Distribution of hazardous heavy metals in commercial herbal medicines classified by plant parts used in seoul

Transcription

1 Printed in the Republic of Korea "/":5*$" 4$*&/$& 5&$)/00(: Vol. 22, No. 6, , 2009 mw w s ½ ³Á½ Áw Áw yá½ Á xáy Á Á½ Á G y, 1 w w w Distribution of hazardous heavy metals in commercial herbal medicines classified by plant parts used in seoul Donggyu Kim, Bogsoon Kim, Eunjung Han, Changho Han, Oukhee Kim, Byunghyun Choi, Insook Hwang, Youngzoo Chae, Minyoung Kim and Seungkook Park X,G Seoul Metropolitan Government Research Institute of Public Health and Environment, QuaCheonSi S Korea 1 Institute of Life Science and Resources, Kyung Hee University, YonginSi S Korea (Received September 29, 2009; Accepted October 27, 2009) : mw w w w sƒ w. s 244t 3152 ICPMS» w. û w (mg kg ) w (0.92)ƒ w (0.43) 1. ù w (0.26) (0.18) ƒ š, e w (0.13)ƒ (0.08). mw e» w ƒ w w. (0.009) w (0.008) ƒ ù,» w (ttest, p<0.05)., û,, w ƒ w ù, e ƒ (ttest, p<0.05). û,, e, û (r=0.386) ù, ƒ (p<0.01). w(mg kg ) 1 (0.422), (0.475)ƒ š, (0.825),» (0.828), (0.861)ƒ š, (1.154), tv(1.634),»(2.238), (6.241) w (ANOVAtest, p<0.05). Abstract: In this study, the safety of commercial herbal medicines was evaluated by determining concentration of hazardous heavy metals. 3,152 samples (244 types) purchased by individual packing unit from market in Seoul, were analyzed using ICPMS and mercury analyzer. As a result, the content (mg kg 1 ) of Pb was higher in the aboveground part (0.92) than underground part (0.43). But in case of As and Cd contents, there is slightly higher in the undergroundparts (0.26, 0.13) than the aboveground parts (0.18, 0.08). There were many herbal medicines exceeding regulatory limits of Cd comparing with other metals. The levels of Hg seemed to be different between aboveground part(0.009) and underground part (0.008) but there was no sample exceeding tolerance limits. In the comparison of imported samples with domestic herbal medicines, it was shown that Pb, As, and Hg were measured highly in the imported ones, Cd was not significantly different (ttest, p<0.05). Corresponding author Phone : +82(0) Fax : +82(0) skpark@khu.ac.kr 504

2 mw w s 505 The significant correlation was observed between Pb and As (r=0.386, p<0.01) but there was no difference in other parts. The heavy metal contamination of herbal medicines measured in total amount of respective heavy metals (mg kg 1 ) was high in Flos (6.241) and Caulis (2.238), and decreased in the order of Cortex (1.634), Herba (1.154), Perithecium (0.861), Rhizoma (0.828), Radix (0.825), Fructus (0.475), and was low in Semen (0.422) (ANOVAtest, p<0.05). Key words: heavy metals, herbal medicines, ICPMS t w ƒ š, w, q, w w,, yy q w w. s» w w j ù w, w w w m w» ( w» ) t m, wy, y mw. 13 w w w ƒ ù., m m» w ù ù, m w š j,,, û, vwƒ k vw e,. w m ph, p. y ƒ y w, w t œ e yw y,, ƒœ, t ƒ m y w. 47 x» 100 ppm w( z : ' ) 30 ppm w( : ' ). ù x t y w w x, yyùp w ùkü y w û ppm ùkü, y w e ¼ w. 8 w Cu, Zn, Fe e g w sw ƒ. w sƒ w š š9,10, Õ x» x Ö( t t š y) w, w. w, w w w l, 1113 w z, w k 14 w w y 15,16 ù, w ƒœ/ w t l, z q w ƒ w š. š mw t ƒ m y ù, m l w, p t t š w û 5, 3, e 0.3, 0.2 mg kg w» wš 1. y, w ƒ y t ƒ, w û,, e, s / w w w. š w w»» œwš w. x w m s w w. e z q w w ƒ xk,, z,,, z ƒ w. x w 17 Vol. 22, No. 6, 2009

