-------
TABLE 12. CHEMICAL COMPOSITION OF FLY ASH AND SLURRY SUPERNATANT SOLUTIONS OF FLY ASH
FROM AN ILLINOIS NO. 6 COAL AT SEVERAL pH'S
Chemical composition of 10',". slurry supernatant
Air
(mg/L)
Constituents
Ag
Al
Au
As
B
Ba
Be
Br
Ca
Cd
Ce
Cl
CODr
Cr
Co
Cu
Cs
Oy
Eu
F
FeTotal
Fe+2
Ga
Ge
Hf
Hg
K
La
Li
Lu
Solid ash
(mg/kg)
<1.8
73,600
—
46
600
490
16
<3
26,100
<1.9
57
28
—
130
25
140
11
9.3
1.6
133
134,400
—
51
15
3.9
0.05
20,900
34
—
0.5
PH
8.82
0.62
—
<1.0
40
<0.1
<.02
—
130
<.03
_
<25
3
<.02
<.05
<.04
—
—
—
1.5
<.05
<0.1
—
—
—
<.0002
36.0
—
0.15
—
PH
7.97
_
<0.3
—
<1.0
46
<0.1
.026
—
435
<.03
_
<25
1
<.02
<.05
<.04
—
—
—
1.4
<.05
<0.1
—
—
—
<.0002
10.2
—
0.24
—
PH
4.08*
_
62.6
—
<1.0
58
<0.1
.052
—
508
0.39
_
<25
. 5
<.02
0.31
0.20
—
—
—
2.5
13.5
9.0
—
—
—
<.0002
1.4
—
0.53
—
pH
2.74
_
419.0
—
<1.0
62
<0.1 •
.094
—
879
0.57
_
<25
10
1.94
0.44
0.84
—
—
—
0.16
155
87
—
—
—
<.0002
10.8
—
0.55
—
PH
9.98
4.12
—
<1.0
44
<0.1
<.02
—
401
<.03
<25
4
<.02
<.05
<.04
—
—
—
1.2
<.05
<0.1
—
—
<.0002
56.0
—
0.11
—
Argon
(mg/L)
PH
7.08
<0.3
—
<1.0
52
<0.1
<.02
—
449
<.03
<25
1
<.02
<.05
<.04
—
—
—
0.72
<.05
<0.1
—
<.0002
17.0
—
0.41
—
pH
4.26*
32.6
—
<1.0
57
<0.1
.043
—
506
0.25
<25
17
<.02
0.25
<.04
—
—
—
3.0
no
92.5
—
<.0002
1.1
—
0.60
—
pH
2.52
406.7
—
<1.0
64
<0.1
1.03
—
872
0.51
_
<25
43
1.91
0.50
0.95
—
—
—
0.13
270
210
—
<.0002
16.1
—
0.66
—
36
-------
TABLE 12. Continued.
Chemical composition
of 10% slurry supernatant
Air
(mg/L)
Constituents
Mg
Mn
Mo
Na
NH,,
Ni
Pb
P
PC*
Rb
STotal
s-2
SO*
Sb
Sc
Se
Solid ash
(mg/kg)
3,500
380
67
13,200
—
160
110
873
—
170
14,900
—
—
3.5
20
16
Si 194,300
Sm
Sn
Sr
Ta
Te
Th .
Ti
Tl
U
V
W
Yb
Zn
7.r
EC (iimihos/cnt)
Eh (electrode
7.7
11
310
1.2
2.0
12
.5,100
1;2
<12
230
6
2.6
560
200
—
niv) —
pH
8.82
0.28
.03
3.5
367}
<0.1
<.07
0.15
—
<.01
—
—
—
3,650
<0.4
—
<0.5
1.33
—
<1.0
0.27
<0.5
—
<0.5
<0.4
<0.5
—
—
.05
6.0
+158.9.
PH
7.97
33.0
0.44
2.0
281}
<0.1
<.07
0.15
—
.06
—
—
—
3,150
<0.4
—
<0.5
4.0
—
<1.0
0.16
—
<0.5
—
<0.5
<0.4
<0.5
—
—
.03
_ n
4.5
+215.5
PH
4.08*
46.1
9.14
<0.3
195
<0.1
1.31
0.15
—
<.01
—
- —
—
2,350
<0.4
—
<0.5
35.0
—
<1.0
2.0
_
<0.5
—
<0.5
<0.4
__
<0.5
—
—
20
3.27
+354.1
PH
2.74
53.9
10.0
<0.3
220
<0.1
1.77
0.20
—
1.2
—
—
3,100
<0.4
—
<0.5
95.5
—
<1.0
3.15
_
<0.5
<0.5
<0.4
1.25
—
—
15
_
7.09
+474.1
pH
9.98
0.05
<.01
6.0
415f
0.1
<.07
0.15
<.01
—
—
4,950
<0.4
—
<0.5
2.0
—
<1.0
0.55
_
<0.5
<0.5
<0.4
<0.5
—
—
.01
7.41
+46.8
Argon
(mg/L)
PH
7.08
40.9
2.25
2.0
271t
<0.1
<.07
0.15
_
<.01
—
—
3,250
<0.4
_
<0.5
6.67
—
<1.0
0.16
_
<0.5
___
<0.5
<0.4
<0.5
—
—
0.33
4.36
+200.3
pH
4.26*
44.9
9.16
<0.3
185
0.2
1.45
0.25
__
<.01
—
—
2,250
<0.4
—
<0.5
22.7
—
<1.0
1.58
_
<0.5
—
<0.5
<0.4
_
<0.5
—
—
16
_
3.27
+263.5
PH
2.52
54.3
10.4
<0.3
230
0.3
1.87
0.25
^
3.0
—
—
___
3,450
<0.4
—
<0.5
93.5
<1.0
3.48
_
<0.5
<0.5
<0.4
_
3.0
—
19
_
7.63
+390.1
*Natural pH of supernatant
Chemical oxygen demand.
•N.iOII iiddoil for pH adjustment
-------
TABLE 13. CHEMICAL COMPOSITION OF WATER-QUENCHED SLAG AND SLURRY SUPERNATANT SOLUTIONS
OF THE SLAG FROM AN ILLINOIS NO. 6 COAL AT SEVERAL pH'S
Chemical composition of
Air
•(mg/L)
Constituents
Ag
Al
Au
As
B
Ba
Be
• Br
Ca
Cd
Ce
Cl
CODf
Cr
Co
Cu
Cs
Eu
F
6Total
pe+2
Ga
Ge
Hf
Hg
K
La
Li
Lu
Mg
Solid ash
(mg/kg)
.80
84,571
—
2.7
200
500
2.4
0.6
43,668
<2
100
100
—
100
17.5
40
14.5
1.83
100
137,267
—
12
0.33
6.88
.01
13,365
53
—
.87
5,066
PH
8.82
_
<.5
<1.0
<.5
<0.1
•c.Ol
—
7.0
<.03
_
<20
13
<.02
<.l '
<.05
—
—
.07
.68
<. 1
—
—
— .
