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Analysis of Water Quality and Heavy Metals for Surface Water and Sedimentsof Upstream and Midstream in Nakdong River  

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(1)Journal of the Korean Chemical Society 2000, Vol. 44, No. 6 Printed in the Republic of Korea.  

(2)   

(3)    .    (2000. 8. 22 ) Analysis of Water Quality and Heavy Metals for Surface Water and Sediments of Upstream and Midstream in Nakdong River Chang-Seop Ri Department of Chemistry, Keimyung University, Daegu 704-701, Korea Received August 22, 2000).  . 

(4)         !" # $ %& '$  () *+%, % ,-./ 012 #34 156 7$  018) *+%9:. ;< => ? 5 # 6@ 22, 23 ABC D!E $ F8G HI AJ K) L 1MN %O,  P) Q % !" R%ST UV UW, X S YZ  %& [$ M) N \ 10] M/ ^;%9:. '$  *+_ '$  ;`ab # cdefg (h, f(Gg (h, COD i \ 22] ab/ %O j%9Nk, ,-._ trichloroethylene i 156 #34 i 11] ab/ %O *+%9:. ,-6 ;< l;`m  G*nmN oo *+%O pq r%9Nk, ;< # #3 4 g*_ 1Hp[ stuv Pl*wmN *+%9, 5x g*_ yz5{ |;`Pm/ %O *+%9:. ABSTRACT. The surface water in the upstream and midstream of Nakdong river, which is being used as tap water and industrial water supply in Daegu city and Kyungpook province, was analyzed in its water quality. In addition, the sediments of which was analyzed in terms of heavy metal and organic substance contents. All the sampling was done in the drought season for 2 days of June 22-23 and carried out in 10 sampling sites. The sites cover the whole Kyungpook provincial region, starting from Yangsam Bridge in Chyeong Ryang Provincial Park as the upper end, to the Ko Ryung Bridge as the lower end sampling site of Nakdong river that flows through Kyungpook province. The 22 items including NH+4 , NO−2 and COD were analyzed for surface water and 11 items including organic constituents(trichloroethylene, etc) and heavy metals were analyzed for sediments. The sediments samples were analyzed by elution testing method and acid dissolution method and then the results were compared with each other. All heavy metals in samples were determined by Inductively Coupled Plasma-Atomic Emission Spectroscopy(ICP-AES) and other constituents were analyzed by standard testing methods of the Korean Ministry of Environment..   R} G ~ €‚ yƒ„ L† ‡on  Nk, ˆ‰  N Š  ƒ„/. n ‹Œ-T އ † Tn _ ‘’ 

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(18) ;  zG;†  ,   G  %  !" 7[-T ƒ„P ï I/ ðµ¾ 5ñ<q *+%9:. 3. Fig. 1 Map of the study area showing the sampling sites of Nakdong Riverside..  . 4. 5-7.     . È ^`/ Fig. 1/ Éx Û ¬’ òŠ !" # $/ ƒ„އ 10] M) #‡N '$  (  ,-. g*‘ q ^;%9:. '$  o M/ 1.5 L œ5 polyethylene Ê ½ 1ÖÊ) %O '$  ó ôõ¾ Z, %& Sš/ ‡Š †Ï ö_ š M Å M) #‡N ÷´ šè) 2i*¾ o M šNzÜ = %9:. = ¾ ;< (ƒ„ | ;`m / n o abv: ;<«øÕÖq ¾ Z ùÏ«Ž%9:. %/ ,-2 ,-.;< => o Mv:  jÆ PmN Oú ì/ ,-.) û­ =>%O ?ü 1ÖÊ/ 1000 g |H ;<q ùÏ, ýþ, « ޾ Z ^`^ ÿÐ%O *+/ %9:. ^`^  ÿÐ2 ,-._ Å™ ì/ 3XC *‰  À‘; : *+;< %9:.

(19) . !" '$  ,-./ ¾ *+ Pm_ (ƒ„ |;`m   56 |;`m / n j%9Nk, Å Ò) Table 1, 2/ Éx Ò:. 11. 11. 12. Journal of the Korean Chemical Society.

