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Geochemical Behavior of Metals in the Contaminated Paddy Soils around Siheung and Deokeum Mines through Laboratory Microcosm Experiments

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(1) , 35, 6 , 553-565, 2002 Econ. Environ. Geol., 35(6), 553-565, 2002.  microcosm   

(2)           * 

(3)   1. 1. 1. 2.    ,

(4) . 1. 1. 2. Geochemical Behavior of Metals in the Contaminated Paddy Soils around Siheung and Deokeum Mines through Laboratory Microcosm Experiments Jung-Hyun Kim1, Hi-Soo Moon1*, Joo Sung Ahn1, Jae-Gon Kim2 and Yungoo Song1 1. Department of Earth System Sciences, Yonsei University, Seoul 120-749, Korea Korea Agricultural & Rural Infrastructure Corporation, Anyang 430-600, Korea. 2. Seasonal variations in vertical distributions of metals were investigated in the contaminated paddy soils around Siheung Cu-Pb-Zn and Deokeum Au-Ag mines. Geochemical behavior of metals was also evaluated with respect to redox changes during the cultivation of rice. Two microcosms simulating the rice-growing paddy field were set up in the laboratory. The raw paddy soils from two sites showed differences in mineralogy, metal concentrations and gecochemical parameters, and it is suggested that high proportions of exchangeable fractions in metals may give high dissolution rates at Deokeum. In both microcosms of Siheung and Deokeum, redox differences between surface and subsurface of paddy soils were maintained during the flooded period of 18 weeks. Siheung soil had neutral to alkaline pH conditions, while strongly acidic conditions and high Eh values were found at the surface soil of Deokeum. The concentrations of dissolved Fe and Mn were higher in the subsurface pore waters than in interface and upper waters from both microcosms, indicating reductive dissolution under reducing conditions. On the contrary, dissolved Pb and Zn had high concentrations at the surface under oxidizing conditions. From the Siheung microcosm, release of dissolved metals into upper waters was decreased, presumably by the trap effect of Fe- and Mn-rich layers at the interface. However, in the Deokeum microcosm, significant amounts of Pb and Zn were released into upper water despite the relatively lower contents in raw paddy soil, and seasonal variations in the chemical fractionation of metals were observed between flooded and drained conditions. Under acidic conditions, rice may uptake high amounts of metals from the surface of paddy soils during the flooded periods, and increases of exchangeable phases may also increase the bioavailability of heavy metals in the drained conditions..   paddy soils, heavy metals, abandoned mines, microcosm, redox environment.    

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(12)  microcosm        !" #$% &'() *+ , 555 “i ) ¨0 2 mm9\ X9: ¡ 2001). ± KL² íÌ LK(loam)\. °K h Îîï ð ÊÎîï LKq wLKV ª ¦ Z microcosm ‡­$ 9 2. ~KL œ çJ¦) —m a, @7, Ù ‘ Îï Â+

(13) ÊÎï wLK, GLK2.  ± KL) ñ(order)-´ñ(suborder)-ò(great -7) D>E ¡ GX bR_\ ¬, ‡ , K çJ\ ¨9 2(Jackson, 1985). Y7  subgroup)-(family)-®(series)-8 "#_\ Í9| ¦) —m.+ 1œq KçJ$ m XRD ¦ Inceptisols-Aquepts-Haplaquepts Aeric-Fluventic Hapla(MXP 18A RINT-2500)) ‡9 _V Cu-Kα ”, quepts-Fine loamy, acid, mixed, mesic-íÌ®-óu 40 kV/30 mA, ˆ×(step-scanning, 0.02 /sec) $ E2(

(14) ôi³õ, 1977). µ¶Y <&öJ ? | Áó¨$ —x _\ zI9 2. 7¨-R _\ pH(ÍH Z 9V ‹ ÷g ø @ùÊ r úçE ¦' 0.1N KCl; Rump and Krist, 1988),  !AOP Ê Z -ûÊ A -ÊÍ\ =C –2(ü (calcium carbonate equivalent; Loeppert et al., 1984), o A, 1971). Yc @ùÊ Z ýþ¬-ûÊ M$ Ð L" #(cation exchange capacity; USDA, 1996), ÑF қ) ÿi9>? Ya ÒHYcV Ö @ 4 OP(total organic carbon; Nelson and =+ Y¦Y7\+ »Ù¦, »¦, @äÙ¦, Ø´¦ Sommers, 1982) A) ¦9 2.  14 NO , צ, electrum, ¦ A(üIE A, 1988) ¯ P ¦) —m $H¦(Ure, 1995)) R9 _V, , @¦,

