Ion speciation in seawater

1
????? ???? ???????? ?? ??? ?????

• Ion speciation in seawater

2
?????? ????? ????? ????????nonideal solution
behavior

• ??????? ????? ?????? A, B ??? ??????? ?? C, D
  ????????? ??????? ????????? ????????? a,b,c,d
  ???? ????? ??????? ????????? ??? ?????
• aA bB ? cC dD ?????? 1
• ???? ??????? ????????? ??? ???? ???????? Keq
• 
  ?????? 2
• ?? ???? ???????? ??? ???????? ??????? ?? ????????
  ???? ????? ??? ???????? ???? ?? ????? ????
  ???????
• ???? ????? ??????? ?? ????? ?????? ???? ????
  ??????. ???? ???? ?????? ????? ????????

3

• ???? ????? ????? ??????? ??? ???????? ?? ????
  ??????
• ???? ?????? ??????? ????????? ??????? ????????
• ????? ??????? ?? ????? ?????? ???? ???? ??????.
  ???? ???? ?????? ????? ????????
• ????? ?????? ???????? ??? ???????
• NaCl(s) ? Na(aq) Cl(aq) ?????? 3
• ????? ???????? ?? ???? ?????? ???? ????????
• ?t -n kf m ?????? 4
• ??? ?t ?? ????? ???????? ?? ???? ??????? n ???
  ??????? ??????? ?? ????? ??? ???? ?? ?????
  (?????? ????????)? kf ?? ???? ???????? ?? ????
  ??????? m ?? ??????? ????? ??? ??????
• ????? ??? ???? ?? ?????? ???????? ???? 2 ??
  ????????? n2 ? ????? ???????? kf 1.86 0C Kg
  H2O-1 ????? ????? ????????
• ?t -(2) (1.86) (1) -3.72 0C

4

• ??? ?? ??? ?????? ?? ????? ???????? ?? ????
  ?????? ?????? ?? ????? ?????? ???????? ??????
  ???????? 1 ????? ?? -3.01 0C ?? ??? ?? ??????
  ???????? -3.72 0C ? ????? ??? ??????? ?? ?????
• ???????? ??????? ???? ?????? ?? ??? ?????? kf
  ?????? ???? m ??? ?????? ??? ?????? ??? ??? ????
  ??? ?????? ???????? ???? ?? ???? ???? n ??? ?? 2
  ???? ???? ??? ?? ??? ???????? ??????? effective
  concentrations ??? ?? ???? ????? ????????
  activity ?? ??????? ????? ??? ?? ??? ????????
  ?????? total concentrations
• ???????? ???????? ??????? ?????? ??? 2 ????
• 
  ?????? 6
• ??????? ????? ?????? ???? ? i ? ????? ????????
  ????? ????????
• ??? ai ?? ?????? ?? ??????? ????? ??????? ?i ??
  ????? ???????? activity coefficient? mi ??
  ????????? ??????
• 
  

?????? 7
5

• ?? ???????? ??????? ???? ???? ????? ???????? ?i
  ??? ???? ??? ????? ?? ?????? ????-????
  Debye-Hückel
• 
  
• 
  ?????? 8
• ??? A ?? ???? ???? ?????? ? zi ?? ???? ?????? ?
  I ?? ????? ???????? ionic strength ???????
• ????? ???????? I ?? ????? ?? ????? ??????? ?????
  ??????? ?? ?????? ??????? ????? ????????
• 
  ?????? 9
• ??? mi ?? ????? ?? ???? ? Zi ?? ???? ?? ????
• ?????? 8 ?????? ?? ???? ???????? ??????? ?????
  ??? ??? ?????? (I) ??? ?? 0.01 ???? ?? ????
  ??????? (??? ?????? 0.002 m) ????? ?????? (???
  ?????? 0.7 m) ??? ??? ?????? ???? ????? ???
  ??????? ??????? ???? ?????? ????? ????? ????????
  ??? ?? ????????? ????? ????? ????????