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(21)         Table 1. The method and instrument used for the analysis of surface water Sample Items. . pH DO COD Cl. Methods and instrument. . pH meter (ORION model 290 A) Winkler Azide.         .  UV(KONTRON UVIKON 860) 

(22) UV(SHIMADZU 1201) 

(23)  "   " T-N T-P CN. F. . " " " ICP(Jobin Yvon JY50P).  

(24) . , pH  55q  %O ¸Ï/ 3ó ±|%9, DO(øGh) ¸Ï / |; ^`^/ *+%9:. COD( Gh µ

(25) 8)  „h (ƒ„ |;`Pm/  %O *+%9Nk, $, cdefg (h, f(Gg (h, TG„ T, T-N, T-P UV/Visible *wwHmN  *+%9, #34$

(26) uL Jobin Yvon JY50P d ) %O 1Hp[ stuv Pl*wm (Inductively Coupled Plasma-Atomic Emission Spe-. ctroscopy, ICP-AES)N *+%9:. ±|; o #3 4 íÏ_ Zn: 213.9 nm Pb: 217.9 nm Cd: 228.8 nm Fe: 248.3 nm Mn: 279.5 nm Cu: 324.7 nm Cr: 357.9 nm. / j%9:. 

(27) . ,-. 0 _ =>¾ ,-.)  40 g|H >%O #8)  ~ ;/  Dry-oven/ 105110 C a8Š ä ²W À‘ %O Dessicator Pù Z #8mN

(28) %9:. ½¾ ,-._ 1 L Jo flask/ ;< 100 g) =>%O  $ 900 mLq †¾ Z 3000 rpmN 1;C!D  Ð%9:. Šq O(5A)/ O¾ Z 100 mLq > o. % O5/: HNO 5 mLq †%O 510 mL |H † ä ²W †%9:. Šq Pù¾ Z $ q †%O 100 mLq Þ΂ *+% l ;`m, ; < 5 g) >%O  flask/  HNO 10 mL’ HOCl 20 mLq ‚ 156Š ÝY‰ *nH© 5 10 mL |H† ä ²W †%O Šq Pù¾ Z $ q †%O 100 mLq Þ΂ *+% G*nm  † PmN É‚ *+%9:. trichlorolethylene, tetrachloroethylene_ l;`m/ n *Ön Û i) 50 mL >%O ¬ŠÂ/ , O5/ hexane) †%O *C о Z, †uœvÅ (Traco 9000 series, U.S.A.) *+%9Nk, ^ `/ ¾ ;Î_ ;# Ù02 6/ ¾ ƒ„) P%5­%O d BÈ Junsei L – Œ Sigma  Aldrich ˆ;) %9:. 3. 3. 3. 

(29)  . !" () ‘%5 ­%O Fig. / ÉxÛ o ‘ M/ ¾ '$  () Table 1, 2/ ÉxÛ PmN *+%9Nk, Å p q Table 3, 4/ ÉxÒ:. Table 3/ « ¬’ òŠ '$   Š 26.8 C9Nk, pH 8.4  Ög) ÉxÒ:. DO d! M/ ›5g ”9Nk, 8MT » Ž/ CODMn"Š 38 mg/L ª_ ¦q «Š N¼ Š M/ #¾ Ï   1¡Š $| k, Š% !" È$/ ¤¥) –% çŠt $±2 :. ½¾ '$ # #34 g* ëH oo 1. o. Zn 0.019 mg/L, Cd 0.0005 mg/L, Fe 0.23 mg/L, Mn. 9, Pb ®l &'Nk Cr_ 5M/ C ®l)ß, 5x  M/ ®l &':. Š *+p !" ( / ¾  ( 5{Š Zn 1.0 mg/L, Fe 0.3 mg/ 0.0369 mg/L, Cu 0.014 mg/L. L, Mn 0.3 mg/L, Cu 1.0 mg/L, Pb 0.1 mg/L, Cr 0.05 mg/. Table 2. The method and instrument used for the analysis of sediments Sample. . Items. !. trichloroethylene tetrachloroethylene.  F, CN. 2000, Vol. 44, No. 6. 549. Methods and instrument Weighing method(105-110 oC) GC(Traco 9000 series) " ICP(Jobin Yvon JY 50p) UV(KONTRON UVIKON 860).