(15) ¦, canfieldite, tetrahedriteA 2 ]M KL !Q<$ E KL`ash ×( ! «Y7t ¦ Z covellite A(Lü I™, , 1996)) , 0.1N HCl ŽÖOPJ ¦9 2. 1986)2. 1938ÝÞ 1942Ýá â 226 kg )  14 -R 8U ¦) —E ŽÖ ‹9 0 1961ÝÞ 1973Ýá+ s â 53 kg BCR ¦(Thomas et al., 1994) Tessier et al.   921 kg ) ‹9 _? T+ }Y_\ (1979) ¦) %9: ‡9 _V  8U  500 m,  30 m,  15 m Ϭ }¦ D (1M MgCl ), ade 8U(0.16M CH COOH), 1 I$. ö 645,160 m  Ϭ Ywh ¥\ ×  8U(0.1M NH OH&HCl), - 8U(30% H O x=C –2(E]¯14, 1996).  ±$ E Z 1M CH COONH ), ëÍc(aqua regia)_\ 9 !-R + ÀÁ A(1997), '¦ ni 2. è ¦$. ŽÖF '$ E Fe, Mn, Pb, (2000), Kim et al. (2002) A$ m Ä$J „ Zn, Cd, Cu IP AAS(atomic absorption spectroC0 –_V ×xF Y}7$ E  !š meter; Shimadzu AA-6701F)r 9: ‡9 2. Z

(16) š7  `a Q0=0 –2.  ± KL² < w LK(silt loam)V °K+ Îî      ï, ÊÎîï wLK ð wGLK, ªK+ ~KL$ E ‡M microcosm ¬ ‡­ èè ÊÎï, Îï, Îîï wGLK Z wLK Y Ywq ;HKL$ RE ( –+ Simms et al. 2. KLÍc_\+ Inceptisols-Aquepts-Haplaquepts (2000) Ritvo et al. (2001) ×) %9: Aeric-Fluventic Haplaquepts-Fine silty, mixed, nonacid, ‡9 2.   microcosm ! 30 cm,  mesic-< ®-9m

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(18) ôi³õ, o. 2. 3. 3. 2. 3. 2 2. 4. 1973).. 

(19) ~KLœ+ ³± µ¶±$. 2000Ý 11 $ Yw @ç tF ~) c_\ ¬o)  9: °K\Þ â 20~30 cm á ž9 2. ‚$. œ+ °KLïJ(Munsell's soil color chart)$ %3 _\ ÊÎï(very dark gray, N-3)) {0 ‡M$. ¯ #" ¡ ³ KL Î Rï(pale red, 2.5Y 6/2), µ¶ »Aï(very pale brown, 10YR 7/4)) {2. ¯q @Ð) m .   Schematic diagram of the experiment microcosm showing sampling positions (D1-D5 and S1-S5)..

(20)  

