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1 J. Fd Hyg. Safety 16(4), (2001) œ } ª ªˆ w Á½ Á w p y A Study on the Contents of Heavy Metals in the Commercial Processed Foods Ock Kyoung Chun, Yeonchon Kim and Sun Hee Han 4FPVM.FUSPQPMJUBO 3FTFBSDI*OTUJUVUF PG 1VCMJD )FBMUI BOE &OWJSPONFOU ABSTRACT This study was conducted to determine the content of heavy metals in canned s and soft s available on the Korean markets. Trace metals (Pb, Cr, Cd, and Sn) were detected in 24 kinds, 120 samples by Atomic Absorption Spectrophotometer. The average concentration of heavy metals in canned s was in the order of Sn (6.930 ppm)>cr (0.050 ppm)>pb (0.030 ppm)>cd (0.008 ppm), which was the same order in soft s as Sn (3.519 ppm)>cr (0.080 ppm)>pb (0.024 ppm)>cd (0.001 ppm). The total contents of heavy metals in canned fruits and fruit juices were relatively higher than those in cans and s made of and fish. It can be supposed that the high acidity owing to the organic acid of fruit itself promotes to extract metals from can materials, and although fish usually contains more heavy metals than s, canned fish revealed low level because internal organs and most of skin which had more heavy metals than meat were removed throughout canning process. Because processed s such as canned s and soft s are very popular with the children and adolescence according to the change of life style and eating habit, and the possibility of exposure to heavy metals by the habitual intake of these is increasing simultaneously, it is suggested that more practical study about the process of exposure and the amount in each step is needed for the assessment of safety. Key words ý canned, soft, Pb, Cr, Cd, Sn t œ y y ƒœ t y w ƒœ t y r, k, ƒ, y y, t kv y w, ³x ƒ y j j w 1). ƒœ t y w š w y ƒ w ƒœ t y w s wƒ w ƒ d ƒ ù t 3 1 ƒœ t w š, tœ sy k w, ƒœ t w t 96% w š w 2). ƒœ t k w, w ƒ w q 3). Author to whom correspondence should be addressed.» v w,,,, g p v, û,, e ùkü w 4), š wwù, w, ü y, x, m ww w 5) e š, x mw n w ü e,,,» w 6). p ùkü š m w š» w vw w ƒ ü» m ƒ š 7-11). w û, j, e, w v w v w w ùkü 308

2 4R i y sp6 y py qapf Fp fw ty sp6 xxpƒhtfwiƒ hp pi9 i 309 š12) w ¾ ƒ š ƒ ù y x t w w» v w. ¾ ù t w w 13-16) t e l ƒ, ƒœ t w š 17-18) š w.» š 19) ƒœ t t w x t ùküš y» w w y w k ùp e ³ x, e ƒ e w, d k e ³x w. ƒœ t ƒ t w m, w ƒ û(pb), e (Cd), j (Cr) (Sn)w wš w» œ wš w ¾ ü x m q m, w w (Table 1). x 1) û(pb), e (Cd), j (Cr) (Sn) 4 d w. 2) 1mg/ml Ÿ t (Wako Pure Chemical Industry Ltd, Japan) w š, 0.5N HNO 3 w w, Nitric acid, hydrochloric acid w d p w. 3) 3g w ky k z 450 C» o zy g. zyƒ óù z š Table 1. Sample size of the experiment Food Canned s Soft divided fruit fish fruit & mixed carbonated item 2~4 ml ƒw e w, zy 0.5N HNO 3 ww k z 25 ml w 20). ƒ w» w. 4) Polarized Zeeman Atomic Absorption Spectrophotometry (Hitachi Z-5700, Z-5300, Hita-chi Co., Japan) w û(pb), e (Cd), j (Cr) Graphite Furnace Atomization w š, (Sn) Flame Atomization w. Table 2. ƒ 3z x w. (ph) phmeter(orion, 920A) w d w. š No. of samples mandarin 5 grape 5 peach 5 pineapple 5 perilla leaf 5 kimchi 5 bamboo sprout 5 corn 5 tuna 5 pacific saury 5 mackerel 5 whelk 5 orange juice 5 peach juice 5 apple juice 5 grape juice 5 grain-based 5 ion 5 youngji 5 chitosan 5 coke 5 cider 5 kids soda 5 fiber 5 Total ¾ ü x m