(30) . 550. Table 3. Analytical results in water quality for the surface water collected at the 10 sites in upstream and midstream in Nakdong River. "#. Items.  ( C) o. pH DO (mg/l) COD (mg/l). 

(31)  (mmol/m ) 

(32)  (mg/l)   (mg/g) 3. T-N (mg/l) T-P (mg/l) (mg/l) CN (mg/l) F (mg/l). . 1. 2. 26.6 8.59 0.113 4 ND 0.24 12.7 0.07 4.4 ND 0.001 0.53. 21.1 7.87 8.715 9 5 0.24 10.9 0.08 3.8 0.0001 0.0015 0.55. 3. 4. 22.9 22.95 7.92 8.63 9.723 9.326 11 4 20 16 0.29 0.23 11.8 12.8 0.09 0.07 4.1 4.4 0.0001 0.0003 0.001 0.001 0.43 0.42. 5. 6. 29.62 26.2 8.53 8.65 9.123 9.527 2 6 17 16 0.22 0.24 12.1 11.9 0.07 0.07 4.2 4.1 0.0009 0.0013 0.0015 0.006 0.32 0.38. 7. 8. 9. 10. 25.2 8.41 8.514 12 2 0.27 11.5 0.08 4.0 0.0016 0.002 0.34. 30.8 9.02 7.908 38 12 0.65 12.8 0.09 4.4 0.001 0.003 0.47. 27.87 8.47 7.906 23 59 0.56 11.3 0.17 3.9 0.0007 0.003 0.63. 28.0 8.07 6.895 19.6 42 1.24 12.6 0.35 4.4 0.002 0.005 0.50. Table 4. Analytical results in water quality for the sediments collected at the 10 sites in upstream and midstream in Nakdong River Zn (mg/kg) Pb (mg/kg) Cd (mg/kg) Fe (mg/kg) Mn (mg/kg) Cu (mg/kg) Cr (mg/kg). ND ND ND 0.0947 0.0562 0.0133 ND. 0.0502 ND 0.0001 0.2804 0.0025 0.0259 ND. ND ND 0.0015 ND 0.0065 0.0194 ND. 0.0505 ND 0.0011 ND ND 0.0054 ND. 0.0102 ND ND 0.9090 0.0069 0.0160 0.0224. 0.0189 ND 0.0021 0.3220 0.0091 0.0138 ND. 0.0027 ND ND ND 0.0035 0.0043 ND. ND ND ND ND 0.0127 0.0106 ND. 0.0588 ND ND 0.5610 0.0897 0.0207 ND. ND ND 0.0004 0.1270 0.1887 0.0148 ND. *Detection limits(mg/kg) Cr: 3 10−4, Pb: 2 10−3, Cd: 2 10−3, Fe: 3 10−4, Cu: 1 10−4. $. $. $. $. $. Fig. 2 The variations in pH values of surface water.. Fig. 3 The variations in concentrations of Chlorine, DO and COD values in surface water.. T ç/ r%O fX (_ ¦q «Š ¢, Š ç_ #34Ί yÑ / §t àY, ¦y  áâ iN ,-. ¡'šN )*¶ Š!%95 ² Št žok, ½¾ ? 5 ;< =>;M #;   PlŠ -N -5 ² T çN $|2:..  / o M '$  (/ ¾ *+ pq ab ÉxÒNk, Fig. 8/ '$ # / Ù02 #34 ëHq H;%9:.  

(33) . Fig. 1/ ÉxÛ o ‘ M/ ,-.) =>%O ,-. ü, +,, 0. L. Fig. 2 7. Journal of the Korean Chemical Society.

