Study on the Heavy Metal Contents in Fishes and Shellfishes of Gyeongsangnam-Do Coastal Area-Part 1

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1 J. Fd Hyg. Safety 19(3), (2004) û q w w - 1 w Á *Áw û y * w y Áyœ lœw Study on the Heavy Metal Contents in Fishes and Shellfishes of Gyeongsangnam-Do Coastal Area-Part 1 Gang-Ja Ha, Ju-Yeong Song*, and Dae-Sik Hah 1VCMJD)FBMUI &OWJSPONFOU*OTUJUVUF(ZFPOHTBOHOBN%P$IBOHXPO,PSFB *%FQBSUNFOUPG&OWJSPNFOUBMBOE$IFNJDBM&OHJOFFSJOH$IBOHXPO/BUJPOBM6OJWFSTJUZ$IBOHXPO,PSFB ABSTRACT As measures against the environmental pollution, maximum efforts to improve of the environmental pollution have also been made; removal of the contaminated sediments of the bay and the coastal area, monitoring of several heavy metal levels in fishes, shell fishes, sea water and sediment, and so on. The objective of this research is to investigate how much metals are included in the sea water, sediment, fishes and shell fishes in kyeongnam coastal area. Specifically, we are investigating the relationships between the metal included in fishes and sea water, and shell fishes and sediment, and heavy metals and heavy metals respectively. Heavy metals over the studied component and area, the average concentrations of Pb, Cd, Cr and Hg in sea water were mg/l, mg/l, mg/l and ND, those of sediment were mg/kg, mg/kg, mg/kg and Hg mg/kg, those of fishes were mg/kg, mg/kg, mg/kg and Hg mg/kg, and those of shellfishes were Pb mg/kg, Cd mg/kg, Cr mg/kg and Hg mg/kg respectively. In the relationship test, Cd was significant in the relationship between fishes and sea water, and Hg was significant in the relationship between sediment and shellfishes. Key words: heavy metal, coastal area sea water, shell fishes, sediment š ƒ œw ƒ wš œ s yw w w w ú w š. w w q mw y š ù w š w ƒ. 1,2)» t ƒ 30 š, w ƒ As, Cr, Be, Ni, Cd, Pb, Hg v w ƒ ƒ Co, Cr(III), Cu, Fe, Mg, Mn, Mo, Se, Zn š w e Al, Bi, Ga, Au, Li, Pt minor toxic metals. 3) Author to whom correspondence should be addressed. wr, w y m, w,,,,, š ƒ ù w w wš. ù, s», s x y š š ù q x w. ù q w ü e w k k ù ù k ƒw j. 4) 1974 FAO/WHO(Food and Agriculture Organization/ World Health Organization) w z yw p û,,, e» w. FAO/ WHO w t l ƒ t w w w, sƒw w e qwš w FAO/ WHO w t³ z(the Joint FAO/WHO Codex 132

2 4UVEZPOUIF)FBWZ.FUBM$POUFOUTJO'JTIFTBOE4IFMMGJTIFTPGà 133 Alimentarius Commission) œw t» w ³ wš. 5) w, w y» w WHO t w w wwš, ù w ù w w w wš, k ü k e w zw m w ƒ w š. 6,7) y ù yw, ƒ», œ ù s, w,, ù ƒ ù w ƒ. w y wš, w d w w ù w n w w w w. w w n ww w n š, w w n d w q. 8) û 7œ w œ w q š y ˆ w w w w ƒ k q wš, q ˆ, w y ƒ w w t y w» š w ¾ 4 û?q 7, š, m, w,,, ûw» w 1z ƒ q, ˆ, w w, m,, w w.»»»» wv»(inductively Coupled Plasma Analyzer, ICP Analyzer)»(Automatic Mercury Analyzer) w, Table 1, 2. w, y Matsunoen Chemicals Ltd. w w, w» y yw 10 g Table 1. Analysis condition of ICP analyzer Instruments Generator Power Pressure Wavelength(nm) SPECTROFLAME(FSP 0A83B) SPECTRO ANALYTICAL INSTRUMENTS GMBH, Germany 1200 W Nebulizer Auxiliary Coolant Pb : Cd : Cr : psi 30 psi 40 psi Table 2. Analysis condition of automatic mercury analyzer Instruments Mercury Automizer Main Unit Mercury Automizer Controller Mercury Detector Pressure gauge Heating Condition Mode selector Pannel time Additive Mercury SP, Nippon Instruments Automizer MA Automizer MA-1 Detector MD-1 Carrier gas pressure : 0.4 kg/cm 2 Combustion gas flow rate : 0.5 L/ min LOW 1st step : 350 o C, 4 min 2nd step : 700 o C, 6 min Shellfish, Fish, Sediment : M+S+M+B+M Sea water : B+S+B+M M : Sodium carbonate : Calcium hydroxide(1:1)(w/w) B : Aluminium oxide S : Sample v p e p(ammonium pyrrolidine dithiocarbamate : APDC, ACROS Chemical Co.) 10g p p p e p(diethylammonium diethyldithiocarbamate : DDDC, Wako Pure Chemical Industries, Ltd.) 500 ml APDC/DDDC yw w. j s Merck p w, Pb, Cd, Cr, Hg t Merck ICP 1,000 ppm t w Hg 0.001% L-Cystein 0.1 N w w. x Pb, Cd, Cr, Hg w 0.1 N w z k w v p š s p» w w w y œ x, w w x w 9)