•c.0002
2.0
—
<.01
—
0.6
pH
7.40
_
•c.5
<1.0
<.5
<0.1
<.01
—
9.5
•c.03
_
<20
13
<.02
<.l
<.05
—
—
.03
.17
•c.l
—
—
—
•c.0002
2.0
—
<.01
—
1.3
pH
3.81*
_
5.5
<1.0
<.5
<0.1
<.01
—
17.5
<.03
_
<20
10
<.02
<.l
.20
—
—
.04
.60
•c.l
—
—
—
< . 0002
3.0
—
.01
—
2.2
PH
2.83
41.0
<1.0
<.5
<0.1
<.01
—
33.5
•c.03
<20
9.4
<.02
<.l
.32
.
.02
10.5
1.8
—
—
—
<-0002
7.2
—
.03
__
4.0
lO'.V. slurry supernatant
pll
9.94
•c.5
<1 0
<.5
<0.1
•c.Ol
—
5.0
<.03
<20
20
<.02
<.l
•c.05
.06
.55
<.l
—
—
—
<.0002
1.9
—
<.01
0.2
Ar
pll
8.30
<.5
<1 0
<.5
<0.1
•c.Ol
—
9.7
<.03
<20
10
<.02
<.l
<.05
.04
.15
<.l
—
—
—
<.0002
2.0
<.01
0.9
gon
/LJ ..
pll
5.65*
<.5
<1 0
<.5
<0.1
<.01
—
12.0
•c.03
<20
8.4
<.02
<.l
<.05
— .
—
.02
12.2
11.0
—
—
—
<.0002
2.6
<.01
__
1.4
PH
3.09
35.5
<1 0
0.6
<0.1
!02
31.0
<.03
<20
29
.06
•c.l
.13
.04
140
125
—
—
—
<.0002
11.8
.03
3.8
38
-------
TABLE 13. Continued.
Chemical composition
Solid ash
Constituents (mg/kg)
Mn
Mo
Na
NH,,
Ni
Pb
P
PO,
Rb
- S
Total
S'2
SO,
Sb
Sc
Se
Si
Sm
Sn
Sr
Ta
Te
Th
Ti
Tl
U
V
W
Yb
Zn
Zr
EC (mmhos/cm)
Eh (electrode mv)
465
2.8
5,935
—
57
20
786
—
100
1,100
100
1,200
4.2
20
<3
222,934
10.8
3.7
200
1.2
2.1
22
4,436
<4
7.7
56
2.5
1.7
62
200
—
—
Air
(mq/L)
pH pH pH
8.82 7.40 3.81*
.03 .06 .78
< . 2 < . 2 < . 2
98* 44t 2.'i
6.0 9.0 . 8.0
<.07 <.07 .13
<.l <.l <.l
— — —
<.025 <.025 <-025
— — —
_ __
< . 2 < . 2 < . 2
97.5 10K5 80.5
<.4 <.4 <.4
— — —
<.5 <.5 <.5
7 7 14.5
— — —
,; 1 . 0 < 1 . 0 < 1 . 0
< . 02 < . 02 .04
— — —
<.5 .-..5 <.5
_ . _ _
•' . 6 < . 6 < . 6
< p 4 < . 4 < . 4
— — —
< . 5 < . 5 < . 5
— — —
_ _ _
.02 <.01 .18
— — —
0.55 0.33 0.32
+244.3 +305.3 +462.1
pH
2.83
.95
< . 2
4.9
9.0
.32
<.l
—
<.025
—
<.2
iog!o
<.4
—
<.5
38
—
<1.0
.14
—
<.5
<.6
<.4
—
<. 5
—
_
.28
—
1.00
+527.4
of 10% slurry supernatant
Argon
(mq/L)
pH pH pH
9.94 8.30 5.65*
.03 .05 .60
< . 2 < 2 < 2
45* 20* l.'e
14 8.0 11
<.07 <.07 <.07
<.l <.l < 1
__ __
.11 <.025 <.025
— —
_
<.2 <.2 <.2
50.5 52.5 51 '.0
< . 4 < . 4 .< . 4
—
<.5 <.5 <.5
9 5.5 8
: —
< 1 . 0 < 1 . 0 < 1 . 0
<.02 <.02 <.02
— —
<.5 <.5 <.5
'' . 6 < . 6 < . 6
< 4 < 4 < 4
— — —
< . 5 < . 5 < . 5
_ _ _
- - . -
<.01 <.01 .02
0.24 0.18 1.64
+89.9 +186.3 +310.3
PH
3.09
.85
< 2
4^8
10
.13
< 1
<.025
<.2
28!5
<.4
<.5
31.5
<1.0
.16
— _
<.5
< .6
<.4
—
<.5
—
_
.28
1.26
+362.1
*Natural pH of supernatant.
^Chemical oxygen demand.
added for pH adjustment.
39
-------
TABLE 14. CHEMICAL COMPOSITION OF CHAR (1800°F) AND SLURRY SUPERNATANT SOLUTIONS OF THE
CHAR FROM AN ILLINOIS NO. 6 COAL AT SEVERAL pH'S
Chemical composition
Air
(mg/L)
Constituents
Ag
Al
Au
As
B
Ba
Be
Br
Ca
Cd
Ce
Cl
COD1"
Cr
Co
Cu
Cs
Eu
F
FeTotal
Fe+2
Ga
Ge
Hf
Hg
K
La
Li
. Lu
Mg
Solid ash
(mg/kg)
.20
17,147
—
3.7
400
100
1.3
1.3
4,574
<0.5
22
200
—
28.9
4.5
14
3.1
0.68
92
23,951
4.4
2.0
1.13
.01
2,656
8.4
—
0.2
603
PH
8.05*
<-5
—
<1.0
2.8
<0.1
<.01
—
93
<.30
_
<20
41
<.02
<0.1
<.05
—
—
1.60
<.l
<.l
—
<.0002
2.0
—
.03
1.8
PH
6.17
<.5
—
<1.0
2.2
<0.1
<.01
—
327
<.30
<20
6.8
<.02
<0.1
<.05
—
—
0.88
.35
<.l
<.0002
2.8
—
.05
3.0
PH
4.33
<.5
—
<1.0
2.5
<0.1
<.01
—
340
<.30
<20
60
<.02
<0.1
<0.05
—
—
0.64
250
230
<.0002
4.0
.06
3.5
pH
2.46
27.0
—
<1.0
3.3
<0.1
<-01
—
370
<.30
<20
190
.06
0.25
<.05
—
—
0.10
1,250
1,140
__
___
<.0002
8.6
.08
4.8
of 10°£ slurry supernatant
PH
7.45*
<.5
<1.0
2.4
<0.1
<.01
no
<.30
<20
31
<.02
<0.1
<.05
1.90
.15
<.l
<.0002
1.4
.03
1.7
Argon
(mq/L)
pH
7.26
3.0
<1.0
2.8
<0.1
<.01
280
<.30
<20
16
<.02
<0.1
<.05
— _
1.85
<.l
<-l
— '
—
<.0002
2.0
_
.04
2.5
pH
4.95
31.5
<1.0
3.0
<0.1
<.01
i
333
<.30
<20
30
<.02
<0.1
<.05
1.50
100
98
<.0002
4.2
—
.05
_„.,
3.6
PH
3.03
3.5
<0.1
<.01
357
<.30
<20
71
.04
<0.1
<.05
•
1.50
415
400
<:0002
9.4
—
.08
6.0
40
-------
TABLE 14. Continued.