3 506 ½ ³Á½ Áw Áw yá½ Á xáy Á Á½ Á Table 1. Classification of herbal medicines used in this experiments Parts used n 1) Latin name (korean name) Cortex 299 Acanthopanacis Cortex( ƒv), Cinnamomi Cortex ( ), Eucommiae Cortex ( ), Kalopanacis Cortex (w v), Magnoliae Cortex (z ), Mori Cortex ( v), Moutan Cortex ( v), Phellodendri Cortex (y ), Ulmi Cortex ( v) Flos 77 Carthami Flos (yy), Chrysanthemi Flos ( ), Lonicerae Flos ( y), Schizonepetae Spika (x ) Fructus 520 Amomi Fructus Rotundus ( ), Amomi Fructus ( ), Armeniacae Semen (w ), Aurantii Fructus Immaturus ( ƒ), Chaenomelis Fructus ( ), Citri Unshius Pericarpium ( v), Citrii Unshius Pericarpium Immaturus ( v), Corni Fructus ( ), Crataegi Fructus ( ), Forsythiae Fructus ( ), Gardeniae Fructus (e ), Hordei Fructus Germinatus ( ), Longan Arillus ( ), Lycii Fructus (» ), Ponciri Fructus Immaturus ( ), Rubi Fructus ( ), Schisandrae Fructus ( ), Zizyphi Fructus ( ) Herba 181 Agastachis Herba ( w), Artemisiae Capillaris Herba ( y), Ephedrae Herba ( y), Leonuri Herba ( ), Menthae Herba ( w), Perillae Folium ( ), Pogostemonis Herba (Ÿ w), Taraxaci Herba (sœ ) Perithecium 102 Polyporus ( ), Poria Sclerotium ( ) Semen 265 Arecae Semen ( ), Carthami Tinctorii Seed, Fructus (yy ), Cassiae Semen ( ), Castaneae Semen ( ), Coicis Semen ( ), Cuscutae Semen (m ), Massa Medicata Fermentata ( š), Nelumbinis Semen ( ), Persicae Semen ( ), Plantaginis Semen ( ), Psoraleae Semen ( ), Raphani Semen (ü ), Thujae Semen ( ), Trichosanthis Semen ( ), Zizyphi Semen ( ) Caulis 95 Akebia Caulis ( m), Cinnamomi Ramulus ( ), Lonicerae Folium et Caulis ( ) Radix 1028 Rhizoma 585 Total 3152 Achyranthis Radix ( ), Aconiti Lateralis Radix Preparata ( ) Adenophorae Radix ( ), Angelicae Dahuricae Radix ( ), Angelicae Decursivae Radix ( y), Angelicae Gigantis Radix ( ), Angelicae Tenuissimae Radix (š ), Araliae Continentalis Radix ( y), Astragali Radix (y»), Aucklandiae Radix ( w), Bupleuri Radix ( y), Clematidis Radix ( ), Codonopsis Pilosulae Radix ( ), Cynanchi Wilfordii Radix ( ), Dipsaci Radix ( ), Glehniae Radix (w t), Glycyrrhizae Radix et Rhizoma ( ), Osterici Radix ( y), Paeoniae Radix ( ), Peucedani Radix ( t), Platycodonis Radix (¼ ), Polygalae Radix ( ), Puerariae Radix ( ), Rehmanniae Radix Preparata ( y), Rhei Radix et Rhizoma ( y), Salviae Miltiorrhizae Radix ( ), Saposhnikoviae Radix ( t), Scrophulariae Radix (x ), Scutellariae Radix (y ), Trichosanthis Radix ( ) Acori Gramineri Rhizoma ( s), Alismatis Rhizoma (k ), Anemarrhenae Rhizoma ( ), Arisaematis Rhizoma ( û ), Asparagi Tuber ( ), Atractylodis Rhizoma Alba ( ), Atractylodis Rhizoma ( ), Cimicifugae Rhizoma ( ), Cnidii Rhizoma ( ª), Coptidis Rhizoma (y ), Corydalis Tuber (xy ), Curcumae Longae Rhizoma ( y), Cyperi Rhizoma (w ), Dioscoreae Rhizoma ( ), Fritillariae Thunbergii Bulbus ( q ), Liriopis Tuber( ), Pinelliae Tuber ( w), Rhei Undulatai Rhizoma ( y), Sparganii Rhizoma ( ), Zingiberis Rhizoma ( ) 1) Numbers of samples. t œ e w w18 w Table 1, Table 2 w. tv(9t 299 ), (4t 77 ), (18t 520 ), (8t 181 ), (2t 102 ), (15t 265 ),» (3t 95 ) š, w (30t 1028 ),» (20t 585 ) 9 244t s š, w»(da280 Gold.A, Daesung ARTLON Co., Korea) z 50y(300 µm) k»» š, þ w x w. û e û,, e w Microwave Digestion System (MARS 5 Version 194A01, CEM, North Carolina, USA) w. x j w» 0.5 g w š (70%, Electronic grade, Dong Woo Fine Chem., Seoul, Korea) 12 ml ƒw z Analytical Science & Technology

4 mw w s 507 Table 2. Herbal medicines classified by its country of origin Country n 1) Latin name South Korea 1663 Acanthopanacis Cortex, Achyranthis Radix, Aconiti Lateralis Radix Preparata, Acori Gramineri Rhizoma, Adenophorae Radix, Agastachis Herba, Akebia Caulis, Alismatis Rhizoma, Anemarrhenae Rhizoma, Angelicae Dahuricae Radix, Angelicae Decursivae Radix, Angelicae Gigantis Radix, Angelicae Tenuissimae Radix, Araliae Continentalis Radix, Arisaematis Rhizoma, Artemisiae Capillaris Herba, Astragali Radix, Atractylodis Rhizoma Alba, Atractylodis Rhizoma, Bupleuri Radix, Carthami Tinctorii Seed, Fructus, Cassiae Semen, Castaneae Semen, Chaenomelis Fructus, Chrysanthemi Flos, Citri Unshius Pericarpium, Citrii Unshius Pericarpium Immaturus, Cnidii Rhizoma, Coicis Semen, Corni Fructus, Corydalis Tuber, Crataegi Fructus, Curcumae Longae Rhizoma, Cynanchi Wilfordii Radix, Cyperi Rhizoma, Dioscoreae Rhizoma, Dipsaci Radix, Eucommiae Cortex, Forsythiae Fructus, Fritillariae Thunbergii Bulbus, Gardeniae Fructus, Hordei Fructus Germinatus, Kalopanacis Cortex, Leonuri Herba, Liriopis Tuber, Lonicerae Flos, Lonicerae Folium et Caulis, Lycii Fructus, Magnoliae Cortex, Massa Medicata Fermentata, Menthae Herba, Mori Cortex, Moutan Cortex, Osterici Radix, Paeoniae Radix, Perillae Folium, Peucedani Radix, Phellodendri Cortex, Pinelliae Tuber, Plantaginis Semen, Platycodonis Radix, Pogostemonis Herba, Polyporus, Ponciri Fructus Immaturus, Poria Sclerotium Poria Sclerotium, Puerariae Radix, Raphani Semen, Rehmanniae Radix Preparata, Rhei Radix et Rhizoma, Rubi Fructus, Saposhnikoviae Radix, Schisandrae Fructus, Schizonepetae Spika, Scrophulariae Radix, Scutellariae Radix, Taraxaci Herba, Trichosanthis Radix, Trichosanthis Semen, Ulmi Cortex, zingiberis Rhizoma, Zizyphi Fructus China 1276 Acanthopanacis Cortex, Achyranthis Radix, Aconiti Lateralis Radix Preparata, Acori Gramineri Rhizoma, Adenophorae Radix, Amomi Fructus Rotundus, Amomi Fructus, Anemarrhenae Rhizoma, Angelicae