.

4/2550

-
(Acid-Base Accounting : ABA)


. 4/2550

-
(Acid-Base Accounting : ABA)

6 . 10400
0 2463 5942
0 2464 2054

2550
20

.
- (Acid-Base Accounting : ABA)
/ .-- :
4 ,
2550.
26 : : ; 30 .
. 4/2550.


.................................................................................................................
...............................................................................................................
......................................................................................................................
................................................................................................
.....................................................................................................
....................................................................
..............................................................................
...................................................................
...................................
....................................................................................
....................................................................................
....................................................................................
.................................................................
Active treatment ...............................................................................
Passive treatment ..............................................................................
..............................
.....................
..............................................
....................................................
.........................................................
.......................
ABA .....................................
........................................
.............................................................................
......................................................................................
.........................................................................
...........................................................................................
.....................................................................
...................................................................................
..................................................................................

VI
VII
1
2
3
3
3
5
7
7
7
7
8
8
9
10
10
10
12
13
13
13
16
16
17
17
17
18
19
19

 .....................................
..........................................................
............................................................................
....................................................................
...........................................................................................................
...................................................................................................................
...........................................................................................................

20
21
22
22
23
25
26

1.
ferric hydroxide ........................................................................... 6
2. (ABA) .............................. 16

1. ........................................
2. ......................................................
3. HCl
NP ........................................................................................................
4. () ABA .............

19
20
20
23

-
(AcidBase Accounting : ABA)

(Acid Base Accounting :

ABA)
(pH)
(Maximum Potential Acidity : MPA)
(Neutralization Potential : NP) acid potential
neutralization potential

ABA

ABA




4

4

(acid base accounting)


1. (acid base
accounting)
2.
(acid base accounting)
3.

(acid mine drainage)

1.
(acid mine drainage acid rock drainage)
(pH)
(Al) (Zn) (As)
(Mn)

(Wikipedia,
2007a)

2.

pyrite (FeS2), pyrrhotite (Fe1-xS), enargite (Cu3AsS4),

marcasite (FeS2), arsenopyrite (FeS2.FeAs2), tennantite (Cu12As4S13) orpiment (As2S3)
pyrrhotite, pyrite marcasite pyritic mineral





(H2SO4)





(Todd and Reddick, 1997)

90 %
Pennsylvania, West Virginia,
Ohio, Kentucky, Maryland, Indiana, Illinois, Iowa, Missouri, Tennessee, Virginia, Alabama
Georgia Pennsylvania Northern West Virginia
(limestone; CaCO3)
Rio Tinto


(Wikipedia, 2007c)
Britannia
2

(Wikipedia,
2007b)

3.
(pyrite; FeS2)

(physical weathering)

(chemical weathering)

3 (LEO and the SERVIT Group, 2004)
1
(S) (SO42-) (II) (Fe2+)
1 (H+) 2
2FeS2 + 7O2 + 2H2O
2Fe2+ + 4SO42- + 4H+
1
(II) (Fe2+) (III) (Fe3+) 2
1
(II) (III)
(pH 23) pH 5

4Fe2+ + O2 + 4H+
4Fe3+ + 2H2O
2
3
ferric hydroxide (Fe(OH)3)
yellowboy ferric hydroxide pH
pH 3.5 pH 3.5
(II) 1 3
4Fe3+ + 12H2O
4Fe(OH)3 + 12H+
3
1 3 4

yellowboy 1

4FeS2 + 15O2 + 14H2O
4Fe(OH)3 + 8SO42- + 16H+ 4



(II)
5 pyrrhotite 6

FeS2 + 14Fe2+ + 8H2O

15Fe3+ + 2SO42- + 16H+
5
2+
2+
Fe(1-x)S + (2-x/2)O2 + xH2O
(1-x)Fe + SO4 + 2xH 6
x 0.000 0.125

1
ferric hydroxide Wikipedia, 2007a

4.


(Todd and Reddick, 1997)

4.1



(reductant)

4.2

4.3



(permeability)

5.

2 active treatment passive
treatment (Environmental Protection Agency, 2007)

5.1 Active treatment

Active treatment

5.1.1 (Limestone)
(Limestone calcium carbonate; CaCO3)

5.1.2 (Hydrated Lime)

(Hydrated lime calcium hydroxide; Ca(OH)2)


()

5.1.3 (Soda Ash)

(Soda ash sodium carbonate; Na2CO3)

()

5.1.4 (Caustic soda)

(Caustic soda sodium hydroxide; NaOH)

5.1.5 (Ammonia)
(Ammonia; NH3)

5.2 Passive treatment

Passive treatment

passive treatment

5.2.1 Constructed Wetland

Constructed wetland passive treatment
wetland

1-2

5.2.2 Open Limestone channel/Anoxic Limestone Drain

Open limestone channel passive treatment

5.2.3 Diversion Well

Diversion well

acid base
accounting, humidity cell, soxhlet extraction, leaching test field lysimeter test
acid base accounting
(Perry, 1998)

1.
(Acid-Base Accounting; ABA)

3 (Paste pH)
(Maximum Potential Acidity; MPA)
(Neutralization Potential; NP) acid potential neutralization
potential