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(35)        . Fig. 4 The variations in concentrations of organic nitrogen (ammonia) in surface water.. 551. Fig. 7 The variations in concentrations of phenols, cyanate and fluorine in surface water.. Fig. 5 The variations in concentrations of organic nitrogen (nitrite) in surface water.. Fig. 8 Analytical results of heavy metals in surface water.. Fig. 6 The variations in concentrations of phosphate and TP in surface water..   trichloroethylene, tetrachloroethylene) *+ %9Nk, Å pq Table 5/ ÉxÒ:. Table 5 2000, Vol. 44, No. 6. / Éx- o ‘M ,-./ §¨ ü) «š H;q 1¾ 6M %$.T 8, 9, 10 M/ / ?ü) ÉxÒNk, $_ r- 156Š  XÑA r0¾ ?ü) ÉxÒ:. 0 _ % $ ÒÆš 156 †/ §t :h ªf ¥Š Þ ¿ r0¾ {Š:. ,-./ Ù02 #34 g* 08) l;`m.

(36) . 552. Table 5. Chemical characteristics and analytical results of sediments 1. 2. 3. 4. 18.6 ND ND Light brown sand ND ND. 19.7 ND ND Light brown sand ND ND. 21.6 ND ND Light brown sand ND ND. 20.3 ND ND Light brown sand ND ND. Trichloroethylene Tetrachloroethylene Particle Shape. F CN. 6. 7. %& %& %& %& '%& %& $ $ $ $ ( $. Color Odor. !. 5. 8. 9. 10. 24.3 ND ND Dark brown sand 0.3830 0.0012. 26.9 ND ND Dark gray clay 0.154 0.003. %& '%& '%& '%& $ $ ( (. 22.4 21.2 20.7 22.6 ND ND ND ND ND ND ND ND Dark Brownish Brownish Dark gray gray gray gray sand sand sand sand 0.2650. 0.123 0.841 0.2210. 0.0062 ND ND 0.0024. Table 6. Analytical results of heavy metals tested by elution testing method and acid dissolution method Items Cr (mg/kg) Zn (mg/kg) Pb (mg/kg) Cd (mg/kg) Fe (mg/kg) Mn (mg/kg) Cu (mg/kg). "#. ) * +, ) * +, ) * +, ) * +, ) * +, ) * +, ) * +,. 1. 2. 3. 4. 9. 10. ND 2.53. ND 1.843. ND 1.479. ND 2.6. ND 4.021. ND 0.261. ND 3.922. ND 5.72. ND 6.405. 0.004 6.123. 0.885 94.659. 0.0612 24.433. 0.2169 23.123. 0.5095 8.333. 0.2781 15.011. 0.5876 9.859. 0.3378 7.81. 0.3714 11.812. 0.4819 7.958. 0.5866 34.773. ND 12.311. 0.364 5073. ND 8.554. ND 4.019. ND 8.102. ND 6.637. ND 4.671. ND 4.233. ND 3.891. ND 9.866. ND 1.594. ND 0.131. ND 0.121. ND 0.095. ND 0.122. ND 0.078. ND 0.089. ND 0.041. ND 0.061. ND 0.103. 5.378 4971. 4.389 1971. ND 2932. 2.855 1948. 9.792 4397. 0.489 2715. ND 2154. 5.354 2799. 29.199 2386. 8.881 4226. 3.8767 301. 1.169 1.7. 1.128 129. 1.445 68. 0.249 95. 1.362 101. 0.276 115. 0.313 73. 2.53 125. 2.7885 91. ND 3.587. ND 1.189. ND 1.179. 0.058 0.928. 0.132 2.072. 0.092 1.109. 0.125 1.304. 0.108 1.602. 0.105 1.157. 0.114 6.418.  G*nmN *+%9Nk, Šq Table 6/ Éx Ò:. ,-. ;< *+_  56|;`Pm/ n l;`mŠÉ 01;`m # ‚1 PmNH *+ pq ';¯ NÉ, ^`p 23g) ­%O È ^`/ l;`m  G*nm  †  Pm) d -%9:. O5 l;`m_ G* nm Ö ;<q 10× 4_ GN $l%O $l2 ) :; G*nmN *+¾ "м,  l;`m/ ¾ *+p 10× 5+2 ëH"N  ';‚ G*nmN *+¾ p«: 10× Š  (_ "N ÉxÉ—É ®låN Éx6:. Table 6/ ÉxÛ ¬’ òŠ, o #34  †  Pm/ n ®l2 *+ëHr(G*nm/lm) d! MÎ/ ¾ ") «š oo Zn 83.0, Fe. 5. 6. 7. 8.  Cu 19.4 Éx6Nk, lmŠ 10 × 4_ G/ ¾ *+p7) Ã%š, oo Zn 8.3, Fe 51.6, Mn 14.1  Cu 1.94 Cu ´ q L8% ¿ G*nmŠ lm«: ª_ * +pq «9:. Š lmŠ ;< # #34 g* ) 4_ GN S $l% Pmм ;< #/  b-g*Š ;< matrix g*/ §t * ‰ l &) H 5 ² Št žok, К / G*nm_ ;<q ”† ä ²W ÝY‰ *n%O *+%5 ² / ;< # b-g*Š rÅ *+ä 5 ² Št žo2:. Fig. 9/ o M ,-./ ¾ l;`m G *nm/ ¾ #34 g* *+ pq ÉxÒN k, Fig. 10/ #34 g* # Cu/ ¾ G*nm 516, Mn 141. Journal of the Korean Chemical Society.