3 310 HhvD yr6s yp fw Table 2. Analytical conditions of A.A.S. 21,22) conditions of A.A.S. Item analysis mode flame type carrier/fuel gas flow rate oxidant gas pressure (kpa) slit (nm) lamp current (ma) wavelength (nm) Pb Cr graphite furnace Ar 30 (ml/min) Cd Sn flame air-c 2 H (L/min) q m, w û(pb), j (Cr), e (Cd), (Sn) w d w Table 3 4. y x y m, e t ƒw š d»w. ƒœ t w ù, ƒœ m» s Table 3. Contents of heavy metals in canned s (mg/kg, wet base) mean (minimum~maxium) Pb Cr Cd Sn fruit fish mandarin (0.046~0.057) (0.036~0.048) (0.001~0.003) (7.420~8.350) grape (0.012~0.052) (0.010~0.082) (0.000~0.004) (0.000~19.582) peach (0.030~0.138) ( ~8.177) (0.001~0.002) (0.000~14.359) pineapple (0.002~0.014) (0.021~0.114) (0.002~0.003) (16.012~42.510) perilla leaf (0.023~0.060) (0.048~0.100) (0.003~0.004) (0.000~3.217) kimchi (0.004~0.011) (0.009~0.023) (0.001~0.005) (0.005~2.015) bamboo sprout (0.015~0.057) (0.011~0.031) (0.002~0.003) ( ~1.960) corn (0.003~0.018) (0.012~0.021) (0.000~0.004) (0.000~0.263) tuna (0.021~0.078) (0.013~0.041) (0.008~0.016) (0.000~6.380) pacific saury (0.003~0.026) (0.019~0.053) (0.005~0.011) (0.000~3.860) mackerel (0.004~0.008) (0.009~0.021) (0.004~0.012) (0.000~0.115) whelk (0.010~0.091) (0.023~0.182) (0.012~0.046) (0.000~4.701) Total (0.002~0.138) (0.009~0.182) (0.000~0.046) (0.0006~1.960) Table 4. Contents of heavy metals in soft s (mg/kg, wet base) mean (minimum~maxium) Pb Cr Cd Sn fruit & mixed carbonated orange juice (0.000~0.022) (0.092~0.340) (0.000~0.003) (2.080~4.957) peach juice (0.006~0.070) (0.017~0.300) (0.000~0.002) (0.000~27.113) apple juice (0.002~0.036) (0.026~0.160) (0.000~0.002) (0.000~10.737) grape juice (0.012~0.090) (0.037~0.304) (0.000~0.001) (0.000~14.913) grain-based (0.001~0.008) (0.008~0.048) (0.000~0.001) (0.000~0.520) ion (0.003~0.020) (0.010~0.062) (0.000~0.002) (0.000~0.507) youngji (0.005~0.144) (0.023~0.058) (0.000~0.001) (0.000~8.777) chitosan (0.006~0.028) (0.021~0.121) (0.000~0.001) (0.000~3.940) coke (0.001~0.107) (0.009~0.173) (0.000~0.001) (0.000~4.263) cider (0.001~0.011) (0.083~0.191) (0.000~0.001) (0.880~3.037) kids soda (0.028~0.053) (0.011~0.065) (0.000~0.010) (0.000~1.427) fiber (0.019~0.129) (0.018~0.024) (0.001~0.002) (0.000~0.000) Total (0.000~0.144) (0.008~0.340) (0.000~0.010) (0.000~27.113)

4 4R i y sp6 y py qapf Fp fw ty sp6 xxpƒhtfwiƒ hp pi9 i ,24), j 25). e t ƒ ³ w q» l. w»» e w j w 26). ù t m û 0.3 mg/kg( m 2.0 mg/kg), 150 mg/kg( m 200mg/ kg) w» w ³ wš. 20) û(pb) w û ƒ wù heme w, x x» 27-30). ALA(aminolevulinic acid) Prophobilinogen yw v w ALAdehydrase z w x ALA ƒ g heme w CPG3 PPG3 y v w Coprophyrinogen decarboxylase z k heme w š ƒw 31,32). w x û ƒ ƒw K ƒ n ƒ x š x ü w x» š x» w x y» x ƒ ƒ. w š û» s segmental demylination»š Schwann's cell mitostreamdria šƒ 33,34). Fig. 1 m û w m 0.041ppm ƒ š, m m 0.024ppm ùkû. w ƒ 0.043ppm ƒ ùkû k (0.029ppm), yw (0.017ppm) ùkû. t û w ùkù w w x 26) š» w ƒ w ƒw w. w Fig. 2 m (0.076ppm)> (0.052ppm) >s (0.026ppm)>q v(0.006ppm) s (0.043ppm)> (0.037ppm)> (0.020ppm)> (0.004ppm) û w ùkû» e» m» ƒ p j w q. w m» ƒw û, w ƒ š š ƒ š š 26). w q û w ùkù» m, m û ùkù m ³ w yww xw w e, e, š m ƒœ w ü Ë ƒ» q. w q m 0.063ppm ùkù q w. j (Cr) j v š35) z 3ƒ xk glucose tolerance factor s y w insulin z w w v insulin w» w, glucose tolerance w ùkü š š 36). 3ƒ j» ƒ Fig. 1. Content of Pb in canned s and soft s. Fig. 2. Content of Pb in canned fruits and fruit juices.