Chemical composition
Solid ash
Constituents (mg/kg)
Mn
Mo
Na
NHu
Ni
Pb
P
PO,,
Rb
sTotal
s-2
SO*
Sb
Sc
Se
Si
Sm
Sn
Sr
Ta
Te
Th
Ti
Tl
U
V
W
Yb
Zn
Zr
EC (mmhos/cm)
Eh (electrode mv)
77
4.1
953
—
20
12
87
—
26
28,700
1,400
300
0.44
4.8
4.1
40,015
1.9
0.9
13
0.33
0.1
5.8
959
2.6
2.0
20
0.63
2.0
48
36
—
—
Air
(mg/L)
pH pH pH
8.05* 6.17 4.33
.28 2.78 4.45
<.2 <.2 <.2
3.' 5 let e.'o
9.0 12 12
<.07 <.07 <.07
<.l .15 .2
— — —
.025 .025 .025
— —
— • — —
<.2 <.2 <.2
100 219 69.' 5
<.4 <.4 <.4
— — —
<.5 <.5 <.5
4 4.3 7
— — —
<1 .0 <1 .0 <1 .0
.22 .42 .50
— — —
<.5 <.5 <.5
— _ ~ __
<.6 <.6 <.6
<.4 <.4 <.4
— — —
<.5 <.5 <.5
— — —
___ __
<.01 .04 .38
— __ _
0.56 1.76 2.62
+140.1 +195.8 +251.7
PH
2.46
5.00
<.2
s'.s
13
.20
.15
—
1.95
—
< .2
106.5
<.4
<.5
27.5
—
<1 .0
.68
—
<-5
_
<.6
<.4
—
<.5
—
_
.90
6.00
+353.3
of 10% slurry supernatant
Argon
(mq/L)
pH pH pH
7.45* 7.26 4.95
.58 1.80 2.52
< 2 <.2 <.2
3.0 4.'o 6.'l
11 8.0 11
<.07 <.07 <.07
<.l .15 .15
— — —
.025 .025 .025
— — —
<.2 <.2 <.2
77 73 33.'?
<.4 <.4 <.4
<.5 <.5 <.5
5 6.5 20
— — —
<1 .0 <1 .0 <1 .0
.28 .40 .54
— — —
<.5 <.5 <.5
_ _ _
<.6 <.6 <.6
<.4 <.4 <.4
<.5 <.5 <.5
_ _ _
_ _ _
<.01 .02 .25
_ _ _
0.60 1.41 2.18
-1.5 +66.9 +159.9
PH
3.03
4.85
<.2
8.4
18
<.07
.15
—
1.80
—
<.2
30.7
<.4
<.5
34
—
<1 .0
.64
—
<.5
_
<.6
<.4
<.5
—
_
.62
_
3.39
+188.6
*Natural pH of supernatant.
^Chemical oxygen demand.
*NaOH added for pH adjustment.
41
-------
TABLE 15. CHEMICAL COMPOSITION OF CHAR (1200°F) AND SLURRY SUPERNATANT SOLUTIONS OF THE CHAR
FROM AN ILLINOIS NO. 6 COAL AT SEVERAL pH'S
Chemical composition of
10% slurry supernatants
Air
(mg/L)
Constituents
Ag
Al
Au
As
B
Ba
Be
Br
Ca
Cd
Ce
Cl
COD7
Cr
Co
Cu
Cs
Eu
F-
FeTotal
Fe+2
Ga
Ge
Hf
Hg
K
La
Li
Lu
Mg
Solid ash
(mg/kg)
.
13,601
—
f
300
66
1.
4.
6,075
0.
24
400
— '
24.
3.
11
3.
t
100
5,860
—
4.
1.
1.
•
3,321
8.
—
,
7,598
51
17
2
0
4
5
4
4
40
4
2
08
01
1
2
PH
9.71
_
2.18
—
<1 .0
11
<0.1
<.02
—
2.0
<.03
^
72
5
<.02
<.05
<.04
—
—
0.64
.08
<0.1
—
—
—
<.0002
5.5
— .
<.01
—
<.01
7
<0
<1
10
<0
<
207
<
72
2
<
.<
<
0
<
<0
<
3
0
pH
.19*
—
.3
—
.0
j
!02
—
.03
—
.02
.05
.04
—
—
.05
.05
.1
—
—
—
.0002
.7
—
.03
—
.13
PH
3.81
_
7.18
—
<1 .0
9.1
<0.1
-------
TABLE 15. Continued.
Chemical composition of 10% slurry supernatants
Air
(mg/L)
Constituents
Mn
Mo
Na
NH,,
Ni
Pb
P
P0»
Rb
ST .
Total
s-2
SO,,
Sb
Sc
Se
Si
Sm
Sn
Sr
Ta
Te
Th -
Ti
Tl
U
V
VI
Yb
Zn
Zr
EC (mmhos/cm)
Eh (electrode
Solid ash
(mg/kg)
57
3.5
8,636 .
—
12 .
8
87
—
23
25,800
900
1,600
.38
2.4
3.3
50,490
1.9
3.5
<10
.3
1.3
4.9
4.318
2.6
1.8
21.8
.63
1.2
42
28
—
mv) —
PH
9.71
<.01
<0.3
22. 4t
<0.1
<.07
<0.1
—
<.01
—
_
655
<0.4
—
<0.5
3.33
— •
<1.0
<.03
—
<0.5
^
<0.5
<0.4
—
<0.5
—
.02
—
2.56
+134.3
PH
7.19*
.57
<0.3
11.0
<0.1
<.07
<0.1
—
<.01
—
_^
500
<0.4
—
<0.5
5.00
—
<1.0
0.55
—
<0.5
_
<0.5
<0.4
—
<0.5
—
.02
—
1.04
+258.0
pH
3.81
3.2
<0.3
16.5
<0.1
0.16
<0.1
—
<.01
—
955
<0.4
—
<0.5
23.0
—
<1.0
0.68
—
<0.5
__
<0.5
<0.4
—
<0.5
—
_
0.59
1.42
+362.6
pH
2.67
4.3
<0.3
27.5
0.1
0.34
0.15
—
<.01
, —
__
200
<0.4
—
<0.5
48.7
—
<1.0
0.93
—
<0.5
_
<0.5
<0.4
—
<0.5
—
_„_
1.0
__
3.71
+491.2
PH
9.72
<.01
<0.3
21.5$
<0.1
<0.7
<0.1
—
<.01
—
__
530
. <0.4
—
<0.5
3.33
—
<1.0
<.03
<0.5
_- -
<0.5
<0.4
—
<0.5
—
_
<.02
^
3.16
+83.5
Argon
(mg/L)
PH
7.63*
.34
<0.3
10.0
<0.1
<0.7
0.15
—
<.01
—
__
170
<0.4
—
<0.5
4.33
—
<1.0
0.49
<0.5
__
<0.5
<0.4
—
<0.5
—
^_
.08
^
0.75
+181.0
PH
4.09
3.1
<0.3
16.0
<0.1
0.19
0.15
—
<.01
—
_ _
860
<0.4
—
<0.5
19.3
—
<1.0
0.74
_
<0.5
^_
<0.5
<0.4
—
<0.5
—
^_
0.28
_
1.42
+321.1
PH
2.42
4.3
<0.3
26.0
0.1
0.34
0.30
_
0.15
—
_
__
175.