(21)   40 cm 1®8 ´)* +$ 18~20 cm \ ~K 

(22) L(12.1 kg)) ,0 c 4~6 cm Hª) @9v ÍH(10L)r - 9 2(Fig. 1). .v þ  KL ÍHr / 0C h&12 ¡ KL +  ~KL$ E çJ¦, pH, CCE, CEC, TOC Z ³ 19 cm, µ¶ 20 cm{_V KL‘ M$ ªJ†\  145 OP) Table 1$ D9 2. çJ °|$ 3 4(0.1 cm )) : \ 56 ! ¦ d ³ ¬ OP 60.1%\ LK(sandy 1 cm,  25 cm 18 @¨ú) éx9 2. + loam)$ 90 µ¶ ‡ 68.3%, K 15.7%\. ^7$.  @¨ú_\ r d9: @¨úM w LK(silt loam)$ E2. KL pH+ ÍH $ €8F ›Hr žÆ H –J9 9 2. ‡­ Z 0.1N KCl zID @9V ³ !, âE u  microcosm ^8R -r ú:9 _V K ¨0 µ¶ ) ?”F2. CCE+ ³$. c L‘ ïc-+ °KLïJ(Munsell's soil color R_\  D) ?”M0 CEC+ µ¶$.  chart)$ %& 99 2. D) Q _V TOC+ G «H µ¶ 24 2 microcosm 18 u ;H={_V ¡  . ~KLM Fe, Mn Z  14 NOP ³ H90 27á #";2. ;Hu W c‘ µ¶$ äm v ?”?V ¸ ± ¬¸ Yw$ m Hq ªJ† ›Hr 20 ml< ž9 _V ž ¡ `aF ~KL_\. ³± Yw cR_\  ÍH 500 mlr - c Hª) @9J9 9 2.  OP) '90 –2(»¼½ <¾¿, 1995). KLœ ž+ ;H ¡ 7, H ¡t 18 ¥¨ 0.1N HCl ŽÖOP ³ !, Pb, Zn, Cd, µ¶ 0 #" ¡t 27$ „Cê_V KL‘$ ! 5  !, Zn, Cd NOP$ äm 90%c ŽÖI ) ?”F2. cm =>) éx90 ?@`>r 9: ªJ† 1œ$ E X-· ÎJ¦ d (Fig. 2), ³ ~ \ ž9 2. œž ¡ 4@ç)  —m = KL Y7 ¦', ‚¦, 0KK, ÚL¦, þ¬, >M 4r Aç90 çr BC9 2. ³ Z µ¶ microcosm$. žE c‘Hq › ×m¦, ÷þ¦V µ¶ ¦', ‚¦, 0KK, þ¬h H œ$ m Eh(TOA RM-12P) Z pH(Metrohm ?”M2. KçJ$ E X-· ÎJ¦ d ³  550 C ÒN¨ OÔ=+ 7P Q)+ 0KK 704 pH meter)r zI9 0 Fe, Mn, Pb, Zn+ ICP-AES(inductively coupled plasma-atomic emission 0 10P 14P$. ?”?+ Q)+ èè þ¬q Ú spectrometer; Jobin Yvon 138 Ultrac)\, SO  IC L¦_\ ÓE2. µ¶ 300 C ÒN¨ OÔ9+ (ion chromatography; Dionex 80)r 9 _V S 14P ¦ 550 C ÒN¨ OÔ=+ 7P 0KK + Methylene Blue(Greenberg et al., 1992))  Z 10P þ¬h ,9v ?”æ2. Fe, Mn Z  145 -R 8U ¦(Fig. 9: ¦9 2. KLœ+ d#"90  1 4$ E ŽÖ¦) ‡9 2. ŽÖ 3)$. Fe !, ¸ ± ¬¸ 90% c ëÍc_ 1~KL œ$ RE × ˆ92. KL‘ c \ ST9 2. Mn ³$.+ RSh\ ëÍc $ 2«R_\ ‹F 7 H¡(18)$ ž9  59%\. ,9v ?”?V   8Uq a : SEM(JEOL JSM-5610LV)/EDS(OXFORD ISIS- 8Uh èè 21%, 17%r «T2. | µ¶$.+   8Uh 65%\ h‚ v ?”æ2. Pb Z Zn 300) ¦) ‡9 2. 556. . . o. 2− 4. o. 2−.  . o. Physico-chemical properties and metal concentrations of the raw paddy soils from Siheung and Deokeum. particle size distribution (%). Siheung Deokeum. pH. sand. silt. clay. DIW. 0.1N KCl. CCE (%). CEC (cmolc/kg). TOC (%). 60.1 16.0. 34.2 68.3. 5.7 15.7. 7.30 4.27. 7.17 4.24. 4.70 0.40. 5.00 12.4. 0.25 0.31. aqua regia-extractable contents (mg/kg). Siheung Deokeum. 0.1N HCl-extractable contents (mg/kg). Fe. Mn. Pb. Zn. Cd. Cu. Fe. Mn. Pb. Zn. Cd. Cu. 42,850 24,470. 900 450. 1,520 300. 2,770 640. 23 5.2. 550 35. 6,070 2,440. 270 240. 1,150 20. 2,480 465. 20 4.6. 160 16.

(23)  microcosm        !" #$% &'() *+ ,. 557. 

(24)  XRD patterns for the bulk samples, and the oriented and treated (ethylene glycol and thermal) clay fractions of paddy soils from Siheung and Deokeum. Chl: chlorite, Mi: mica, Tre: tremolite, Ka: kaolinite, Qz: quartz, Fd: feldspar, Cal: calcite, Dol: dolomite..  !, ³$. a de 8Uh, µ¶$.+   8Uh cR_\ ,9v ?”æ2. Cd Cu+ ¸ ± ¬¸ èè   8Uq - 8Uh v ?”?0 –2. XR_\ pHh  ³$.+   145 a de 8Uh ,9V | pHh U µ¶$.+   8Uh v ?”?0 –2.    . ;Hu  microcosm ^8R -\. KL ‘ h ³$.+ ;H ¡ 2V 18 cm, 9$ 17.5 cm, 18 H<$ 17 cm\ « 549 2. | µ¶$.+ 2 ¡ 21 cm\ h9 2h ¡ 19 cm\ @={2. ÂE µ¶ KL‘ c$ 2 ¡ Aï(reddish yellow, 5YR 6/8) ;<7 ?”? š9: H< H mm ¸W\ 8={2. 10$ +  ;<7 —$ 'c ²»îï(yellow, 10YR 7/6) ‹7 ?”? š9: ¡ KL‘ cr XY0 –{2. ³$.J 5$ ²îï(strong brown, 7.5YR 5/6) ;<7 KL c$ 8=0 ¡ H.   Fractionation patterns of metals in paddy soils from Siheung and Deokeum.. mm ¸W\ ¸Þ-ê_? 'c 7 ?”? Z[2. H ¡ 27$+ microcosm ~KL ³  ÎRï(pale red, 2.5Y 6/2), µ¶ »Aï(very pale brown, 10YR 7/4)) ?”MV #"={2.   : ;Hu  c‘H/›H ¦d r ;H ¡ Å(2~6), (8~12), ¡ (13~18)\ ?\C ¥ sD_\ †, ªJ† -r E´Q[2(Fig. 4). Eh+ ³ µ¶ ¬¸ 9  ›H$ äm KL/c‘H !ː ›Hq c‘ H$.  Ehr ?”MV ;H <$ ’“ c9 «r @T2. ] µ¶ !, 9 45.0~152.8 mV, c 661.8~728.6 mV\ ^_E «r tÆ H –{2. pH+ ³ !, c9h E ¨ "#_\ ch `a  pHr ?”M{2. µ¶ ³ + \ c$. 3.22~3.75\ 9$ äm a U û.