3 134 (BOH+B)B, Pore Sizeƒ 0.45 µm w z APDC/DDTC yw j s w w z jš w w k z 1.0 N w ICP» w d w. ˆ n w y œ x 9), w n w m, w, w œ w z m 1 g w w 5 ml w 5 ml ƒw ƒ ww z 1.0 N w ICP» w d w q Ë ¼ z 2 w ˆ w z ³ yw z A.O.A.C. (Association of offical analytical chemists) 10) 20 g ƒ š, ky k 450~550 C o zyw. zyƒ w 30% 2~5 ml ƒw w zy k z 0.1 N ww z w w ICP» w d w. Ë w z ƒ 100 g w ³ yw z 20 g q w w. w w 0.5 ml, ˆ, q 50~100 mg ƒ»y 11)» d w. z d q, ˆ w A.O.A.C. 10) ƒ d w, ƒ w z q ƒƒ z» w ƒ 5 kw Hg, Cd, Pb, Cr t ƒ w w w d w s³ w z w. zy q 1 kw 10 g A.O.A.C. 10) y - w zy zy w Pb, Cd, Cr w d w z w. m q ˆ w w ƒ w Statistical Package for Social Sciences (SPSS) m v w, mw v (Pearson correlation coefficient, r) w y d w. w x w, w ƒ., d ƒ t (+)»» sw ƒ š, (-)»» ƒ À sw. N l X Y ƒƒ r pearson. 12,13) Œˆ š u = Y ( ) Y u Y š ( ) Y u z q w ü ³ e» w 14)» w, q ˆ w w š w. w d q, ƒƒ 84.6, 84.9% w ùkûš, w û ù p w 68.4% ƒ û ù. ˆ w ˆ w, ûw ˆ 30.5% ƒ ù (Table 3). ƒ w z (%) x Cr 96.4Û0.9 ƒ Pb 93.7Û0.7 ƒ û ùkû (Table 4). zy zy w ƒ x r, Table 5. q Pb (3.5~4.7%) ù š, Cd (3.2~5.6%) ù, Cr q, ƒƒ ù. s³ 4.1% k zy kw w.

4 4UVEZPOUIF)FBWZ.FUBM$POUFOUTJO'JTIFTBOE4IFMMGJTIFTPGÃ 135 Table 3. Moisture content of samples Species Seadiment Geoje Goseong Namhae Masan Sacheon Tongyeong Hadong Oyster Butter clam Short neck clam Mussel Red seabream U-Reog Rock fish Finespotted flounder Spottybelly greeling Gray mullet Sea-bass Yellow tails Table 4. Recovery rate of trace metals Element S.D : Standard deviation Moisture(%) Recovery rate(%) Û S.D Hg 97.4 Û 0.9 Pb 93.7 Û 0.7 Cd 96.1 Û 0.9 Cr 96.4 Û 0.9 Table 5. Comparison of wet and dry ashing digestion (mg/kg) Shellfishes Fishes Species Pb Cd Cr Wet Ashing Digestion Dry Ashing Digestion Wet Ashing Digestion Dry Ashing Digestion q,, ˆ w w q ü ƒ s y t q w ù e, ü ƒ e w e 2:1( : e) û 10:1( : e) ü w ƒ ƒ š. 15~17) ƒ w Table 6, Pb s³w (0.0440~1.8692) mg/kg, û wƒ mg/kg ƒ š mg/kg Table 6. Average contents of heavy metals in shellfishes (mg/kg) Local region Pb Cd Cr Hg Geoje Goseong Namhae Masan Sacheon Tongyeong Hadong ƒ û. ½ (1990) 22) 0.39 mg/kg, ûw w ½(1988) 23) 0.28 mg/kg ùkû. ü ³ e e û q Pb û. Cd s³w (0.0140~ ) mg/kg, š mg/kg ƒ š ƒ mg/kg ƒ û. w 20) 0.12 mg/kg, x 18) mg/kg, 19) 0.58 mg/kg, ½ (1990) 22) 0.44 mg/kg, ûw w ½(1988) 23) 0.36 mg/kg, 21) mg/kg û. ü ³ e e û Pb ƒ Cd û š. Hg s³w (0.0008~0.0953) mg/kg, mg/kg ƒ š ƒ mg/kg ƒ û., x 18) mg/kg. Hg ù, ü ³ e e û q Hg û š. Pb s³w (0.0135~1.1479) mg/kg, m mg/kg ƒ š mg/kg ƒ û. ü ³ e { e w. ˆ w Table 7, Pb s³ w (5.4569~ ) mg/kg, š mg/kg ƒ š mg/kg ƒ û. š w, x 18) mg/kg š 37) mg/kg, w (1989) 38) 32.35~40 mg/kg, wá w w (1986) 39) 29 mg/kg û ùkù ƒ û. Cd s³w (0.0917~0.3776) mg/kg,