<0.4
—
<0.5
48.3
—
<1.0
0.90
__
. <0.5
__
<0.5
<0.4
<0.5
—
^_
0.66
_
6.32
+358.2
*Natural pH of supernatant
Chemical oxygen demand.
added for pH adjustment.
43
-------
TABLE 16. CHEMICAL COMPOSITION OF HIGH-SULFUR CLEANING WASTE (GOB) AND SLURRY SUPERNATANT
SOLUTIONS OF THE GOB FROM AN ILLINOIS NO. 6 COAL AT SEVERAL pH'S
Chemical composition of
10% slurry supernatant
Air
(mg/L)
Solid ash
Constituents (mg/kg)
Ag
Al
Au
As
B
Ba
Be
Br
Ca
Cd
Ce
ci
CODf
Cr
Co
Cu
Cs
Eu
.F
FTotal
Fe+2
Ga
Ge
Hf
Hg
K
La
Li
Lu
Mg
.
56,522
—
13
9.
300
2
1.
28,159
<1.
92
300
—
45.
10.
29
9.
1.
1,105
86,157
—
11
1.
3.
.
9,962
43
—
.
1,869
20
3
2
4
3
3
6
2
2
24
02
34
PH
8.34
<0.3
—
<1 .0
<0.5
<0.1
<.02
—
21.8
<.03
28
7
<.02
<.05
<.04
—
—
1.40
<.05
<0.1
—
—
—
<.0002
11.4
—
.03
—
.09
7
<0
<1
<0
<0
<
480
<
28
5
<
<
<
0
<
<0
<
11
0
pH
.45*
—
.3
—
.0
.5
j
!02
—
2
.03
—
.02
.05
.04
—
—
.47
.05
.1
—
—
—
.0002
.9
—
.07
—
.95
PH
3.43
' —
4.7
—
<1 .0
<0.5
<0.1
-------
TABLE 16. Continued.
Chemical composition
of 10% slurry supernatants
Air
(mg/L)
Constituents
Mn
Mo
Na
NH,,
Ni
Pb
P
PO.,
Rb
c
Total
S'2
SOu
Sb
Sc
Se
Si
Sm
Sn
Sr
Ta
Te
'Th
Ti
Tl
U
V
W
Yb
Zn
Zr
EC (mmhos/cm)
Eh (electrode
Solid ash
(mg/kg)
310
3.2
2,419
—
48
55
829
—
100
108,800
76,100
13,500
.2
9.1
12.6
145,490
6.9
3.3
100
.8
.6
13
4,668
8.2
2.9
35.3
2.5
2.1
300
100
—
mv) —
PH
8.34
<.01
-------
TABLE 17. CHEMICAL COMPOSITION OF LOW-SULFUR CLEANING WASTE (GOB) AND SLURRY SUPERNATANT
SOLUTIONS OF THE GOB FROM AN ILLINOIS NO. 6 COAL AT SEVERAL pH'S
Chemical composition of
10% slurry supernatant
Air
(mg/L)
Constituents
Ag
Al
Au
As
B
Ba
Be
Br
Ca
Cd
Ce
Cl
COOT
Cr
Co
Cu
Cs
Eu
F-
Fe
• Total
Fe+2
Ga
Ge
Hf
Hg
K
La
Li
Lu
Mg
Solid ash
(mg/kg)
.30
97,008
—
68
200
400
3
3.2
21,227
1.8
100
700
—
78
13
36
15.2
1.5
900
24,813
—
19
4.1
7.94
.05
17,102
50
—
.42
3,859
PH
9.19
—
4.4
—
<1.0
1.0
<0.1
<.02
—
4.6
<.03
—
30
10
<.02
<.05
<.04
—
—
1.7
1.1
<0.1
—
—
—
<.0002
4.5
—
<.01
—
.02
PH
7.79*
<0.3
—
<1.0
<0.5
0.72
<.02
—
568 2
<.03
28
6
<.02
<.05
<.04
—
—
.94
1.08
<0.1
—
—
—
<.0002
17.8
—
.07
—
0.79
PH
3.50
8.53
—
<1.0
<0.5
2.54
<.02
—
,287 2
.08
__
28
12
<.02
.45
.28
—
—
2.2
10
2.3
—
—
—
<.0002
29.0
— •
.16
—
80.0
pH
2.54
29.0
—
<1.0
<0.5
1.90
.034
—
,595
.09
34
26
.06
.64
1.68
—
—
1.9
130
52
—
—
—
<.0002
38.0
—
.26
—
119.7
PH
9.24
0.62
—
<1.0
1.0
<0.1
<.02
—
4.6
<.03
30
4
<.02
<.05
<.04
—
—
1.7
1.2
<0.1
—
—
—
<.0002
3.0
—
<.01
—
.05
Argon
(mg/L)
pH
7.21*
<0.3
—
<1.0
<0.5
1.64
<.02
—
943 1
.04
28
9
<.02
<.05
<.04
—
—
1.1
.08
<0.1
_
—
—
<.0002
20.0
—
.09
—
30.0
PH
4.88
<0.3
—
<1.0
<0.5
1.82
<.02
—
,973 2
.08
28
11
<.02
.27
<.04
—
—
1.1
2.2
0.5
—
—
—
<.0002
25.0
—
.15
—
68.7
PH
2.43
57.0
—
<1.0
<0.5
2.54
.034
—
,784
.09
—
34
61
0.13
.48
1.34
—
—
.48
360
285
—
—
—
<.0002
40.0
—
.33
—
138.9
46
-------
TABLE 17. Continued.