(25) 558.  

(26)  .   Depth profiles of Eh, pH, Fe, Mn, Pb, Zn, SO42− and S2− at early, mid and late stages during the flooded periods of microcosm experiments.. ) Q 2. Fe Mn .\ @E >) ?”MV ³ µ ¶ ¬¸ c$ äm 9$. a  Ö) Q 2. ÂE µ¶ 9 Ö ³$ äm Fe  11 , Mn  9.4\ 3[2. ³ µ¶ ¬¸ ; H , ¡\ îH9 9 Ö )v 549: c 9 «h 549: ?”æ2. Mn Fe$ äm c$.J ;H Å cbP Ö ˆCæ2(³ 11.5 mg/l, µ¶ 169.4 mg/l). Pbq Zn+ Fe Z Mn \ c$. a 3. Ö ˆCæ2. ³ !,  Pb 0.81 mg/l, Zn 2.7 mg/l, µ¶ !, Pb 1.8 mg/l, Zn 29.7 mg/l_\, µ¶ Pb+ 2.2, Zn 11 3 Ö) Qt2. ³ !, c !Ë| ›Hq c‘H Pb Z Zn

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(30) Jh !Ë| ›HQ2 A] v ?”?V  ¡$J .\ @E

(31) J\ @90 –2. 9 !, wwE «.

(32)  microcosm        !" #$% &'() *+ , 559 f 9? ³  Pb 0.17 mg/l, Zn 1.4 mg/l JP -R 8U -+ Fig. 5q ¹2. KL‘ \ µ¶$ äm a  Ö) ?”M0 –2. 9 ªJ 4m  œ$ E ¦d , JO SO  ³ !, Å$+ cq 9h > P -R 8Uh G -H @9v ?”?  «r ?”M Z2h , ¡\ îH9 D d r s9: 9‘(subsurface)_\ °90 KL c 1,490 mg/l, 9 900 mg/l\ ^_E «r ?” /c‘H !Ë|(interface) d q ä9 2(Fig. 5). ‡ g2. µ¶ Å$ `]Ÿ 9$.  2,740 mg/ ­u  7q 18+ cR_\ 1 !_\  ] 18+ 1 ap ijF cUV 27+ c l_\ a  Ö) ?”M2 $ h.˜ 9 Ö d59|. c$. a 3 Ö) Q 2. R - !& Æ H –2. Fe ¸ ± ¬¸ ¥ OP !Ë|$. 1œ$ ³, µ¶ ± ¬¸ S +  ›] U

(33) J\ ?”æ_V è $. ¥  ª9 2. ³ äm h9: 9$.Q2 v ?”M2. ] µ¶ ;H ÅQ2 $ ¥

(34) Jh _V 9 ›H 7 !Ë|$. OP 3.5%á h9 _V 1 $.  2.4 mg/lá ?”æ0 h žF œ$  8Uh ^_ ?”? Ù-7 ‹) E2. . »ijr k) H –{2. µ¶ ¥

(35) Jh c ³$.J 9$ äm !Ë|$. 1 8Uh  R_\ U0 Å$ 9 ›H$. 0.05 mg/l  h9: ?”?0 –_V c - !$. ÙD) QV ¡ <XR_\ 549: ¡$ ¦E 7 8n) Q:2. † -R 8U -+ ¸ ± ¬¸ ëÍc 90% c) «9: ^_E Ëx(0.002 mg/l) 9\ lÖ= Z[2.  : microcosm KLM  †, ªJ† -r o Cp2. 2− 4. 2−.   Sequentially extracted Fe, Mn, Pb and Zn (mg/kg) in raw paddy soils and microcosm soils..