Dahuricae Radix, Angelicae Decursivae Radix, Arecae Semen, Arisaematis Rhizoma, Armeniacae Semen, Asparagi Tuber, Astragali Radix, Atractylodis Rhizoma Alba, Atractylodis Rhizoma, Aucklandiae Radix, Aurantii Fructus Immaturus, Bupleuri Radix, Carthami Flos, Carthami Tinctorii Seed, Fructus, Cassiae Semen, Chrysanthemi Flos, Cimicifugae Rhizoma, Cinnamomi Cortex, Cinnamomi Ramulus, Citri Unshius Pericarpium, Citrii Unshius Pericarpium Immaturus, Clematidis Radix, Codonopsis Pilosulae Radix, Coptidis Rhizoma, Corydalis Tuber, Crataegi Fructus, Curcumae Longae Rhizoma, Cuscutae Semen, Cynanchi Wilfordii Radix, Cyperi Rhizoma, Dioscoreae Rhizoma, Dipsaci Radix, Ephedrae Herba, Eucommiae Cortex, Forsythiae Fructus, Fritillariae Thunbergii Bulbus, Gardeniae Fructus, Glehniae Radix, Glycyrrhizae Radix et Rhizoma, Kalopanacis Cortex, Liriopis Tuber, Longan Arillus, Lonicerae Flos, Lonicerae Folium et Caulis, Magnoliae Cortex, Menthae Herba, Mori Cortex, Moutan Cortex, Nelumbinis Semen, Osterici Radix, Paeoniae Radix, Perillae Folium, Persicae Semen, Peucedani Radix, Phellodendri Cortex, Pinelliae Tuber, Plantaginis Semen, Platycodonis Radix, Pogostemonis Herba, Polygalae Radix, Polyporus, Ponciri Fructus Immaturus, Poria Sclerotium, Psoraleae Semen, Puerariae Radix, Raphani Semen, Rehmanniae Radix Preparata, Rhei Radix et Rhizoma, Rhei Undulatai Rhizoma, Rubi Fructus, Salviae Miltiorrhizae Radix, Saposhnikoviae Radix, Schisandrae Fructus, Schizonepetae Spika, Scrophulariae Radix, Scutellariae Radix, Sparganii Rhizoma, Taraxaci Herba, Thujae Semen, Trichosanthis Radix, Trichosanthis Semen, Ulmi Cortex, zingiberis Rhizoma, Zizyphi Semen Vietnam 73 Amomi Fructus, Cinnamomi Cortex, Cinnamomi Ramulus, Longan Arillus, Nelumbinis Semen Indonesia 43 Agastachis Herba, Amomi Fructus Rotundus, Arecae Semen, Cinnamomi Cortex, Persicae Semen, Pogostemonis Herba Myanmar 24 Amomi Fructus, Curcumae Longae Rhizoma, Psoraleae Semen, Zizyphi Semen North Korea 21 Atractylodis Rhizoma Alba, Atractylodis Rhizoma, Lonicerae Flos, Lycii Fructus, Phellodendri Cortex, Pinelliae Tuber, Poria Sclerotium, Rubi Fructus South Africa 19 Persicae Semen U.S.A. 18 Massa Medicata Fermentata Guatemala 7 Amomi Fructus Rotundus Tailand 5 Longan Arillus Laos 3 Amomi Fructus 1) Numbers of samples. Vol. 22, No. 6, 2009

5 508 ½ ³Á½ Áw Áw yá½ Á xáy Á Á½ Á Hood ew w z,» swš 600 W(y 1200 W:»ƒ 30 ) Power C¾ k z 5 o wš, C¾ k z 5 o wš C¾ k z 5 o w ww. ¾ þ, k»wš» y (EPS, Electronic grade, Dong Woo Fine Chem., Seoul, Korea) 1 ml ƒw k k z ƒw 50 g wš z x w. Inductively coupled plasmamass spectrometer (Agilent 7500ce, Agilent, Tokyo, Japan) w w,»» Table 3.»» w t (ICPMS 10 µg ml 1, Agilent, USA) 5% 0.5, 1.0, 2.0, 5.0, 10, 20, µg kg t 1 w w š, œ x w w w. {»ƒ Mercury analyzer (Model MA2, Nippon Instruments Co., Japan) w. 50 mg š ƒ ww»y g œ t gqw s» s, w d w ƒ»y Table 3. Operating conditions for ICPMS Parameter