Chemical composition of 10X slurry supernatant*'
A1r
(mg/L)
Constituents
Mn
Mo
Na
NH*
N1
Pb
P
PC-
Rb
s
"Total
s-2
SO,
Sb
Sc
Se
Si
Sm
Sn
Sr
Ta
Te
Th
T1
Tl
U
V
W
Yb
2n
Zr
£C (mmhos/cm)
£h (electrode
Solid ash
(mg/kg)
310
<1
3,635
—
55
55
1,397
—
200
5,100
4,600
400
2.7
15.2
3.3
261,380
8.0
7.2
79
1.2
2.2
20
8,298
8.0
3.1
39.8
2.9
4.3
500
200
_
mv) —
PH
9.19
.02
_
485t
<0.1
<.07
.15
• ' —
.08
—
__
43
,<0.4
_
<0.5
19.3
—
<1.0
.03
. —
<0.5
_ .
<0.5
<0.4
_
<0.5
—
^
.16
.»
.74
+122
PH
7.79*
.59
__
245
1.8
<.07
.15
—
.04
—
__'
96
<0.4
—
<0.5
13.7
—
<1.0
2.60
—
<0.5
__
<0.5
<0.4
_
<0.5
—
.^
<.01
_
4.4
+189.8
PH
3.50
1.2.6.
_
250
3.9
.69
.40
—
14.5
_
—
73
<0.4
_
<0.5
64.6
_
<1.0
7.06
_
<0.5
^
<0.5
<0.4
_-
<0.5
—
• 27
^
9.3
+314.1
pH
2.54
24.4
.
250
4.5
1.06
.50
_
3.0
__
L
67
<0.4
_
<0.5
96.2
<1.0
8.00
<0.5
nm^
<0.5
<0.4
^
<0.5
—
_
1.55
mi^
12.1
+404.7
PH
9.24
.07
_
5051=
<0.1
<.07
<0.1
_
.06
.^
_ r
24
<0.4
-
<0.5
15.0
_
<1.0
.03
^
<0.5
«.
<0.5
<0.4
„
<0.5
—
_
2.25
^^^
.71
+53.4
Argon
(mg/L)
PH
7.21*
2.06
_
260
1.8
<.07
.20
—
2.75
„-. •
_
60
<0.4
^
<0.5
25.3
_
<1.0
3.70
_
<0.5
__
<0.5
<0.4
^
<0.5
' —
^^
.06
• _
5.4
+168.4
PH
4.88
9.9
__
245
4.0
.33
.40
_
3.25
_
--i-i-
49
<0.4
_ _
<0.5
55.0
_
<1.0
6.83
<0.5
<0.5
<0.4
—
<0.5
—
••••
.12
__
8.5
+210.4
PH
2.43.
30.7
255
4.9
.85
.70
_
44.0
__
45
<0.4
<0.5
116.5
<1.0
9.12
__
<0.5
<0.5
<0.4
<0.5
—
_
1.40
__
12.5
+319.8
*Natural pH of supernatant
Chemical oxygen demand.
added for pH adjustment
47
-------
Calcium values exceeded the recommended levels for all but the slag acid
leachate; however, although several of the calcium concentrations were in the
range of 1000 to 2000 mg/L, they did not present the environmental hazard that
the four constituents mentioned.above do. Additional trace metals were found
in some of the most acid leachates at concentrations slightly above the recom-
mended levels for certain water types. They were not found in solution at
detectable concentrations in the intermediate acid leachates (pH 5.5 to 4.0).
Boron was present in amounts exceeding the recommended level for irrigation
water (0.75 mg/L) in all but two of the most acid leachates, and over the entire
pH range in eight of the slurry sets. The current assessment of boron's ef-'
feet on the environment, however, leaves some question as to whether the
boron concentrations found in this study are hazardous to the environment.
Sulfate was the dominant anion in solution with concentrations that
ranged as high as 5000 mg/L. Sulfate, however, along with Cl, K, and Na,
showed no pH dependency in their solubility.
Nonetheless, the most easily leached constituent does not always possess
the greatest potential for pollution. Although, under acid conditions, many
constituents exceeded the U.S. EPA recommended levels, it was felt that those
that exceeded the recommended levels over the entire pH range had the greatest
potential for pollution. Table 18 lists those constituents that were found to
exceed the recommended levels over the pH range studied (including both aerobic
and anaerobic solutions), and under the laboratory conditions described
earlier. Also included in
table 18 is a summary of the pH
ranges for the supernatant solu- TABLE is.
tions for each waste along with
the natural (unadjusted) pH for
both the aerobic and the
anaerobic series. .
Sample
ELEMENTS WITH CONCENTRATIONS EXCEEDING
RECOMMENDED WATER QUALITY LEVELS UNDER
THE LABORATORY TEST CONDITIONS
• Natural pH
pH range Air Argon Constituents
. The two most important fac-
tors affecting the solubility of
minerals were probably the pH and
the redox potential. The solid
waste that has the lowest pH
value would also pose the great-
est potential threat to the
environment. Indeed, the power
plant slag and fly ash natural
leachates appear to present
greater hazards because of their
dissolved constituents than the
natural pH leachates from the
other wastes. The experimental
conditions described above, how-
ever, may not have been as condu-
cive as natural conditions to the
development of naturally acid pH's
for several of the other wastes,
such as the gob samples.
Lurgi Ash
(111. #6 Coal)
Lurgi Ash
(111. #5 Coal)
Lurgi Ash
(Rosebud Coal
Mont.)
SRC
H-Coal
Char (1200°F)
Char (1800°F)
Low-sulfur gob
High-sulfur gob
Slag
Fly ash
8.
10.
11.
10.
11.
9.
8.
9.
8.
8.
10.
8-2
9-3
1-3
2-2
3-2
7-2
1-2
2-2
9-2
8-2
0-2
.7
.1
.1
.9
.3
.4
.5
.4
.5
.8
.5
7.
8.
8.
6.
8.
7.
8.
9.
7.
3.
4.
6
3
4
4
8
2
1
2
5
8
1
8
10
11
7
11
7
7
9
7
5
4
.8
.9
.1
.5
.3
.6
.5
.2
.4
.7
.3
B,
Mn,
SO,,
B,
NHi,
Sb
B,
K,
Pb,
B,
Mn,
B,
B
B,
NH,,
Ca,
NHi,
, Sb
Ca,
, Pb
Ca,
Mo,
SO,,
Ca,
NH'I,
Ca,
Ca,
Cd
»
K,
1
Cd
, K,
Pb,
•Mn,
so,,,
, F,
NH,,,
»
Fe
»
Sb
*
SOi,
NHi,
Mn
t
None
K,
NH,,
B,
NH,,,
Ca,
SO,,
SO,,
48
-------
There is reason to believe that using 10 percent slurries in large
volumes may prohibit complete oxidation of the iron sulfides in several of
the solid wastes because of oxygen's slow diffusion rate through water.
Complete oxidation would result in sulfuric acid production and a lowering of
pH, along with a subsequent increase in constituent solubility for those
wastes containing an appreciable amount of pyrite. Under different experi-
mental conditions, therefore, the natural pH's of some of the waste leachates
may be greatly decreased. It was felt that pH adjustment to the low values in
table 18 helps to simulate the acid conditions that may develop under different
environmental conditions.