(36)  

(37)   $ 1œ$ äm JOP 54q OW ëÍc) Mn !, ³$.+ Feq RSh\ !Ë|$. 1œ$ äm OP h9:(1,220 mg/kg) ?”? D^E 8Uh 5490 18$ OP h9|. ™ µ¶$.+ 27$ h.˜ !ː OP )v a de 8Uq 1 8Uh ?”M2. 27$+ hE2(600 mg/kg). -R 8U+ ³ 9$.  9q RSh\   8Uh )v hE2. KL/c‘H !Ë|$ 2«R_\ 8F 7$+ ä  8Uh 549: ?”?V !Ë|$.+ a de8Uh h9: ?”M2. µ¶ !,   8 I Â+ dIJh U Ù-7 2P €9+ Uh ,9v ?”?V 27$ JOP hq OW º_\ Ó=V SEM/EDS ¦$. Ù-7 Y7 ç¯ °|$ ;<F 8U? c 8eX 8U\ \  8Uh 84.3%\ 3 ) «E2. ú:={2. ] µ¶$. 8F ;<7$. q¹ Pbq Zn OP -+ ³ !, Fe Z Mn RSh\ !Ë|$. 7Þ )v h9: ?”?  Lc) qv ú:Æ H –{_V c 8eX$ V ¡ « 5490 –2. | µ¶$.+ \ E X-ray r+$. Feq Oh ^_ ¦=0 !Ë|$. 1œ$ äm )v 5490 18$ 1 4P S, Si, Al AJ €9+ º_\ ?”æ2(Fig. œq @E OP), 27$+ Q2  OP_\  6A). µ¶ c‘ ' 7 w‹7Rt % h9: ?”M2. -R 8U -+ ³$. Pb Z 7\ ŽI=V ;<7 ×c Ø@ 7 X 0t cU\ ?”æ2. :$.+ f  8Uh  Znh !Ë|$. \ a de 8Uq 1 8 Uh 1œ$ äm hE Lc) Q:V 9$. \ ú:=0 EDS ¦d Fe, S Z Oh \ € + 1œq @E 8U€r Q0 R_\J 9+ º_\ ?”æ2(Fig. 6B). G -h H2. µ¶ !, 9$. ;Hut 7 q 18$ 1œ$ äm   8U+ 5490   a de Z - 8Uh h90 –_V + 18$ a ^_92. 27$+ 9J - !_\     -=V  8Uh )v hE2. !Ë|$.+ 7 ³ Z µ¶ Y ± ~KL -R  560. .

(38) .   Scanning electron micro-photographs and X-ray spectrums of the surface materials from the Deokeum microcosm. (A) in Fe-rich precipitated layer, (B) in glutinous material..

(39)  microcosm        !" #$% &'() *+ , 561  pHh ^_E «r QV ³±$. µ¶Q r @90 –2. µ¶ 9+  pHr ?”MV 2 v ?”M2. ¸ ± ¬¸ »-Y7) O@9+ + 1 !$. »-Y7 IO) E2.  Yw$ m `aF KL¤\ »-Y7 -$  | ³ !, - !t cQ2 1 !t 9 E  pH 8 yc=™ ³±$.+ KL $. 24 U pHh ?”?V ¡ h9: c M aY7 m I$. H4") 4¬9: pH q «h 5490 –2. + ;HÅ 9KL M S - 4

(40) {$ m pHh cR_\ r cs º_\ ÓE2(Blowes et al., 1998). 54F º_\ Ó9V iRt 3hÙ H-7 CaCO +H tCa +HCO (at pH>6.3) »a 1%_\ tm pHh csy H –2 CaCO +2H tCa +H CO (at pH<6.3) (Bachmann et al., 2001). ;H $. S

(41) J hh [E »a 1%) E2. X-· ÎJ¦ d ³± ~KL$. ×m¦ Z ÷þ¦ t={_V  !AOP(CCE)J c Fe(OH) +3H +e =Fe +3H O R_\ v ?”? r u*;E2. SO +2H O+2H =H S+2CO +2H O KL çJ€ Z Y7"$.J «r QV ¸ ± ¬¸ ;Hu  cR_\ c+  \ tm ;Hu  microcosm KL‘  -$ «h ?”?0 –2. µ¶$. KL‘  - !, 9+ 1 !) „0 –_V µ¶$. c h+ Q2 3 K OP ¦) €OE K 9u pH «h a )v ?”?V EhJ ^_E « r Qt2. vÀ$ tE º2. ;Hu  Fe 9$. \ 1 m   OP ¸ ± ¬¸ ˆKLM OP c_\ Ö=0 –_V c\ (diffusion) F (Sposito, 1989)) Å 9: ?”?V ³±$. Pb, 2h Ù KL/c‘H !Ë| - !$. Ù-7 Zn, Cd, Cu$ E `a, µ¶$.+ Pb, Zn, Cd$ E `a ?”?0 –2. ³± cR_\  8U\ ;<=+ º_\ ÓE2. !Ë| ;<7$   OP Yw wR @ç$ E `a) '9 E SEM/EDS ¦$.J t ={_V 7 Z 18 V YwM ) O@9+ »-Y7 OP µ¶ $ žE KLœ$. !Ë|$. Ù