Operating condition R.F. power 1500 W Argon gas flow rate Plasma 15.0 L/min Auxiliary 0.27 L/min Carrier 0.85 L/min He gas flow rate 3.0 ml/min Interface cones Platinum Acquisition parameters Points/mass 3 Intergration time/mass 0.1 sec Total acquisition time/replicate 7.28 Replicates 3 Total acquisition time/sample sec Pb/Mass 208 As/Mass 75 Cd/Mass 112 (CombustionGold Amalgamation Method) nm w. t 1000 mg kg 1 (Kanto Chemical Co., Japan) 0.001% l 2.0, 5.0, µg kg 1 w t w. HGMHT, HGBHT (Nippon Instruments Co., Japan) w. t t š wwš, 1922 x» w ³ ISO/IEC w» (KOLAS, Korea Laboratory Accreditation Scheme) û,, e x, t, x w œ x» z w š, k w t x (SOP, Standard Operation Procedure) xw. 23» w matrix ü w» w w. ICPMS ù w, ƒ w j». p 75 w 40 Ar 35 Cl ƒ š + k. w w š z» w ORS (Octopole Reaction System) 8 x w w w w w. +ƒ Agilent ORS x Ar 35 Cl +, As ù x 40 Ar 35 Cl + polyatomic w Ar 35 Cl ù, 40 Ar 35 Cl + polyatomic x w š» ƒ w + 40 Ar 35 Cl w š š w. x ORSƒ 24,25 ICPMS w.», š x l y w w w, w q w» w ƒw š w e œ x w š, ƒ z œ x w Analytical Science & Technology

6 mw w s 509 w. š ICPMS w w»» k w» w t x (SOP)» t (10, 100 µg kg 1 ) y w. z d z x» k t ƒw. (Paeoniae Radix) 0.5 g û 1.0, 10.0 mg kg 1, 1.0, 5.0, e 0.1, 1.0 š 0.01, 0.1 ƒw z w xw d w. w z w» w w wš t (Certified Reference material: CRM) w w d 3z xw. kw t» w t (NIST, National Institute of Standards & Technology) NIST w (LOD, Limit of detection) w (LOQ, Limit of quantitation) t r»» w t 3z d w s³ y w w. LOD = 3.3 σ/s LOQ = 10 σ/s σ t r (the mean standard deviation) S»»(the individual slope). m m SPSS package (version 12.0KO) w s³, t r, w., t ttest, ANOVAtest w z Duncan's multiple range test(p<0.05) w. š x ICPMS» w û,, e, w 0.089, 0.011, 0.020, µg kg 1 š, 1 w 0.272, 0.034, 0.062, µg kg š» {. û,, e µg kg (r=0.9997) š, µg kg r= z t ƒw d w, û %, %, e % š %, ƒw ƒ z ùkü (Table 4). w z w» w w wš t (CRM:NIST 1547) w w d 3z d w, t s³ z û 90.8, 100.5, e 97.3 š 96.1% (Table 5). w w Table 6, w Table 7 ùk Table 4. Recovery rate of spiked metals in Paeoniae Radix Elements Pb As Cd Hg Addition (mg kg 1 ) Recovery 1)# (%) C.V.2) (%) LOD 3) (ug kg 1 ) LOQ 4) (ug kg 1 ) ) Mean values obtained from three measurements using a closed vessel microwave digestion. except mercury by combustiongold amalgamation method 2) Coefficient of variance 3) 3.3 σ/s 4) 10 σ/s (σ: the mean standard deviation, S : the individual slope) Vol. 22, No. 6, 2009

7 510 ½ ³Á½ Áw Áw yá½ Á xáy Á Á½ Á Table 5. Heavy metals contents in CRM Elements 1) Certified Measured Recovery (%) C.V. 3) (%) Mean± SD (mg kg 1 ) 2) Mean±SD (mg kg 1 ) Pb 0.870± ± As 0.060± ± Cd 0.026± ± Hg 0.031± ± ) The CRM's of Pb, As, Cd and Hg was Peach leaves (NIST 1547) 2) Mean values obtained from three measurements using a closed vessel microwave digestion. except mercury by combustiongold amalgamation method 3) Coefficient of variation Table 6. Heavy metal contents 1) in herbal medicines