2.
(Maximum Potential Acidity;
MPA)
31.25
7
(CaCO3) 1000
(part per thousand; ppt CaCO3)
FeS2 + 2CaCO3 + 3.75O2 + 1.5H2O

2SO42- + Fe(OH)3 + 2Ca2+ + 2CO2 7

1 (molecular weight = 32) 1

CaCO3 (molecular weight = 100) 1 3.125
CaCO3 100 1
1 3.125 CaCO3

 1000 1 31.25
CaCO3 (%S)
31.25 MPA
62.5 8 MPA
CaCO3
MPA
31.25

FeS2+ 4CaCO3 + 3.75O2 + 3.5H2O

2SO42- + Fe(OH)3 + 4Ca2++ 4HCO3- 8

3




(chalcopyrite; CuFeS2) (galena; PbS) (sphalerite; ZnS)

(gypsum;
CaSO4) (jarosite; KFe3+3(OH)6(SO4)2) (alunite; KAl3(SO4)3(OH)6)






MPA

 MPA

MPA
MPA

3.
(Neutralization Potential; NP)
(carbonate mineral) (exchangeable
base) (silicate mineral)




NP CaCO3 1000
(part per thousand; ppt CaCO3)
(calcite;
CaCO3) (dolomite; CaMg(CO3)2) (chlorite; ClO2-) (biotite;
K(Mg, Fe)3AlSi3O10(F, OH)2) (siderite; FeCO3)

pH
NP

9 12
FeCO3 + 2H+

Fe2+ + CO2 +H2O

Fe2+ + 0.25O3 + H2O + H+

Fe3+ 3H2O

Fe3+ + 1.5H2O

Fe(OH)3 + 3H+

9
10
11

9 11 12
FeCO3 + 0.25O3 + 1.5H2O

Fe(OH)3 + CO2

12

9 10
(II)

 11
NP

NP

13 pH
6.4 14 15 pH 6.4
CaCO3 + H+

HCO3- + Ca2+

13

CaCO3 + 2H+

H2CO3 + Ca2+

14

CaCO3 + H2SO4

CaSO4 + CO2 + H20

15

4.
(Paste pH)





paste pH meter

5.
(Net Neutralization Potential; NNP)
NP MPA (NNP = NP-MPA)
(Neutralization Potential Ratio; NPR)
NP MPA ABA
(NPR = NP/MPA)

6. ABA

Thiobacillus ferrooxidans
CaCO3 pH
Acid-base accounting

ABA



ABA

ABA
%S, paste pH, NNP NPR, NP
MPA ABA
(Fey, 2003; Perry, 1998)
1) NNP 20 ppt CaCO3

northern Appalachian

2) NNP -20 ppt CaCO3

3) NNP -20 20 ppt CaCO3

ABA
humidity cell, soxhlet extraction leaching test

4) NPR 1

5) NPR 3
California Nevada

6) NPR 4
British Columbia
7) paste pH 4.0

northern Appalachian

8) %S 0.5 %
northern
Appalachian

ABA

ABA


1.


6
48 90 oC
(sieve) 70 mesh (desiccator)
(Colorado School of Mine, 2000)
(ABA) 2

ABA Analysis

Paste pH

Fizz Rating Carbonate Rating

%S

NP

MPA

NNP NPR
2 (ABA)

2.
2.1
2.1.1
2.1.2 pH meter
2.1.3 hotplate
2.1.4 C&S Analyzers
2.1.5
2.1.6 (vacuum filter assembly)
2.1.7 50 250 .
2.1.8 Erlenmeyer flask 250 .
2.1.9
2.1.10 0.45 m (Whatman 40) 0.20 m
2.1.11
2.1.12

2.2
2.2.1 (NaOH) 0.5 Normality (N)
2.2.2 (NaOH) 0.1 N
2.2.3 Bromothymol blue 0.1 %
Bromothymol blue 0.1 100 .
2.2.4 (HCl) 1.18
2.2.5 (HCl) 25 %
75 . 250 .
( 2.2.4) 25 .
2.2.6 (HCl) 0.5 N
700 . 1
( 2.2.4) 42 . 1
standardization NaOH

 0.5 N ( 2.2.1) 20 . Erlenmeyer flask 250 .

HCl bromothymol blue ( 2.2.3) indicator
HCl 1
N1 = (N2V2)/V1

N1 = normality HCl (N)

V1 = HCl (.)
N2 = normality NaOH (N)
V2 = NaOH (.)
2.2.7 (HCl) 0.1 N
600 . 1
0.5 N ( 2.2.6) 200 . 1
standardization NaOH 0.1 N ( 2.2.2)
20 . Erlenmeyer flask 250 . HCl
bromothymol blue ( 2.2.3) indicator
HCl 1
2.2.8 pH 4.0 7.0
2.2.9 (H2O2) 30 %

3.
(Jeffrey and Paul, 1996)
1) 10 50 .
30

2) 10 .