6
(No Transcript)
7

• ?? ?????? ?????? ???? ai mi ????? ???? ?????
  ?????? ????? 1. ?? ???????? ??????? ???? ??? ??
  ????? ???? ???? ??????? ????? ?????? ?????
  ????????
• ??????? ??????????????? electrostatic attraction
  ??? ???????? ????????? ??????? ??? ?? ?????
  ??????? ??????? ?????? ???????? ?????? ?????
  ???????? ???????? ??????? ?? ?????? ????? ?????
  ????????

8

• ??? ??????? ?????
• ????? ??? ???? nonspecific ??? ????? ???? ?????
  ??? ?????? ??????? ????? ???????? ????????
  ??????? ?? ??? ???? ???????? ??? ?????? ??????
  ????? ?????? ????? ??? ???????? ???????? ?????
  free ions ????? ????? ?????? ????? hydrated
  (????? ?????? a)
• ????? ???? specific ???? ??? ????? ?????? ???
  ???????? ?? ??????? ??? ???????? ?? ????? ?????
  ????? ?????? ????? ?????? ?????? ????? ????
  ion-pair ????? ?????????? (????? ?????? b)

9
???? ?????

• ??? ??? ?????? ?????? 0.5 ??? ?? ?????? ????????
  (NaCl) ? 0.1 ??? ?? ??????? ?????????? ?? 1 ???
  ?? ????? ??????. ???? ????? ???????? ???????
  ???????

10
??????? ???????? competitive complexing

• ????? ???? ???????? ??? ????? ???? ??? ???????
  ??????????? ????? ??? ??????? ???? ??? ?? ?? ????
  ????? ?????????? (????? ????) ????? ?????
  ???????? ?????????coordination complexes
• ??? ???? ???? ??????? metals ??????? ?? ???? ???
  ????? ???????????? ????? ???? ?????? ligand

11

• ???? ??????? ?? ????? ????? ??? ????? ????????
  ?????????
• ???? ??????? ?? ?????? ?? ??????????? ?? ???? ??
  ????
• ????? ??? ??????? ????????? ???? ?????? ????? ??
  ?????? ??? ?? ?????? ??? ??????? ??????????
  electronic configuration

12

• ???? ????? ????? ????? ?? ?????? ??? ?????

?????? 10
?????? 11
?? ???????? ???? ????? ?????? ?? ??????? ????????
?? ??????? ????? ?????? ?? ??????? ???????????
?? ???????? ????? ???? ???? ????????? ??? ???????
?????? ???? ????? ???????
?? ??? ??? ???????? ??? ????? ????? ???????
????????? ??? ?????? ???????? ?? ??????? ?????
(??????? ????? ?? ???? ??????? ?????? ????????)
???????? ?? ????? ??? ??????? ?????? ?????
?????????? ??????? ?????? ????? ??? ???????
????? ???? ????? ??? ????? ??? ???? ???????
?????? ???????? ????????? ??????? ?
13
??? ????? ?????? ??????? ??????? ????????
???????? ??????????? ??? ????? 35 ?????? 25 ?????
?1 ??? ???
14
????? ????? ??? ????? ??????? ??? ???? ???????
???????? ??????? ???????
?????? 12
?????? Kc ???? ???????? ????? ????? ????
??????? speciation calculations ????? ?????
???????? ???????
???? ???? ????????? ??????? ??? ???? ???????
?????? ????? ??? ?????? ??????? ???????? ????
??????? ??? ?? ?????? ??????
15
???? ?????? ?? ????? ????? ?????? ?? ????????