5 312 HhvD yr6s yp fw Fig. 3. Content of Cr in canned s and soft s. Fig. 4. Content of Cd in canned s and soft s. ùkü 6ƒ j chromate xk g,, y» m ³ w ù chromate-worker y» š š. x û w m j w ùkû ù j w 3ƒ j 6ƒ j w ƒ w ƒ. e (Cd) e w œ,, w w wš e, e, w», w œ w w w». w e m j œ q w š š š 37,38). Fig. 4 e w w m m w û ùküš. e t» 0.1ppm ù 19) š x t ƒ œ k wš w» w šƒ v w q. (Sn) ww ù n, w, ü y, x, m w e š39,40), x mw n w ü e,,,» w ƒ 40). p e t» ¼ w ƒw š š 17,26). e ü w, ph w w y w w. ww y 41). Fig. 5 m w w ƒ w ùkü m p m w š ppm ùkü ƒ m w ƒœ w» w w y w ƒ û» w q. yw t t ƒ ƒw» ù ³»k w ³ 20) w,,, jm w, š sw t w,, jm w w t š xy. Fig. 5. Content of Sn in canned s and soft s.

6 4R i y sp6 y py qapf Fp fw ty sp6 xxpƒhtfwiƒ hp pi9 i 313 Fig. 6. Contents of Pb, Cr, Cd, and Sn and ph in canned s and soft s. Fig. 6 û, j, e, w ph ùkü ph k ƒ 2.5~3.1 s³ ph 2.8 ƒ û k w w» ü e k ƒ. xw ƒœ t w wš x te e ƒ x t r w w š 42). w w x v w ƒœ t e w w sƒƒ w w š q. ƒ ƒœ t w m, w wš w» œwš ¾ ü x m q m, w û(pb), j (Cr), e (Cd), (Sn) w d w, m û s³ w m 0.041ppm ƒ š, m m 0.024ppm ùkû ƒ 0.043ppm ƒ k (0.029ppm), yw (0.017ppm) ùkû. t û w ùkù w w» w ƒ w ƒw ew q, w m û w, m û ùkù e, e, š m ƒœ w ü Ë ƒ» q. j w û w m ùkû ù j w 3ƒ j 6ƒ j w w ƒ w ƒ. e w m m w û ùkþ p t» 0.1ppm w ppb ùkù» v w šƒ v w q. m w ƒ w ùkü m p m w š ppm ùkü ƒ m w ƒœ w» w w y w ƒ û» w q. ù ƒœ t w ƒwš y e ƒwš x w ƒ œ t e w w sƒƒ w w ƒ. š x 1.. w. w wz 29(4), (1996). 2. «k,». w y ywz 8(4), (1993). 3., z, x,. w w t s³ (1990 ) y. w t wz 15(2), (2000). 4. E.J, Underwood : Trace elements in Human and Animal Nutrition (1962). 5. De Groot, A.P.: Subacute toxicity of inorganic tin as influenced by dietary levels of iron and copper. Food and Cosmetics Toxicology. 11, (1971). 6. Greger, J.L. and Johnson, M.A. : Effect of dietary tin on zinc, copper and iron utilization by rats. Food and Cosmetics Toxicology. 19, (1981). 7. œx,,,,,,,