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(38)        . 553. / Rh") ÉxÒ:† %$ ÒÃ? © :; ëH† 9%9Nk, 10 M/ Zn 34.77 mg/kg, Pb 9.87 mg/kg, Cd 0.103 mg/kg, Fe 4226 mg/kg, Cu. Fig. 9 Analytical results of heavy metals in sediments.. 6.418 mg/kgN ÉxÉ %$ ÒÃ? ©   † Ï 5-N 1¡‚ w6¡ áâ  Zn, Fe, Cu  ¹àY iN Tn ,-. # #34 ëH† ª¶ ÉxÉ çN $|2:. r- ϊ - X:Š z*T 3, 4  7 M/ #34 g* Š r- (_ ¦q ÉxÒ:. ÅúÉ 5 M/  d! abŠ ª_ ëHq ÉxÒ ¢, Š ;  6 <=Š — |¿ ,-. #/ 1 5 6(Š :8 01‚ ‚ 156(/ ¾ áâ  #34 ¹àY iN Tn #34 g* ëH † ª¶ ÉxÉ çN $|2:.   !" #$$%. '$ ’ , -. #/ Ù02 #34 ëH  ŽŽ† Nk, Š ƒ„g* ~ž  Š! >Ëe? @ i/ #µ¾ <† ¼ Šq *+%9:.  ‚A Ž  g(/ %š Ž (r) −1 Br B1 ") †k, r "Š +1/ †W´š "¾ A Æ; Žq, −1/ †W´š "¾  Æ; Žq ÉxÒ, r "Š 0/ †WC © Æ;Ž n™:. œ5 nT <q (x , y ), (x , y ), ..... (x , y )t % š, 'È Ž (r) : òŠ |k, Š · ) %O '$ ’ ,-./ Ù02 #34 g*  ŽŽq G%, Å pq Fig. 1112/ É xÒ:. 1. 1. 2. 2. n. n. n. ∑ (x i – x )( yi – y ). i=1. γxy = ------------------------------------------------n. n. i=1. =. ∑ ( xi – x )i∑1( yi – y ). Fig. 10 Comparison of analytical results for the Cu concentration in acid dissolution method (I) and elution testing method (II)..  l;`m/ ¾ *+pq r%O ÉxÒ :. G*n/ ¾ *+ pq 5{N «š #34 g* ëH 1 M/ ¿ ª_ ëHq «Š ¢, Š "   zP  wG/ ¾ ¤ ¥N $±2:. ½¾ #34 g* ëH 4 M 2000, Vol. 44, No. 6. BÐ-N %& '$ #/ Ù02 #34 7 $  08_ D ƒ„  o7 T i/ § t ; Ñ † ~žä h† NÉ, ,-._ ' $ /  ƒ„2 6(Š Ï5C/ E˜ Fe./ àY ½ áâ‚ ;gGNH, B;-T ;M/ ±|¾ '$ ’ ,-. #/ Ù02 #34 g* 08 š/ ŽŽ† ÐÌ; B|¾ ¥) I &:. È ^`/ '$  ( ,-. Ž Žq *+n È p Zn, Fe  Cd_ oo r= −0.357, r=0.29, r= −0.21 (_ ŽŽq ÉxÒNk,.