• ????? ???? ????? 1 ??? ?? ??????? ????????? MgSO4
  ? 1 ??? ?? ?????? ????????? CaF2 ?? 1 ??? ??
  ?????
• ???? ??????? ????? ??? ???? ?? ??????? ?? 1 ?????
  ????? ???????? ???? ???? 2 ?????
• ??? ??????? ???? ????? ??????? ???????? ??
• Mg2(aq)? Ca2(aq)? SO42- (aq)? F- (aq)? MgSO40
  (aq)? MgF (aq)? CaSO40 (aq)? CaF (aq)
• ??? ???? ???? ????? ?????? ?????? ??? ???? ??
  ???????

16
?????? ?????? ????????? ???? ??? ?????
?????? 13
?????? 13 ???? ??????? ??????
?????? 14
???? ????? ??????? ?????? ??? ?? ?????????
?????????? ????????? ?????? ??????
?????? 15
?????? 16
?????? 17
17
?????? 18
???????? ???????? ???????
?????? 19
18
?????? ????? ????????
?????? 20
???? ???? ????? ??????? ?????? ??? MgF
?????? 21
??? ???????? 14? 15? 16? 17 ??? ?????? ??
????????? ????????? ????? ??????? ????? ??? 1
????? ????????? ? 2 ????? ???????? ? ???? ??????
20? 21 ????
?????? 22
?????? 23
19
??????? ???????? 22? 23 ?? ?????? 14
?????? 24
?????? 25
???? ????? ??????? ?????? ?????????
?????? 26
?????? 27
20
??? ??????? ??? ???? ?? ?????? ????? Mg2 ?
Ca2 ?????? ??? ??? SO42- ? F- ????????
????????? 16 ? 17
?????? 28
?????? 29
??? ??????? ??? SO42- ? F- ??????? ??????
???? ??? Mg2 ? Ca2 ????? ????? ???????
?? Mg20.034m ? Ca20.10m
??? ??? ?????? ???? ???? ???? ???? ??????? ?????
iteration ???? ????? ???????? ??? ???? ????? ??
?????? ??????? ???? ??? ????? ????? ????????
21
??? ????? ???????? ???? ??? ???????? ?????
??????? Mg20.050m ? Ca20.15m ?
SO42-0.37m ? F-0.83m
22
????? ??????? ???? ??????? ??????????? ???????
23
???? ???? ??????? ???????? ??? ??? ???? ?????
24
??? ?????? ??????? ???????? ?? ??? ?????
25

• ???? ?????????? ???????? ???? ??? ???? ?????? ???
• ????????? ?????? ??? ???? ???? ?? ????? ????? ??
  ??????? ???????????
• ???????? ????? ?? ???????? ???? ????? ????? ???
  ????? ??? ??? ??????
• ????????? ?????????? ?????? ????? ???? ??
  ???????? ???????????? ??? ?????? ????? 10 ??
  ????????? (???? ?? ????? 20-40 ?? ?????????)
• ????????? ??? ????????? ????? (??????????
  ???????????? ????????) ???? ?????? ?????? ?????
  ?? ???????? ??????????
• ???? ?? ????? ?????????? ???? ?? ????????? (?????
  ????????) ??? ????? ????? ?????????? ??? ?????
  ????????? ???? ???? ??? ??? ??????????

26

• ??????? ??????? ?????? ???? ??? ?????? ?????
  ???????

27
??? ?????? ??????? ??????? ?? ??? ?????

• ???? ??????? ????????? ???? ??????? ??????? ????
  ??? ???? ????? ????????? ?? ??????
• ?? ?????? ???????? ????? ??????? ??????? ??
  ?????????????? ????????? ?????????? ?????????
  ????? ?? ?????? ???????? ???? ???????? ??
  ????????? (S2-) ?? ??????
• ???????? ?? ?????? ??????? ???? ??? ?? ???????
  ????????
• ?? ???? ??????? ????? ?????? ???? ?? ????? ?????
  ?????? ????? ????? ???????? ???? ???? ??? ???????
• ?? ????? ?????? ??? ??????? ????? ??????? ???????
  ???? ???? ????????? ?????? ?????? ??????? ??? ??
  ????? ??????? ?????? ?? ????? ??????? ??? ??????
  ???? ???? ?????? ?????? ??????? ???? ????? ??
  ??????? ????????