classified by parts used Group Above ground parts Underground parts Pb As Cd Hg Total n 2) mg kg 1 n mg kg 1 n mg kg 1 mg kg 1 N 3) mg kg Total ±3.59 (ND~87.2) 0.43±0.87 (ND~16.7) 0.67±2.59 (ND~87.2) ±0.68 (ND~20.0) 0.26±0.35 (ND~2.44) 0.22±0.54 (ND~20.0) ±0.13 (ND~1.94) 0.13±0.15 (ND~1.78) 0.11±0.14 (ND~1.94) 0.009±0.012 (ND~0.144) 0.008±0.011 (ND~0.130) 0.009±0.011 (ND~0.144) 92/ ±3.945 (ND~91.83) 94/ ±1.097 (ND~17.53) 186/ ±2.872 (ND~91.83) Cortex ±2.61 b (ND~19.6) 0.18±0.25 ac (ND~2.41) ±0.10 c (ND~0.65) 0.011±0.010 cd (ND~0.068) 18/ ±2.746c (ND~21.64) Flos ±14.0 c (0.01~87.2) ±1.61 d (0.02~11.9) ±0.08 c (ND~0.51) 0.022±0.024 f (0.001~0.144) 14/ ±15.180e (0.09~91.83) Fructus ±0.76 a (ND~10.5) 0.09±0.15 a (ND~2.08) 0.04±0.05 a (ND~0.29) 0.006±0.009 ab (ND~0.12) 1/ ±0.852a (ND~11.70) Herba ±1.04 a (ND~6.62) ±0.45 c (0.01~4.00) ±0.15 c (ND~0.94) 0.015±0.008 e (0.001~0.057) 18/ ±1.273bc (0.05~6.97) Perithecium 0.64±0.98 a (0.01~4.20) 0.11±0.17 ab (ND~0.79) ±0.23 c (ND~1.49) 0.010±0.014 c (0.001~0.132) 10/ ±1.116ab (0.04~5.34) Semen 0.19±0.44 a (ND~4.93) ±1.23 ac (ND~20.0) ±0.08 b (ND~0.44) 0.004±0.007 a (ND~0.048) 5/ ±1.377a (ND~21.20) Caulis ±1.74 b (ND~8.11) 0.24±0.27 bc (0.01~2.07) ±0.26 d (ND~1.94) 0.013±0.009 de (ND~0.042) 26/ ±1.855d (0.03~8.82) Radix ±0.89 a (ND~16.7) 0.27±0.37 c (ND~2.44) ±0.11 c (ND~1.04) 0.008±0.011 b (ND~0.130) 29/ ±1.117ab (ND~17.53) Rhizoma ±0.83 a (ND~12.8) 0.23±0.31 bc (ND~2.44) ±0.19 d (ND~1.78) 0.008±0.010 b (ND~0.090) 65/ ±1.063ab (0.08~15.98) 1) MeanÛstandard deviation. The same letters (ac) in the same column are not significantly different at p<0.05. Numbers in parenthesis are range. Not Detected (ß0.001). 2) Number of sample exceeded heavy metal standard 3) Number of sample exceeded its criteria/total number of sample analyzed, Herbal standard criterion announced by KFDA (Not more thanpb:5, As:3, Cd:0.3, Hg:0.2 mg kg 1 ) 4) pvalue indicates significant differences of individual heavy metal contents between aboveground part and underground part of herbs (ttest, <0.05). ü. û w (mg kg ) ,» 1.80, tv 1.35, 0.77, 0.64, 0.34, 0.19 š s³ 0.92 š, w 0.43,» 0.42 š s³ 0.43.,», tv ƒ û Analytical Science & Technology

8 mw w s 511 Table 7. Comparison of heavy metal contents 1) Group Above ground parts Underground parts Korea (unit:mg kg 1 ) China (others) (unit:mg kg 1 ) n 2) Pb As Cd Hg n Pb As Cd Hg 24/ ± ± ± ±0.007 (ND~4.32) (ND~4.00) (ND~1.94) (ND~0.065) 45/ ±0.64 (ND~12.8) 0.25± ± ±0.011 (ND~2.44) (ND~1.78) (ND~0.126) Total 69/ ± ± ± ±0.009 (ND~12.8) (ND~4.00) (ND~1.94) (ND~0.126) Cortex 1/81 Flos 1/16 Fructus / ±0.29 (ND~2.4) 0.83± ± ± ±0.006 (ND~4.32) (0.01~1.31) (ND~0.41) (0.001~0.029) 0.37± ± ± ±0.011 (0.02~1.57) (0.02~1.29) (ND~0.45) (0.001~0.035) 0.05±0.08 (ND~0.59) Herba 15/ ± ±0.42 (ND~3.31) (0.01~4.00) Perithecium 3/33 Semen /64 Caulis 4/ ± ±0.006 (ND~0.29) (ND~0.065) 0.14± ±0.006 (ND~0.94) (0.002~0.037) 