Comparison of the constituent concentrations of the two sets of slurries
for each waste was difficult because the sets were equilibrated to slightly
different pH values for the air and argon slurries. Although it was
attempted to pair the pH values between the sets of slurries, the values
often varied by as much as 0.5 pH units. The iron concentrations were in-
structive in cases where the acid pH's were similar: generally, the leachates
equilibrated under argon exhibited higher concentrations of iron (predomi-
nantly ferrous iron) in solution—especially at the intermediate acid pH
level (5.5 to 4.0). Undoubtedly this was caused by the lack of available
oxygen in the slurries equilibrated under argon. Similar results could be
expected for several other metals present.
Table 18 also indicates that the soluble constituents found in solid
wastes were similar for the same treatment no matter which feed coal was
used; i.e., the three Lurgi ashes yielded nearly the same major soluble con-
stituents for all three feed coals. The same was true for the two liqui-
faction wastes. The Illinois No. 6 Coal was used in both the Lurgi and
H-Coal processes, but quite different soluble constituents were derived from
the wastes. The Cd, K, Mn, Na, Pb, SO.,, and Sb found in the Lurgi ash leach-
ates indicated that they were more soluble than those same constituents from
the H-Coal residue under the conditions used.
49
-------
SECTION 7
EQUILIBRIUM SOLUBILITY MODELING
OF THE LEACHATES FROM COAL SOLID WASTES
The application of equilibrium solubility models can lead to useful in-
sights into the chemistry of aqueous systems. Equilibrium models provide, at
a minimum, boundary conditions within which questions may be framed. For
example, a typical environmental problem solved by equilibrium models is that
of predicting what is the highest concentration of a given constituent that
can be achieved in solution before precipitation occurs with a given solid
phase. Solutions to such problems can be sueful in developing a "worst case"
scenario for a given pollutant that is leaching from a solid waste, by
setting the upper boundary for concentrations of the pollutant that will have
to be dealt with under a given set of conditions.
The results of applications of solubility models to environmental prob-
lems must be interpreted carefully. For example, it is not uncommon to find
large discrepancies in literature values for the solubility products of some
mineral phases. The value of the solubility product may depend on the direc-
tion of approach to equilibrium, the use of well-defined crystals versus pre-
cipitation, and phenomena such as phase transitions, aging, colloid formation,
and differences in particle size. These factors, along with slow attainment
of equilibrium and the fact that impure minerals are found in nature as
opposed to the pure minerals used to determine solubility constants, may
obscure solubility relationships and their application to practical environ-
mental problems.
Important factors controlling the solubility of mineral phases include
pH, the redox environment of the system, the oxidation state of the mineral
components, the concentration and speciation of individual inorganic and
organic ions and complexes in solution, and the ionic strength (total soluble
ions). Applying the results obtained from solubility models to real environ-
mental conditions requires considerable caution; nevertheless, assuming that
the activities are calculated correctly and that the equilibrium constants
are numerically factual, these models should accurately predict the solubil-
ity of an ion under a given set of conditions for a long list of solid phases.
EQUILIBRIUM SOLUBILITY MODEL
Explaining the aqueous chemistry of a complex system such as the leach-
ates from coal conversion solid wastes is diffucult. Possible complexation,
ion pair formation, and the effects of organic components on the formation of
50
-------
organo-metallic complexes hinders the description of these systems. On the
other hand, it is still important to examine these systems and account for
their soluble components, and we progress if we prepare diagrams showing the
relations of the known aqueous species to the mineral solid phases.
Solubility and mineral stability diagrams were prepared according to
Garrels and Christ (1965). The thermodynamic solubility model used in this
study (WATEQF) considered the speciation of 115 aqueous inorganic ions and
complexes and computed saturation data for over 100 minerals. The theory of
the model and its computer implementation have been discussed previously by
Truesdell and Jones (1973; 1974) and Plummer, Jones, and Truesdell (1976).
The stability relations of the iron oxides and sulfides in water were
plotted as a function of Eh and pH in figure 4. Data from the leachates of
the eleven wastes and a pyrite standard, equilibrated under the same
01 23456789 10
pH
Figure 4. Stability relations of iron oxides and sulfides in waste at 25° C when Fe*2
10~3M (native sulfur field excluded).
II 12
14
10 M, and the sum of sulfur species is
51
-------
conditions as the solid wastes, were also plotted. Some explanation of
figure 4 may help to interpret the data. The upper and lower limits of water
stability are shown; they mark the upper and lower boudaries of the Eh and
pH of concern. Thus, water decomposes into oxygen gas at Eh and pH values
above the upper boudary; water decomposes into hydrogen gas at the lower
boundary. Eh and pH values outside this range, therefore, are not normally
of concern when interpreting the aqueous chemistry of natural systems.
The solid lines between solid phases such as hematite and magnetite mark
the boundaries of mineral stabilities. Data points falling within these
regions indicate that the samples are within the stability field of that
particular mineral. Most of the data points in figure 4 fall within the
hematite stability field. This is reasonable because x-ray diffraction
showed hematite to be present in most of the samples; however, magnetite and
pyrrhotite were also shown to be present in some of the solid wastes. The
diagram illustrates that these two minerals are unstable in these systems
and, given sufficient time, they will decompose to other mineral phases.
Data points that fall on or near a boundary line, such as the pyri.te
standard (fig. 4), indicate that a solution is in simultaneous equilibrium
with the various solid phases described by the boundary. The pyrite used in
this study was a technical grade material that contained impurities in the
form of hematite and magnetite; thus it is reasonable that the solution
would be in equilibrium with these three mineral phases, and that the elec-
trodes used in the measurements were operating properly.
The boundaries between solid phases and aqueous species (such as between
hematite and the aqueous Fe+2 ion) serve as true "solubility" boundaries;
they are a function of the activity of the ion in solution. Two such bound-
aries are shown in figure 4—one for 10~6M, and another for 10~2M Fe+2aq.
The 10~6M boundary is chosen by convention, on the premise that if an
ion's activity in equilibrium with a solid phase is less than 10~6M, the
solid will be immobile in that particular environment. This convention was
developed largely from experience but seems to correlate well with natural
geologic systems (Garrels and Christ, 1965). The 10"2M boundary was chosen
because it corresponds to the upper limit of Fe+2 concentrations measured in
the leachates from the solid wastes.
The boundary between two aqueous species such as the Fe+2 and Fe+3 ions
is drawn where the concentration of each ion is equal; thus the labeled
areas are those where the particular ion is dominant, even though small con-
centrations of other ions may also be present.
The 10~6M boundaries of the metastable minerals maghemite and freshly
precipitated ferric hydroxide are drawn as broken lines. Maghemite and
ferric hydroxide are unstable with respect to hematite, pyrite, and magne-
tite, and given sufficient time, they will convert to the thermodynamically
stable minerals. However, maghemite and ferric hydroxide are clearly of
more than transitory existence in natural environments and warrant considera-
tion as mineral phases that probably control iron concentrations during the
initial leaching of solid wastes, which is probably the environmentally
critical period.