5 136 (BOH+B)B m mg/kg ƒ š mg/ kg ƒ û. x 18) mg/kg š w?w w (1986) 39) 0.34 mg/kg w (1986) 38) mg/kg û ùkû. Cr s³w (1.1702~3.1143) mg/kg, ûwƒ mg/kg ƒ š w mg/kg ƒ û. Hg s³w (0.0021~0.0354) mg/kg, š mg/kg ƒ š mg/ kg ƒ û. x 18) mg/kg š w w 19) 0.03 mg/kg. w w Table 8, w w w 42) (Hg 0.03 µg/l, Cd µg/l, Pb µg/l, Cr µg/ L), y 43) w? w s³ w (Cd, Pb : Interminable, Hg µg/l), ½ 44) w Table 7. Contents of heavy metals in sediment Local region Geoje Goseong Namhae Masan Sacheon Tongyeon g Hadong Total No. of sample (mg/kg) Variables Pb Cd Cr Hg Min Max Mean Min Max Mean Min Max Mean Min Max Mean Min Max Mean Min Max Mean Min Max Mean Min Max Mean Table 8. Contents of heavy metals in sea water Local region Geoje Goseong Namhae Masan Sacheon Tongyeong Hadong Total (mg/kg) No. of Variables Pb Cd Cr Hg sample Min ND 4 Max ND Mean ND Min ND 4 Max ND Mean ND Min ND 4 Max ND Mean ND Min ND 4 Max ND Mean ND Min ND 4 Max ND Mean ND Min ND 4 Max ND Mean ND Min ND 4 Max ND Mean ND Min ND 28 Max ND Mean ND (Pb 0.010~0.237 µg/l, Cd 0.012~0.103 µg/l), 45) wœ w (Pb 0.013~0.12 µg/l, Cd 0.007~0.021 µg/l) 46) ƒ w (s³ Pb µg/l, Cd µg/l, Cr µg/l, Hg µg/l) š. Pb s³w (0.0004~ ) mg/l, ûwƒ mg/l ƒ š mg/l ƒ û, w w 42) w e ùkû. Cd s³w (0.0001~0.0019) mg/l, mg/l ƒ š mg/l ƒ û, 45) w w (1996) š ½ 44) (1994) e w 46) (2000) ƒ w û. Pb s³w (0.0004~ ) mg/l, ûwƒ mg/l ƒ š

6 4UVEZPOUIF)FBWZ.FUBM$POUFOUTJO'JTIFTBOE4IFMMGJTIFTPGà mg/l ƒ û, w w 42) w e ùkû. Cd s³w (0.0001~0.0019) mg/l, mg/l ƒ š mg/l ƒ û, 45) w w (1996) š ½ 44) (1994) e w 46) (2000) ƒ w û. Hg»» w ( µg/l) w w. q w ˆ w w w, q ˆ q ˆ w Hg w š, ˆ q w Pb w. q w w w û ù q yy, 47)» ù ƒ wì w w. q ( Š) yw w, z ƒ ù p ü ww ù y ƒ k š 59) ù š 58), 55-57) Tacnet (1990) Bobilya (1992) e transport site w w affinity ƒ š šw. w 60) š transport system e w e k š w š, x e w e, e w ùkù š w. ƒ y. q ˆ w m v w Table 8 q ˆ Hg r=0.401 š, w Cd r=0.493 w ùkü. s» w ƒw q ˆ Table 9 Cd (r=0.519) Pb(r=0.418) ƒƒ w ùkü, w Table 10 Pb(r=1.000), Cd(r=0.975)ƒ w ùkþ š Cr(r=-0.659) m ùkü Table 8. Correlation coefficient of heavy metals between shellfishes and sediment, and sea water and fishes Samples Metals r Shellfishes Sediment Hg Sea water Fishes Cd* *P<0.05 Table 9. Correlation coefficient of heavy metals between shellfishes and sediment in each local region Local region Metals r Geoje Cd Goseong Cu Masan Pb Table 10. Correlation coefficient of heavy metals between fishes and sea water in each local region Local region Metals r Masan Pb** Cd** Cr ùkü. ƒ Table 11~13 ùk Table 11. Correlation coefficient of heavy metals in shellfishes Pb Cd Cr Hg Pb - Cd 0.280* - Cr 0.609** Hg Table 12. Correlation coefficient of heavy metals in sediment Pb Cd Cr Hg Pb - - Cd Cr 0.433** Hg 0.712** ** - Table 13. Correlation coefficient of heavy metals in fishes Pb Cd Cr Hg Pb - Cd Cr Hg

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