28
???? ??? ?????? ?????? ?????? Cu? ?????? Pb?
????? Zn? ????????? Cd ??? ?? ??? ???????? ??????
???????? ???? ??? ?? ???? ???????? ???????
29
???????? ??????? ?????? ??? ???? ??????? ???????

• ????? ???????? ??????? ??? ?????? ?? ?????????
  ??????? ????? ???? ?? ???? ??? ???????? ?? ????
  ?? ?????
• ?????? ??????? ?? ??????? ???????? ????? ?????
  ????? ????? ??? ????? 99 ?? ??????? ???????
  organic ligands ??? ?????? ??????
• ??? ????? ?? ????? ??????? ??????????
  bioavailability ??????? ??? ?? ????? ????? ????
  ???? ???????? ???????
• ??? ??????? ???????? ??????? ????????? ??
  ???????? ????? ???? ???? ??? ????? ??? ????? ???
  ???? ??????? ?? ??? ?????
• ????????? ??????? ????? ????? ?? R-COOH? R-OH?
  R-NH2? R-SH

30
???????? ??????? ?????? ??? ???? ??????? ???????

• ?????? ?? ???????? ??????? ????? ??? ???? ??
  ?????? ????? ???????? ???? ???? ?? ????? ?? ?????
  
• ??????? ??????? ??? ?????? ????? ???????? ??
  ??????? ????? ????? ???????? ???????
  biomolecules ?? ???????? ??????? ????? ????
  ?????? ??????? ?? ????? ???????? ??????? ?????
  ????? ??? ??????? ?????? ?? ??? ?????

31
???????? ??????? ?????? ??? ???? ??????? ???????

• ??? ???????? ??????? ?????? ???????? ??????? ????
  ????? ????? ?????? ????? ????? ????? ??? ????
  ???????? ???????? ??????????? ?? ???????
  ??????????
• ???? ????? ferrichrome ?????? ???????? ???????
  ???? ???????? ?????? Fe3 (K1020-1060) ????
  ????? ???? ???? ??? ?? ??? ??? ?????? ???? ??????
  
• ?????? ???????? ??????? ?? ??? ????? ????? ??
  ?????? ???? ????? ?????? ???????? Humic subtances

32
???????? ??????? ?????? ??? ???? ??????? ???????

• ?????? ???????? ?? ????? ?? ?????? ?? ????????
  ??????? ????? ??? ??????? ????? ????? ??????
  ????? ?????? ?????? ????????? ???????? ???????
  ????? ???? ???? ?????? ????????? ?????? ???????
  ???????
• ?? ????? ?????? ??? ??????? ?????????
• ??? ?????? ????? ???????? ?? ??????? ?????
  ????????? ???????
• ????? ???? ???? ??????? ??????? ???? ?? ????????
  ???????? ?????? ?????? ???????? Uptake? ????????
  Nutrition? ????????? toxicity
• ???? ??? ??? ??????? ??????? ??????? ????????
  ??????? ?????? ??????? ??? ???? ???? ?? ?????? ??
  ???? ??????? ???????? ?? ????? ??? ?? ???? ?????
  ?????? ????? ??? ?? ???? ?? ?????? ??????

33
???????? ??????? ?????? ??? ???? ??????? ???????

• ??????? ???????? ????? ?? ???????? ??????? ??
  ?????? ???? ?????? ???????? ???????
• ??? ???????? ?????? ???? ????? ?????? ??? EDTA ?
  Tris
• ??? ?? ????? ??? ?? ?????? ???? ????? ???????
  ????? ?? ???? ??? EDTA ?????? ???? Tris (????? a)
• ????? ?? ????? ??????? ?????? ????? ?? ??????
  ??????? ???? ?????? (????? b)