52
-------
The data plotted in figure 4 indicate that amorphous ferric hydroxide is
probably a control on iron concentrations in the leachates at pH values less
than 7. Indeed, computations of ion activity products for the leachates
agree with the solubility constant for the amorphous ferric hydroxide in the
acid solutions. The mineral phases that were identified through chemical
equilibrium modeling as contributing to the control of the ionic composition
of the leachates were summarized (table 19).
Iron concentrations tended to drop below detectable levels in the alka-
line solutions. These low concentrations were predicted by the solubility
.modeling, and they support the interpretations given in the mineral stability
diagram (fig. 4).
The plot of the data in figure 4 shows that the Eh-pH relations of the
alkaline leachates are not being controlled by equilibria between minerals
given on the diagram. Figure 5 shows the aqueous stability relations of the
manganese oxide-carbonate system. The manganese oxides and carbonates are
very likely in equilibrium in the
alkaline leachates, whereas the
acid leachates fall in the aqueous
Mn+2 ion field— facts that are sup-
ported by the computations of the
ion activity products for the man-
ganese minerals (table 19). These
computations showed that the alka-
line solutions were generally in
equilibrium with the manganese
oxides or carbonate on whichever
boundary the particular data points
shown in the diagram fell. The
acid leachates were undersaturated
with respect to the various manga-
nese minerals (fig. 5). Thus, it
appears that manganese oxides are
controlling the Eh-pH relations of
the alkaline leachates and the
metastable, freshly precipitated
ferric hydroxide is controlling the
Eh-pH relations in the acid leach-
ates.
+ I.2-1
1.0-
+0.8-
' +0.7-
+0.6-
_ +0.5-
I +0.4-
§ +0.3-
+0.2-
+0.1-
-0.2-
-0.4-
-0.6-
-0.8-
Hausmannite
Mn,0
Rhodochrosite
MnCO.,
• Lurgi-l B
• Lurgi-l 6
A Lurgi-Rosebutl
• H-Coal
» SRC-I
O Fly ash
D Bottom ash
O High temperatui
O Medium temperaluic char
* High S refuse
9 Low S refuse
e chat
01 23456
7
pH
8 9 10
12 13 14
Figures. Stability relations of manganese oxides and carbon-
ates in water at 25°C when total carbonate species
isio"3M.
The solubilities of gypsum and
anhydrite exerted a dominant
influence over calcium and sulfate
concentrations in the leachates at
all pH levels, with the exception
of the H-Coal, bottom ash, high-
temperature char, and low-sulfur
refuse leachates (fig. 6). Whereas
theS6 Achates W6re all
Saturated With respect tO
gypsum still provided the upper
53
-------
TABLE 19. MINERAL PHASES CONTRIBUTING TO THE CONTROL OF THE IONIC COMPOSITION OF-LEACHATES FROM COAL UTILIZATION SOLID WASTES
en
-p.
Lurgi
111. #5
Mineral
Magnesite
Dolomite
Calcite
Stronti-
anite
Rhodo-
chrosite
Anhydrite
Gypsum
Barite
Fluorite
Fluor-
apatite
Hydroxy-
apatite
Strengite
Manganese
phosphate
Magnetite
Hematite
Maghemite '
Goethite
Amorphous
Fe(OH}3
Pyrolusite
Birnessite
Nustite
Bixbyite
riausmanite
Manganite
Amorphous
Al(OH),
Diaspore
Boehmite
Amorphous
Si02
Quartz
Formula
MgC03
CaMg(C03)2
CaC03
SrC03
MnC03
CaSO,,
CaSOu-2H20
BaSO,,
CaF2
Cas(POj3F
Ca5(POi,)3OH
FePO,,-2H20
MnHPOu
Fe30,,
Fe203
-Fe203
FeOOH
Fe(OH)3
Mn02
Mn02
Mn02
Mn203
Mn30,,
MnOOH
A1(OH)3
A100H
A100H
Si02
Si02
Base
EQ
EQ
EQ
EQ
EQ
EQ
EQ
SS
SS
SS
SS
SS
SS
-SS
SS
EQ
EQ
SS
SS
SS
EQ
EQ
Acid
EQ
EQ
EQ
SS
SS
SS
SS
EQ
SS
EQ
EQ
SS
Lurgi
111. #6
Base
EQ
EQ
EQ
EQ
SS
EQ
SS
SS
SS
SS
SS
EQ
EQ
SS
EQ
EQ
EQ
Acid
EQ
EQ
EQ
SS
SS
EQ
SS
EQ
EQ
SS
SS
EQ
SS
Lurgi-
Rosebud
Base
EQ
SS
EQ
SS
EQ
EQ
EQ
EQ
EQ
SS
EQ
SS
SS
SS
SS
SS
EQ
EQ
EQ
SS
SS
SS
EQ
EQ
Acid
EQ
EQ
EQ
SS
EQ
EQ
SS
EQ
SS
EQ
EQ
SS
SS
EQ
SS
H-Coal
Base
EQ
EQ
SS
EQ
EQ
EQ
SS
SS
SS
SS
SS
SS
SS
EQ
EQ
EQ
SS
SS
SS
EQ
EQ
Acid
EQ
EQ
EQ
SS
SS
SS
EQ
EQ
SRC
Base
EQ
SS
SS
SS
EQ
EQ
EQ
EQ
SS
EQ
SS
SS
SS
SS
SS
EQ
EQ
EQ
EQ
EQ
EQ
Acid
EQ
EQ
EQ
EQ
EQ
EQ
SS
EQ
EQ
EQ
EQ
EQ
Fly
Base
EQ
SS
EQ
EQ
EQ
EQ
EQ
EQ
SS
SS
SS
SS
SS
SS
EQ
EQ
EQ
SS
EQ
EQ
SS
EQ
EQ
EQ
ash
Acid
EQ
EQ
EQ
EQ
EQ
SS
EQ
SS
EQ
EQ
EQ
EQ
SS
Bottom
ash High-temp.
(slag) char
Base
EQ
EQ
EQ
EQ
EQ
EQ
SS
SS
SS
SS
SS
SS
EQ
EQ
EQ
SS
EQ
EQ
EQ
EQ
EQ
EQ
Acid
EQ
EQ
SS
EQ
SS
EQ
EQ
SS
Base
EQ
EQ
EQ
EQ
EQ
SS
EQ
SS
SS
SS
SS
EQ
EQ
EQ
SS
EQ
EQ
EQ
Acid
EQ
EQ
SS
SS
SS
EQ
EQ
EQ
EQ
Medium-
temp.
char
Base
EQ
SS
EQ
EQ
EQ
SS
EQ
SS
SS
SS
SS
EQ
SS
EQ
EQ
SS
SS
EQ
SS
EQ
EQ
EQ
Acid
EQ
EQ
EQ
EQ
SS
SS
EQ
SS
EQ
EQ
EQ
SS
High-
sulfur
refuse
Base
EQ
EQ
EQ
EQ
EQ
SS
SS
SS
SS
SS
SS
EQ
EQ
EQ
EQ
EQ
EQ
Acid
EQ
EQ
EQ
EQ
EQ
SS
EQ
SS
EQ
EQ
SS
Low-
sulfur
refuse
Base
EQ
EQ
EQ
EQ
EQ
EQ
SS
EQ
EQ
SS
SS
SS
SS
EQ
EQ
EQ
EQ
EQ
EQ
SS
EQ
EQ
EQ
Acid
EQ
EQ
SS
EQ
EQ
SS
SS
SS
EQ
SS
EQ = Equilibrium.