(42) Jh ) Q2 ³±$. v ?”M d q ˆxE2(»¼ v h90 1 8Uh ^_ ?”? r u* ½ <¾¿, 1995; ÀÁ A, 1997).  - ;90 –2. ;H  ¡ 9 ÖP 54+ Q R 8U ¦d $. - 8U$ äm ³$.+ 2 IE 8Ut a de 8U Z »-7 8U\ a de8Uh, µ¶$.+  8Uh ,9v  < ) wE2. ] µ¶ microcosm$. !Ë| ?”?0 –_V + »-7 8U\ @çF  Fe

(43) J hh 7$ ^_ ?”?V ' 7 Rt x-š_\ w 3 -'() *[_  8F º) | h w‹7 š$ m Ù-7 V KL pH A -R "#$ %& -R 8 ‹ }iF º_\ ÓE2. ˆR_\ Y Uh  F º_\ ÓE2. ³  J OP Hq ¹  pH "#$. Ù- ~¨´ $ äm   8U OP  µ¶$.  (Thiobacillus ferroxidans A)h 2h Ù -r }i 0 ÙH-7(ferrihydrite) 8$ :9+ º_  Ö v ?”• H –2. \ EŸk –2(Kasama and Murakami, 2001). ÂE ü A(1999) $. }Y @ÖH H\q 8

(44)   !" #$ ;Hu ³ µ¶ microcosm cq 9 H »ï Z Rîï ;<7t (`W$. €È + ^_E - 1 Z pH ! «r Q:{2. c Z c ~¨´ 7) t9 0 5 ;H<$ ’“ ³ cq 9, µ¶ 9+ ~¨´h \ ;Ù¦ Z RÙ¦_\ =+ -Ù ¯H '±$ 9™ µ¶ c+ Ehh 577~ \ Y7- š) ˆ_+ º_\ Q0E ( –2. © $.J pHh  ³Q2+  pH "#t 763 mV, pHh 3.1~3.9\ YH '±$ E2. ¸ ± ¬¸ Yw @ç$ m »-Ù ¹ »-Y µ¶$. q ¹ w‹7 š yc=V !Ë|$ 7 -q 2«R_\ ‹F »a Y7 m 8F ' 7 YH$. ú:=+ ( I_\  pHh 8y H –™ ³ !, `W  J ˆx90 –2(ü A, 1999). a Y7 m$ %3 zÿš_\ âE ¨ pH KL c‘$ 8F Ù-7 ‘ wP L" Z 3 3. +. − 3. 2+. +. 2+. 2. 3. 2−. +. 3. 4. 2−. 2. −. +. 2+ 2. 2. 2. 2.

(45)  

(46)   ¶"$ E B6 _V(Alloway, 1995)  \ ŽIE2. + U pH !$.+ Pb Z Zn 14 c‘H\ ) DC9+ ‚±Æ) Hj Jh h9: Ù-7  de qv ˆC? Æ H –2. Holmstrom and Ohlander (2001)   Z hù2(Alloway, 1995). ;Hu  KL $.J ;HF Yw c‘$. Ù/ƒu -7 x 9$. -R 8U -(7 Z 18)$.  E ‘ 8=0 :$  145) B6   8U+ 5490 a de Z - 8Uh  + ;<_\ c) „D9+ º_\ ?”M ( h90 –C 9  pH !$. -R 8U -h ЋO) Q:2. ¡ 27$+ KL‘ 9 –2. J - !_\ < =V pH 54h yc=V c Mn !, S Mn + Fe @9v >9: ;HKL$. 1=C =0 c$.+ -=C 9‘ ¬¸   8Uh )v h9: ?”M2. Pb Z Znq ¹  14+ - 1 ! Mn(IV) -7 8U\ ;<=™ ;H Å !Ë| ›H Z c‘H$.J cbP Ö=0 –_V  $ ˆ5E 14h ´L™ q ¹ pH "#  + Fe $ äm Mn  -IJh =C ?”ö) -h )v ?”?+ !$.+ - 1 ! -$ wE2(Ponnamperuma, 1972). ] ³$ äm %3 -R 8U -h ?”• H –¶) Q: 2(Gambrell, 1994). pHh U µ¶$.+ ;H  ¡$J !Ë|  ;H Å ³ Z µ¶ »a

(47) J+ c9 ‘ ›H Z c‘H$. 100 mg/l c

(48) Jh ?”?V !Ë| KL$.J ^_E OP hr Q Z0 ¬¸  Ö c) QV + microcosm$. –C ^_E Mn -7 ‘) 89 Z[¶) D »-7 -‰™ ´L& w 2«R_\ ‹F » a Y7 Â+ Ù-7$ B6F »a mc E2. J )v ˆC?0 –¶) wE2. ˆR_\ »Pb Z Zn+ Fe, Mn  >) QV !t c$. »-7 8U Z   8U m Y7 - I$. »a 2«Rt »a Y7 \ ցc ?”?+ º_\ ÓE2. ]  (¯\, ¦0 A)) 89>? äI ÙH7 °|$ B6F 8U\ STÆ H –_V(Rose and pH "#t µ¶$. 1KLM NOP ³Q2 U[ ™ ëÍc ^ 8U Ö\ a  OP ?” Elliot, 2000), © ± ~KL$J Yw @ç ?0 –2. ÂE ³$.+ ;H Å c‘H