0.77± ± ± ±0.005 (0.01~4.20) (0.01~0.79) (ND~0.65) (0.002~0.023) 0.11±0.16 (ND~0.90) Radix 13/ ±0.53 (ND~4.38) Rhizoma 32/ ±0.80 (ND~12.8) 0.04± ±0.05 (ND~0.24) (ND~0.25) 0.004±0.005 (ND~0.027) 0.90± ± ± ±0.007 (ND~4.21) (0.01~2.07) (ND~1.94) (ND~0.042) 0.27± ±0.09 (ND~2.44) (ND~0.60) 0.23± ±0.16 (0.01~2.42) (ND~1.78) 0.008±0.012 (ND~0.126) 0.006±0.008 (ND~0.09) 68/ ± ± ± ±0.014 (ND~87.2) (ND~20.0) (ND~1.49) (ND~0.144) 49/ ± ± ± ±0.010 (ND~16.7) (ND~2.44) (ND~1.30) (ND~0.130) 117/ ± ± ± ±0.012 (ND~87.2) (ND~20.0) (ND~1.49) (ND~0.144) 17/ ± ± ± ±0.011 (ND~19.6) (ND~2.41) (ND~0.65) (ND~0.068) 13/61 1/195 3/74 7/69 5/201 22/ ± ± ± ±0.026 (0.01~87.2) (0.03~11.9) (0.01~0.51) (0.001~0.144) 0.60± ± ± ±0.012 (ND~10.5) (ND~2.08) (ND~0.24) (ND~0.120) 1.22± ± ± ±0.009 (ND~6.62) (0.01~2.44) (0.01~0.46) (0.001~0.057) 0.57± ±0.16 (0.01~3.26) (ND~0.73) 0.21±0.50 (ND~4.93) 0.20±1.41 (ND~20.0) 0.11± ±0.017 (ND~1.49) (0.001~0.132) 0.08± ±0.007 (ND~0.44) (ND~0.048) 3.50± ± ± ±0.008 (0.29~8.11) (0.04~0.35) (ND~0.58) (0.001~0.039) 16/ ± ± ± ±0.009 (ND~16.7) (ND~2.40) (ND~1.04) (ND~0.130) 33/ ± ± ± ±0.011 (ND~4.49) (ND~2.44) (ND~1.30) (ND~0.078) 1) MeanÛstandard deviation. Numbers in parenthesis are range. Not Detected ( 0.001). 2) Number of sample exceeded its criteria/total number of sample analyzed Herbal standard criterion announced by KFDA (Not more than Pb:5, As:3, Cd:0.3, Hg:0.2 mg kg 1 ) 3) pvalue shows significant differences of heavy metal contents between domestic and imported medicinal herbs (ttest, <0.05). ƒ ,» ND8.11, tv ND19.6 w sƒ., w û (ANOVAtest, p<0.05)., tv ƒ w š,, ƒ w w š19,21 w w. û ƒ w (ttest, p<0.05). û» w tv 14, 9,» 3, 2, 1 29, w 3,» 1 4, ƒ w û. w 0.36, 1.01, š(ttest, p<0.05),» w 1, w 32. š / û w t v 0.83/1.54, 0.18/0.60, 0.45/1.22,» 0.90/ 3.50, 0.36/0.54,» 0.29/0.6 w ƒ š, / ƒ, e, w (ttest, p<0.05). w (mg kg ) , 0.25,» 0.24, tv 0.18, 0.16, 0.11, 0.09 š s³ 0.18 š, w 0.27,» 0.23 š s³ w ƒ (ttest, p<0.05).» w 3, 1, 1 5, w. w 0.19, 0.25 š(ttest, p<0.05),» w 1, w 4. š / w ƒ 0.05/0.15, 0.19/0.34,» 0.29/0.14 w ƒ, š,» (ttest, p<0.05). Vol. 22, No. 6, 2009

9 512 ½ ³Á½ Áw Áw yá½ Á xáy Á Á½ Á Table 8. Correlation coefficients among heavy metal contents 1) As Cd Hg Cd Hg Hg Group n Pb As Cd Above ground parts ** 0.160** 0.234** 0.106** 0.134** 0.219** Underground parts ** 0.354** 0.158** 0.084** 0.315** 0.051** Total ** 0.145** 0.196** 0.101** 0.182** 0.115** Cortex ** 0.402** 0.160** 0.176** 0.235** 0.202** Flos ** NS NS NS NS NS Fructus ** 0.288** 0.092** 0.230** 0.155** NS Herba ** NS 0.457** NS NS NS Perithecium * NS NS 0.625** 0.450** 0.294** Semen * NS NS 0.165** NS NS Caulis 95 NS 0.410** 0.569** 0.247* NS 0.428** Radix ** 0.258** 0.165** 0.152** 0.380** NS Rhizoma ** 0.514** 0.144** NS 0.159** 0.094* 1) Total number of sample analyzed *, **= p<0.05, p<0.01, respectively, NS; Not significant e w (mg kg )» , 0.12, 0.11, tv 0.10, 0.07, 0.04 š s³ 0.08 š, w» 