(39) 554. . Fig. 11 Relationships in concentrations of heavy metals in surface water and sediments. (a) Cu, (b) Mn, (c) Fe, (d) Cd. Fig. 12 Relationships in concentrations of heavy metals in surface water and sediments in heavy metals. (a) Pb, (b) Cr, (c) Zn.  Cu ´/ oo r=0.111, r=0.04 — Æ;Žq I J%9:. Š Mn Cu† žŸ% Mn. É Ï    1¡N T¾ çŠ fet ~ž -T T/ ¾ ç7) ;% :. Journal of the Korean Chemical Society.

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(41)        .   !" # $ %& # F8G HI AJ /zÜ UV UW, %& [$M i  ;- ¤¥) K M žŸ% , Ï  i 1 ¡N ƒ„Š ° 10] M '$  ,.) =>%O *+%9Nk, *+pq ¬LN :  ò_ pM) Hl%9:. 1) '$  ,-./ Ù02 #34 08 0 _ $/ %$ ÒÃ? © †% ¥) «9NÉ °8 Éx- M(site 1,2)H Nk, Š  "   zP  w/ ¾ ¤¥N žo2:. 2) '$ # #34 08_ oo Zn 0.019 mg/L, Cd 0.0005 mg/L, Fe 0.23 mg/L, Mn 0.0369 mg/. Š, Cr_ 5 M/Þ –8 ®l, Pb ®l Éx6Nk, Š d  (5{ Š% "Š:. ,-. #/ Ù02 # 34 08_ Zn 23.78 mg/L, Pb 6.8 mg/L, Cd 0.24 mg/L, L, Cu 0.014 mg/L. Fe 3350 mg/L, Mn 120.5 mg/L, Cu 2.06 mg/L, Cr.  Éx6:. M/ '$  ,-. #34 ëH† ª _ {N Éx- ç_ 6 |¿¸ ² T çN  $|k, 6, 7M/ '$  ,-. # #3 4 g* ëH Óh† Š/ T)   çN  $|2:. 4) '$ ’ ,-./ Ù02 #34C ŽŽq 3.49 mg/L 3) 5. 2000, Vol. 44, No. 6. 555. ®n È p, d! ab/ (_ ŽŽq «9 Nk, Š o &/ 1¡ %&/ ¾ #34  ƒ„Š — N) ÉxÛ:.. . ;  ; ; ;

(42) ; ;  , , 1975, 8, 23. 2. ; ;

(43)  ;

(44) ;

(45) ; 

(46) , 1982, 4, 199. 1.. 3. Ra, J. K. Pollution of heavy metals on the sediments of the lower Nakdong river; Yeungnam University: Ms. thesis, 1986, p 36. 4. Study Group on Minamate Disease Minamate Disease; Kumamoto Univ: Japan, 1968. 5. Pardo, R.; Barrad, E.; Perez, L.; Vega, M. Water Research, 1990, 24(3), 373. 6. Hurumay, H.; Ohgaki, S. Water Research, 1989, 23(6), 677. 7. Fox, I.; Malati, M. A.; Pery, R. Water Research, 1989, 23(6), 725. 8. Suh, S. D. Characteristics of heavy metals in sediments of small streams polluted by industrial waste water; Yeungnam University: Ms. thesis, 1991; p 1. 9. Boyden, C. R, Mar pollut. Bull., 1975, 6, 180. 10. Perhac, R. M, in Water transports of heavy metals in solution and by different particle size of particular solids; Office of Water Resources Research: National and Technical Information Service, vs Department of Commerce, 1974; PB-report PB-232427. 11. ; : , 1992. 12. ; : , 1992..        .

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