 5 Â~, Ú Ö 5 >«j :ûb. Fig. 9. Mass spectrum of chlorpyrifos detected from white ginseng. A, C: Chlorpyrifos in standard solution; B, D: Chlorpyrifos in white ginseng.. öò¢ F;~ *þ»(2002)ö ~~ GC-ECDf GCNPD ªC &Ë ³£(36«)ö &~ ªC ê GC-MS {~ ªC~& . 16« 139®Ïö &~ ªC Ö" 19®ÏöB ³£ ¦ Â>îb, ÚÖ öòf >« öò~ ¦Â *f, ÚÖ öò~ ãÖ 61®Ï 7 12®Ï ¦Â>î, >« öò~ ã Ö 78®Ï 7 7®Ï ¦Â>î . ÚÖ öò â~ ãÖ 13®Ï 7 3®Ï ¦Â>î, ÚæªUf 4®Ï 7 2®Ï, V¶º 4®Ï 7 3®Ï, J¶º 5®Ï 7 2®Ï, Â§ 4®Ï 7 2®Ï ¦Â>î . >« öò~ ãÖ âf 8®Ï 7 3 ®Ï ¦Â>îb, sâf 4®Ï 7 1®Ï, ÚæªU 6®Ï 7 1®Ï, f 5®Ï 7 1®Ï, Â§ 5®Ï 7 1®Ï ¦Â >î . ³£ê ª*j C 16« 139®Ïö &~ ® ¦Âf 120îb, chlorpyrifosº 13b &Ë ¸² ¾æ Ò . º ;B ò¢ ªC ©¾, ;VË®.

(14) GC/ECDf NPD¢ Ï ;VË® "º öò 7 Wª º~³£ ªC. ö ÒÏ>º öò~ º~³£ Ò{f æ³' ÎîVç ~ jºWj " ® . $ ;VË®Ë WË^ ¢ ®º º^ö ;VË® S ê ¦·Ï B ~& º öòö & *ªCj ~º ®ÚB~ V. ¶ò f ÚöB V&ÁÏ J;>Ú ®æ pf ® öòö & V&ÁÏ~ ¦Æ ¶ò Ï &ËW V&B .. 6Ò~ *W Bö b. º ~òVFBB Òë~ ;VË ®~ n ï& VFBB 5 *þ öòö & 'Ï " ~~ >¯>îb, ãæO®~£®n*Ó~ êæ ê¯>îÛî . ö p 6Òãî .. ^. ò. 1. Kim HK. Current status and prospect of nutraceuticals. Food. Ind. Nutr. 9: 1-14 (2004) 2. Shim CK. Implementation and policy direction of the Korean health functional food law and its regulations. Food. Sci. Ind. 37: 37-40 (2004) 3. KFDA. Monitoring the harmful ingredients of functional health foods-case surveys and consumer surveys on side-effects of functional health foods. Korea Food and Drug Administration, Seoul, Korea. pp.1-134 (2002) 4. Kim DB. Regulation for health supplements standard. Food. Sci. Ind. 37: 50-54 (2004) 5. Bahk GJ, Kim YC, Lee HS, Rho MJ, Cho YH, Lee YH, Lee KM, Roh WS, Yang JH, Kim JS and Lee SP. A study on attitudes toward food safety issues in Korea-Focus on the public official related to food hygiene-. J. Food Hyg. Safety 14: 34-44 (1999). 871. 6. Korea Food and Drug Administration. The unsuitable present condition of each item in Korea in 2003. Available from: http:// gyeongin.kfda.go.kr. Accessed Feb. 3, 2004. 7. KFDA. Korean Food Code. Korea Food and Drug Administration, Seoul, Korea (2002) 8. FDA. Pesticide analytical manual(PAM). Available from: http:// www.cfsan.fda.gov/~frf/pami3.html. Accessed Feb. 3, 2004. 9. Kim GR. Gas Chromatographic, 1st ed. Free Academy, Seoul, Korea. pp. 179-181 (2000) 10. Cho HJ, Hwang IS, Choi BH, Bae CH, Kim MH. Determination of residual pesticides in crude drugs-Gas chromatographic analysis of 18 pesticides-. Korean J. Pharmacogn. 32: 200-211 (2001) 11. Hur SJ, Lee HS, Lee KU, Kwon O, Im MH, Jeong JS, Hong KH, Na HK, Choi YH, Kim KS, Lee HJ, Choi JD, Sung JH, Choi JH, Hong MK, Kim WS, Lee DH, Kim HS, Lee HJ, Ryu MK, Moon BW, Chang JS. A study for improvement of rapid bioassay of pesticide residues. Ann. Rep. KFDA 4: 99-110 (2000) 12. KFDA. Detection of pesticide residues of use prohibition from agricultural products. Available from: http://www.kfda.go.kr. Accessed Feb. 15, 2004. 13. Pesticides Lab. Dong-A University. Structure and classification of organophosphorus insecticides. Available from: http://pesticides.donga.ac.kr/data/data/organ.htm. Accessed Mar. 10, 2004. 14. Food Safety Dictionary Compilation Commission. Food Safety Dictionary. 1st ed. Korea Dictionary Research Publishing, Seoul, Korea. pp. 126-146 (1997). 15. IPCS INCHEM. Inventory of IPCS and other WHO pesticide evaluations and summary of toxicological evaluations performed by the Joint Meeting on Pesticide Residues (JMPR) evaluations through 2002. Available from: http://www.inchem.org/pages/ jmpr.html. Accessed Jul. 10, 2004. 16. Gyeongin KFDA. A strict inspection of chinese white ginseng. Available from: http://gyeongin.kfda.go.kr. Accessed Feb. 20, 2004. (2004j 9ú 14¢ %>; 2004j 11ú 30¢ j).

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