0.17, 0.11 š s³ e»,»,, ƒ (ANOVAtest, p<0.05). w ƒ e w (ttest, p<0.05). e» w» 23, 15, 10, 4, t v 4, 2 58 š, w» 64, e w ƒ ƒ. 3152» w 186, e» w 148 û, w w. w e w 0.11, 0.10 š(ttest, p<0.05), e» w w 81, 67. š / e w 0.05/0.08,» 0.10/0.35, 0.12/0.09 w ƒ,» š, (ttest, p<0.05). w (mg kg ) , 0.015,» 0.013, tv 0.011, 0.010, 0.006, š s³ š, w 0.008,» š s³ w ƒ ù(ttest, p<0.05),» w. w w 0.007, (ttest, p<0.05). š / w tv 0.009/ 0.012, 0.004/0.008, 0.013/0.018,» 0.010/ 0.020,» 0.006/0.010 w ƒ (ttest, p<0.05). w(mg kg ) , š, 0.825,» 0.828, š, 1.154, tv 1.634,» 2.238, (ANOVAtest, p<0.05). mw û,, e, w Table 8. û (r=0.418), w (r=0.331), e (r=0.160), w (r=0.354), ƒ w (p<0.01). û w, w, e ƒ. e û,, Ÿ w w š26 w w. e ƒ w š, w (r=0.315) ƒ. e ƒ w (p<0.01)., û tv,,,», e, (p<0.01). tv,,, e,. e t v,,» (p<0.01). Analytical Science & Technology

10 mw w s 513 y, ½,,,,, ½ Ì. š x 1. y,, w s», 15, ƒ, w, t t, š y, w, 6965y( ) 4. t t, w t œ e, 3, w, w t m, 2, w, GU B. Jung, B.Y. Kim, K. S. Kim, J.S. Lee and I. S. Ryu, Korean J. Soil Sci. Fert., 29, 158(1996). 7. G. G. S. Holmgren, M. W. Meyer, R. L. Chaney and R. B. Daniels, American J. Environ. Qual., 22, 335(1993). 8. ½x, w, 346, q g ù, w, S. D. Lee, and K. S. Park, Korean J. Oriental Preventive Medical Society, 5, 31(2001). 10. J. S. Kim, S. W. Hwang, J. M. Kim and J. Y. MA, Korean J. Yakhak Hoeji, 45, 448(2001). 11. J. H. Kim, J. Y. Yang and Y. S. Moon, Korean J. of the Environmental Sciences, 16, 1287(2007). 12. Y. Y. Cha, S. K., Hea, B. C. Cha and S. H. Sea, Korean J. Oriental Physiology & Pathology, 21, 226(2007). 13. D. H. Jung and M. K. Park, Korean J. of the Environmental Sciences, 17, 129(2008). 14. S. H. Lee, H. Y. Choi and C. H. Park, Korean J. of Biotechnol Bioeng., 18, 90(2003). 15. M. K. Park, Korean J. of the Env. Sci., 16, 241(2007). 16. S. D. Lee, H. M. Park, J. C. Lee and Y. B, Kook, Korean J. of Oriental Med., 24, 59(2003). 17., x, y, «,, w w, 29,, w, w t xz, w w, 1538,, w, Y. Shin, J. E. Kwak, C. H. Han, Y. S. Hwang, A. S. Park, D. G. Kim, E. J. Han, S. J. Jung, B. S. Kim, B. H. Choi, Report of Seoul Institute of Health and Enviroment, Korea, 43, 226(2007). 20. J. E. Kwak, Y. Shin, C. H. Han, Y. S. Hwang, A. S. Park, D. G. Kim, E. J. Han, S. J. Jung, B. S. Kim, B. H. Choi and M. Y. Kim, Report of Seoul Institute of Health and Enviroment, Korea, 43, 129(2007). 21. I. S. Yu and Y. J. Hong, Report of Seoul Institute of Health and Enviroment, Korea, 42, 62(2006). 22. Y. J. Hong, J. E. Kwak, W. H. Park, Y. S. Hwang, E. J. Kim, A. S. Park, Y. Shin, E. J. Han, J. M. Lee, B. S. Kim and B. Y. Choi, Report of Seoul Institute of Health and Enviroment, Korea, 42, 286(2006). 23. KOLAS (Korea Laboratory Accreditation Scheme), KT208y. 24. ½, w w, 58(2007). 25. w, ICPMS, 2839, w, Raymond Niesink, Mannfred A. Hollinger, John De Vries, ToxicologyPrinciples and Applicationsv, 1738, CRC Press, Inc., Florida, USA, Vol. 22, No. 6, 2009