3) pH meter calibrate pH meter

pH 7.0 0.4 ( 2.2.8) electrode

4) pH calibrate pH meter
10

4.
(Fizz Rating)
(NP)
(Jeffrey G. and Paul T.Z., 1996)
1) 0.5 50 .
2) HCl 25 % ( 2.2.5) 2-3

4 1
1
Fizz Rating

2-3

NP
(Carbonation Rating) 5

5.

(Carbonate Rating) (Jeffrey and Paul, 1996)

1) 2 Erlenmeyer flask 250 .

2) HCl 0.1 N 20 .
(CO2)
3) 40 105 oC
4) vacuum suction

5) 105 oC ()
6) ()
7) (insoluble residue)
2
2
Carbonate Rating

% Insoluble residue

95-100

90-94

75-89

<75

6.
(Neutralization Potential; NP) (Jeffrey
and Paul, 1996)
1) 2 250 . blank
2) HCl ( 2.2.6 2.2.7)
3
3 HCl
NP
Fizz Rating/Carbonate Rating

HCl (ml)

HCl (N)

20

0.1

40

0.1

40

0.5

80

0.5

3) 100 . hotplate
5 ( blank chip
)

4) Whatman 40 Erlenmeyer flask

250 . 0.20 m
5) H2O2 (30%) 5 .
5
6) NaOH
HCl 2 bromothymol blue indicator
pH 7
30 H2O2 (30%) 5 .

7)
A = [B-(C x D/E)] x 25 x N

A = neutralization potential (ppt CaCO3)

B = HCl (.)
C = NaOH (.)
D = HCl blank (.)
E = NaOH blank (.)
N = HCl (N)

7.
(Maximum Potential Acidity; MPA)
CaCO3 1000 (ppt CaCO3) (Jeffrey
and Paul, 1996)
1) 1 C&S Analyzers
(% S)
3

2)
MPA = 31.25 x (% S)

8.
(Net Neutralization Potential; NNP)
NP MPA
4
NNP = NP - MPA
NNP
NP

= (ppt CaCO3)
= (ppt CaCO3)

MPA = (ppt CaCO3)

9.
(Neutralization Potential Ratio; NPR)
NP MPA 5
NPR = NP/MPA
NPR
NP

=
= (ppt CaCO3)

MPA = (ppt CaCO3)


ABA
() 6
4

ABA

4 () ABA

Paste pH

4.39

4.41

4.82

5.51

6.55

6.39

Fizz rating

NP (ppt CaCO3)

3.52

10.56

11.26

7.26

4.21

3.57

%S

0.001

0.16

0.056

0.009

0.006

0.001

MPA (ppt CaCO3)

0.03

5.00

17.50

0.28

0.19

0.03

NNP (ppt CaCO3)

3.49

5.56

-6.24

6.98

4.02

3.54

NPR

117.3

2.1

0.64

25.9

22.2

119

NNP, NPR, NP MPA
6

 ABA

(acid mine drainage acid rock drainage)

(pH)




(H2SO4)

Active treatment Passive treatment

(ABA)
(Paste pH) (Maximum Potential Acidity :
MPA) (Neutralization : NP) ABA

humidity cell, soxhlet extraction, leaching test

field lysimeter test ABA

ABA


Environmental Protection Agency, 2007, Treatment for Acid Mine Drainage, viewed
27/11/2007, http://www.epa.gov/reg3wapd/nps/mining/treatment.htm, 2 p.
Fey

D.L., 2003, Acid Base Accounting, viewed 23/08/2007,

http://www.swrcb.ca.gov/academy/courses/acid/supporting_material/usgs_acidbaseacct
.pdf, 34 p.

Jeffrey G. and Paul T.Z., 1996, Acid Mine Drainage Control and Treatment (2nd): West
Virginia University and the National Mine Land Reclamation Center, p. 21-68.
LEO and the SERVIT Group at Lehigh University, 2004, The Science of Acid Mine Drainage,
viewed
23/08/2007,
http://www.leo.lehigh.edu/envirosci/enviroissue/amd/links/science1.html, 3p.
Perry E. F., 1998, Chapter 11 INTERPRETATION OF ACID-BASE ACCOUNTING,
viewed
23/08/2007,
http://www.dep.state.pa.us/dep/deputate/minres/Districts/CMDP/chap11.html, 24 p.
Colorado School of Mines, 2000, Sample Preparation, viewed 21/07/2007/,
http://www.mines.edu/fs_home/jhoran/ch126/samprep.htm, 2 p.
Todd J. and Reddick K., 1997, Acid Mine Drainage, viewed 23/08/2007,
http://www.cee.vt.edu/ewr/environmental/teach/gwprimer/acidmine/acidmine.html, 4 p.
Wikipedia,
2007a,
Acid
Mine
Drainage,
http://en.wikipedia.org/wiki/Acid_mine_drainage, 6 p.

viewed

17/08/2007,

Wikipedia, 2007b, Britannia Beach, British Columbia, viewed 17/08/2007,

http://en.wikipedia.org/wiki/Britannia_Beach%2C_British_Columbia, 3 p.
Wikipedia,
2007c,
Rio
Tinto
(River),
http://en.wikipedia.org/wiki/Tinto_River, 2 p.

viewed

17/08/2007,