(49) J ¡ Rt x-š_\ 2P »a w Ö h !Ë| ›H$ äm @9>? 24  OP =C —q ¹ 8U\ STÆ º_\ ycE2. µ¶ _\ ?”æ_?  ¡$+ )v 549: ?”? ± c$. 9$ äE

(50) J 54+ ;HÅ V !Ë| KLœM OPJ 7Þ h9: ?” Þ c‘$ ‹F Ù-7$ »a " 2P M2. + $. †dE (q ¹ !Ë|$ 8F B6F º_\ ÓE2. ;H  ¡ KL 9 Ù Z ƒu -7 ‘$ Pbq Znh B6=>? ;  »a "

(51) J 54+ »a 1%)  <=C c‘H\  DEF º_\ ycE2. - 9V S 

(52) J h\ ?”M2.  SO  O R 8U ¦$. a de 8Uq 1 8U P$ äm S  Ö IJh W, Uv ?”?+, h ^_ h9: pHh  !$. Ù/ƒu - ˆR_\ SO h S \ 1=a&J ScU\ 7$ B6F  a de 8U\ <  zIy H –+ S

(53) J+ 0.1 mg/lc =h Š‹ ˆCö) DE2. ³ 9 KL$. ;H Å Zn º_\ EŸk –_V(Ponnamperuma, 1972), ‹F h 1.0 mg/l c

(54) J\ ?”?V + 1KLM S h Ù Z  14q de9: (\ ;<9 1 8U\ ST9‡ Zn Ö\ ÓE2. R hù2. µ¶ 9 KL$. Pb Z Zn - 8 _\ ³ 9 KL$. 27 KL <Xh - ! Uh 1KL$ äm 24 h9 _V [E @\ _\  =CJ -R 8U -+ ?”? Z0 µ¶ S 

(55) Jh ³$ äm ap U º_\ –2. | µ¶$.+ c‘H

(56) Jh !Ë| ›H ycE2. $ äm v ?”?V !Ë| KLM OPJ )v 5 49: Pb Z Zn Ö DC= Z0 –¶) Q %&' ()* +, :2. ¡$J !Ë| ›Hq c‘H

(57) J ˆR_\ G7  BHJ+ KLM JO h @9v ?”?V KL c‘$ 8F Ù-7 PQ2+ KL 7¨-R  $ %3  ‘ ‚±Æ U>? =C ?”?0 –+ º_  -R 8U$ SE2. KL 7¨R  Y 562. 2+. 2+. 2+. 2+. 2− 4. 2−. 2−. 2−. 2− 4. 2−. 2−. 2−.

(58) .

(59)  microcosm        !" #$% &'() *+ , 563 7", çJ€, KOP, KL›H OP A$  r Q+ 9$.+ Mmt a de 8Uh m «h ?V -R  pH, Eh, @7 OP =™ #" ¡$+ 2   8Uh )v hE Z a »-7 ¹ §-e7 OP A_\ 2. %&. µ¶±$.+ ;Hu ] c‘H «h M2. èè £t$ %3 Šš7  B Z KL 9 ›H$ SF  Šš7 H !( ‚ OW 2L9v ?”?™,  ‹‚$ '() w º_\ yc=V ¡ H$J  BHIJh v ?”• H –2. pH "# - !ˆ !,  mJh ´ V G7 BHJh (cn Q0F ( –2(Giblin et al., 1989; Khalid et al., 1981).. KLM  -R 8U+ ›H$ SF 8 Uq 2LE ŽÖ¦$ %& KL 087M$   8U, a de8U, 1 8U, - 8 U Z ëÍcA_\ Í=Ci2. ›HM$ SF 8U+ wR_\ Šš7\ BHh h‚ 9V,   8U+ Œ I<R de Â+ " 8 U A_\ B6F 8U\ de â9: qv 7$  mF 8Uh y H –C ÂE BHJh 2. a de 8U+ pH$ ˆ59: E ¨t !, Mm ?  pHˆ !,$+ mJh / H –2. 1 8U+ \ Fe, Mn -7 deF 8U\. - !$.+   ûE de_\   ) „D9™ Šš7 ‹Œu ¹ 1 ! $. Ö ´i2. - 8U+ @7 Z » -7 deF 8U\., KL c - "#Q2 9 1 "#$. a û9v deF Mm F2. ëÍc 1 Y7 dI "M$ deF M m2(Gambrell, 1994). E ¨ pHr + ³ !, Pb, Zn KLM JP ä`a KL sOP) Å 9 0 ;H u Pb, Zn !, Å$ c‘H$. 