7 314 HhvD yr6s yp fw :, m,, š w w. w. 26, (1994). 8. ½,»,, ½ : ü m w. w y w, 7, (1993). 9. ½, : y, m w. w š, 12, (1984). 10. ½, ½ w,,»,», Ÿ, : w m ü w w. y, 2, (1980). 11., y, : w m w w. w y wz, 20(2), (1994) ,, (1996). 13. ½¼, ½,,,,,, ½, w : t» w. 31, (1994). 14. t, ½,,,,,, ½, ½x, ½¼ : t w. 32, (1995). 15., x,,,, k, w, :» w w. p y 31, (1995). 16. ½, ½,»,, ½,, k,, š :» w. p y 32, (1996) 17. Lee, N.K., Yoon, J.Y. and Lee, S.R. : Changes in heavy metals and vitamin CG content during the storage of canned and bottled orange juices. Korean J. Food Sci.GTechnol., 27, (1995). 18. Chung, J.K., Lee, K.H., Lee, S.J., Park, S.W., Park, W.W., Shin, S.C. and Moon, S.I.G : Study on the heavy metal contents of canned s. Annual Report of KyongGSang Buk-do, Institute of Health and Environment. 6, (1993). 19., w :» w w. w t wz 15(4), (2000). 20. ªƒ ª «. ª (2001). 21. Flame Atomization Analysis Guide for Polarized Zeeman Atomic Absorption Spectrometry. Hitachi, Ltd. 1st ed. Japan. (1997). 22. Graphite Furnace Atomization Analysis Guide for Polarized Zeeman Atomic Absorption Spectrometry. Hitachi, Ltd. 1st ed. Japan. (1997). 23. Reilly, L.: Metal contamination of. Applied Science Publishers, London, p. 1 (1980). 24. ½ z: m t.., p. 147 (1984). 25. y : yw w. y,, p (1985). 26. xûe, ½,, ùy : m» ph y. w t wz. 29(3), (2000). 27. Klomme, D. R. and Johnson, D. R. : Amelroration of mercuric chloridenduced acute renal failure by dithiothreitol, Toxicol. Appl. Pharmacol., 70, (1983). 28. Little. C., Olinescu, R., Read, K. G. and Brien. P. J.: Properties and regulation on glutathione peroxidase. J. Biol. Chem. 245, (1970). 29. Bakir, F., Rustam, H., Tikriti, S., A1-Damluji. S.F, Shihristani. H. : Clinical & epidemiological aspects of methylmercury poisoning. Postgrad. Med. J., 56, 1-10 (1980). 30. Sakurai H. Sugita M. Tsuchiya K. : Biological response and subjective symptoms in low level lead exposure. Arch Environ Health : WHO. 29, Zielehuis RL. Interrelationship of biochemical responses to the absorption of inorganic lead. Arch Environ Health, 23, (1971). 32. Aiert, ED. : Pollution indicator, fish consumption and the accumulation of Mercury in human hair, Marine Pollution Bulletin, 15, (1984). 33. Wimeyer, Stanley N., Bernad M. Mulbern, Frank J. Ligas, Richard J. Hensel, John E. Mathisen, Fred C. Robards and Sergei Postuplasky : Residues of organochlorine pesticides, Polychorinated Biphenyls and Mercury in Baldi Eagle Eggs and changes in shell thickness: 1969 and Pesticides Monitoring Journal, 6, (1972). 34. Hutzinger,. and A. A. M. Roof : Polychlorinated biphenyls and related halogenate compound, Analytical techniques in environmental Chemistry, Pergamon seris on Environmental Science, 3, (1978). 35. Schwarz, K. and Metz, W. : Arch. Biochem. Biophys., 85, 292 (1959). 36. Mertz, W., E.W. Toepfer, E.E. Roginski and M.M. Polansky : Present Knowledge of the role of chromium. Fed. Proc. 33, 2275 (1974). 37. Langolf F D, Chaffin D B, Henderson R, Whittle H. P. : Evaluation of workers exposed to elemental mercury using quantitative test to tremor and neuromuscular functions, Am Ind Hyf Assoc. J. 39, 976 (1978). 38. Yamada, M. and Tonomura, K. : Formation of methyl mercury compounds from inorganic mercury by Clostridium Cochlearium. J. Ferment Technol., 50, (1972). 39. De Groot, A.P. : Subacute toxicity of inorganic tin as influenced by dietary levels of iron and copper. Food & Cosmetic Toxicology, 11, (1971). 40. Greger, J.L. and Johnson, M.A. : Effect of dietary tin on zinc, copper and iron utilization by rats. Food & Cosmetic Toxicology, 19, (1981). 41.,, ûª : t w. y,, p. 220 (1987). 42. x : ù. w wz. 27, (1994).

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