(60) J\ Ö={2. ¥[?  KL/c‘H!Ë|$ Ù, ƒ u -7 8_\ c‘H\   d5 9 0 ¡$+ c9 <X$.  0.1 mg/l  9 H_\ Ö={2. -R 8U ± 1œt a de 8Uh ) «9V ;H&H < Xu$ ’“ c9 ¬¸ ^_E -R 8U -r Q Z[2. %&. ³±$.+ ;H Å Pb q Zn 

(61) J+ CŽ ¬ ‹‚$ '()  H –_? ¡ ;H ¡q H$+ ¥ BHIJh U) º_\ ycE2. c$. U pHr ?”M+ µ¶ Pb, Zn K LM JP ³$ äm cR_\ U OP ™ ;Hu c‘H\ ÖF OP ³$ äm v ?”æ2. -R 8U+ 3 ) «9‡   8Uh ;Hu $  M E ¨ pH. .

(62) . ~KLM  -R >) "9 —E ‡M microcosm ‡­$. ³ Z µ¶ ± ~KL  ;Hu  KL c9 ‘u$ ^_E - 1 ! «r Q 2. Fe Z Mn ¸ ± ¬¸ KL 9 1 !$.  ÖLc) QV 1  m c) ?”M{2. KL c‘$. ¥

(63) J+ ) v 5490 Ù-7 xE ;<7 ‘) 89 _V µ¶±$. ^_9v ?”? w‹7š yc F2. Pb Z Zn !, KL c - !$. Ö  v ?”?V pHh  ³   OP ) 0 –_? cR_\ ÖIJh U0 ;H& H <Xu$ ’“  -R 8U -+ ˆC ? Z[2. pHh U µ¶ !, cR_\ U  OP) 0 –_? ¥ ÖIJh _V KL c Ù-7 ‘ ‚±Æ U>? =C   Ö R_\ ˆCæ2. ÂE ;H 9 KL$.+ a de Z - 8Uh h90  H ¡$+ c9 ‘ ¬¸   8Uh )v h9 : ?”? †\ ST 8Uh -9 2. `a H cR_\ U29a&J û ~K L ;H$ KL c‘$. Šš7  BH Jh hÆ H –_V H ¡$+   8U  h\ ± ¥ BHJh ´ º2. !ƒ1 «1 $. `a H + úËH pHr + º `a F ~KL ƒ1$ W, £92 9‘2. ÂE  ä? !š_\ tE KL -h ijy !, µ¶ $ äm  JP  ³ ’TR `a h# ´ ªèE ùDr ˆ_“ H –2. µ¶ !, U pH\ tm - !$.  14  Ö qv ˆC?0 –C C”E Ym× "xh =C – Z+ c»$. Šš7 Qmh yzF2..   © + E] T ñRÅ( D•¼:.

(64)  

(65)   Fortescue, J.A.C.F. (1980) Environmental geochemistry. R01-2000-000-00057-0) äq Œ 1 BK 21 Springer-Verlag, New York, 387p. ! – 1$ m „Cê2. Gambrell, R.P. (1994) Trace and toxic metals in wetlands564.  Š‹Œ (1970) mŠ Œ" Ž9 m 23  . 3‘, p. 172-175. ’“”, •–#, —˜, b™m (1999) š ›  œ, 0%F  9P" !7" h € VW. B768<ˆ, 32ž, 3‘, p. 261-271. iŸ ¡ (1973) ¢, £¤j¥, mŠ|¦j (1:25,000)-21. iŸ ¡ iŒ§. iŸ ¡ (1977) ` ¢, 3j¥, mŠ|¦ j(1:25,000)-35. iŸ ¡ iŒ§. mŒ ¨3 (1968) mŠ" . 1‘, p. 40-41. ©ª«, ’   (2000)

(66)  ¬œH " !9 m #?­#$%n &9 m . B7 68<ˆ, 33ž, 2‘, p. 91-100. `˜–, ® , ’¯# (1999) › ° bZ#9 "S VG‰ ±K²y" ³F=% . mŠF =´<, 12ž, 1‘, p. 32-42. ˜, <|µ (1986)

(67)  F" ¶jH 2$. <ˆ, 19‘, p. 227-237. ˜|m, ·Y7, ·¸¹ (1988) mŠ Pºa"

(68) » · ›9 m ¼«<*=% . <ˆ, 21ž, 4‘, p. 389-400. K˜“, žª›, Kn (1971) mŠ<ˆj u½j¥. »= §¾, Š‹<ˆ23j, 25p. K€ª, Kn‘, K¿ª (1996) !  " , ÀF 0Á" !9 m <*=% - G 8. B768<ˆ, 29ž, p. 597-613. K #, ·¸¹, ’8à (1997) k<E ÄÅÆ› &'< E9P" ¼«--ÀFr- ǀ% ÈG7É" & » K. B768<ˆ, 30ž, 6‘, p. 587-601. KÊË, ©ª«, ©Áª, | , (1997)

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