SS = Supersaturation.
-------
2-
O 3
in
a.
6-
• Limit I [>
• Luifii I 6
A Lurcji Rosebud
• H - Coiil
* SRC I
O Fly iish
Q Botiom ush
Medium ti:mp<;r;iUin! chili
Hi(|h S ll!lllU!
LnwSiofiiM!
SUPERSATURATED
UNDERSATURATED
4 3
pCa'2
Figure 6. Calcium sulfate equilibria of leachates from coal utilization solid wastes.
boundary for prediction of calcium and sulfate concentrations. This is sig-
nificant for the H-Coal residue, because it contained high concentrations of
sulfur, but had low water-soluble sulfur levels, for all the sulfur species
considered. This illustrates the need for information on mineral forms in
the solid waste, in addition to chemical analysis of the waste.
The three Lurgi ashes, the medium-temperature char, and the SRC-I resi-
due were generally in equilibrium with gypsum, whereas the fly ash and high-
sulfur cleaning refuse were in equilibrium with anhydrite. The exceptions in
these samples were those at high pH, where Ca concentrations in solution were
limited by CaC03 equilibria.
The calcium carbonate equilibria of leachates from the eleven solid
wastes in contact with air are shown in figure 7. Calcium concentrations in
the acid leachates were usually controlled by gypsum and anhydrite equilib-
ria; they appear as a vertical line independent of carbonate activity. Cal-
cium concentrations in highly alkaline solutions in contact with atmospheric
carbon dioxide should be controlled by calcite solubility. The data plotted
in figure 7 indicate that leachates with pH values between 7.0 to 7.5
were undersaturated with respect to calcite, whereas those leachates with pH
values greater than 7.5 were generally supersaturated with respect to calcite.
55
-------
o-
1-
2-
3-
4-
5-
6-
7-
8-
9
10
11
12
13
14
15
16
17
18
19
20
SUPERSATURATED
UNDERSATURATED
• Alkaline leachates
o Acidic leachates
pCa+:
0
ISGS 19/9
Figure 7. Calcium carbonate equilibria of leachates in contact with air from coal utilization solid wastes.
Other researchers have noted that calcite is more soluble when the Mg
ion is present, which was the case in these leachates. Hassett and Jurinak
(1971) found that calcites with low levels of Mg increased in solubility.
Similarly, Berner (1975) showed that incorporation of Mg within the calcite
crystal caused the resulting mangnesian-calcite to be considerably more
soluble than pure calcite. Furthermore, Akin and Lagerwerff (1965) demon-
strated that Mg and SOi, enhanced the solubility of calcite. It seems, there-
fore, that the mixed-salt system occurring in these leachates yields a cal-
cium carbonate mineral with higher solubility than either pure calcite or
aragonite. Using the solubility product for pure calcium carbonate minerals
to predict the calcium concentration of the alkaline leachates could result
in error by underestimating the true Ca concentrations.
Figure 8 shows the silicon dioxide and aluminum hydroxide solubility
equilibria. Most samples fell within the range of Si solubilities that a
expected from amorphous glass and quartz.
range
This
is consistent with the
are
56
-------
SUPERSATURATED
Figure 8. Silicon dioxide and aluminum hydroxide solubility equilibria of le.ichates from coal utilization solid wastes.
experimental design, which employed glass carboys as the equilibration vessel,
and in which quartz was identified in all the solid wastes. Clearly, amorphous
SiOa is not the most stable phase, and silica concentrations, after long
periods of time, would probably be controlled by alumino-silicate minerals or
quartz.
The Al equilibria, similar to the Fe and Si equilibria, were dominated
in the mid-acid and alkaline pH range by the amorphous hydroxide; a meta-
stable mineral phase was apparently controlling the solubility. These
metastable mineral phases must be considered when estimating possible environ-
mental impact during the initial leaching of coal conversion solid wastes.
The aqueous chemistry of other potential contaminants were examined
(table 19); and it was found, for example, through computation of ion activity
products for BaSO.,, that Ba concentrations in the leachates would never exceed
0.1 ppm, even in very acid solutions. Fluoride concentrations in the
57
-------
leachates seemed to be controlled by precipitation of fluorite (CaF2) and
fluorapatite (Ca5(PO.»)3F). Phosphate levels in the alkaline leachates would
never exceed 1 ppb; this was indicated by the ion activity product calcula-
tions for fluorapatite and hydroxyapatite (Ga5(POtt)3OH). In the acid leach-
ates, the precipitation of iron and manganese phosphates apparently controls
the phosphate levels.
The results of this study have several implications concerning heavy
metals. The data suggest that removal of trace metals such as Cd, Co, Cr,
Cu, Ni, Pb, and Zn from slurry pond leachates may be controlled by adsorption
on or coprecipitation with iron, manganese, and aluminum oxides and hydroxides.
Trace metals would continue to be removed this way for long periods of time
because the adsorptive capacity of the solid phase would be continually
replenished by formation of new metal oxides in the leachates. In any case,
partitioning between trace metals and solid phases must be considered when
evaluating trace metal mobility in these systems, and furthermore, sulfate,
hydroxide, and carbonate are the major inorganic ligands that must be con-
sidered.
Thus, application of thermochemical solubility models to the coal solid
waste leachates examined in this study has yielded some valuable insights
into the potential these wastes have for pollution. Application of these
models has shown that, whereas the concentrations of chemical constituents
in the solid wastes and leachates varied over a wide range, similar mineral
phases controlled the aqueous solubility of many major, minor, and trace
ionic species for all of the solid wastes.
58
-------
SECTION 8
SOIL ATTENUATION OF CHEMICAL CONSTITUENTS
IN LEACHATES FROM COAL SOLID WASTES
INTRODUCTION
When evaluating the potential coal solid wastes have for pollution, it is
important to consider where the soluble constituents of the wastes go during
land disposal. Of primary importance is the characterization of the waste and
waste leachate and the soil or receiving medium; these characterizations can
be conducted by a number of laboratory techniques and are not difficult to
determine. What is more difficult to determine, however, is the interaction
that takes place when the wastes or waste leachates and soils are brought
together, as in a simulated landfill condition. The problems in duplicating
field conditions in the laboratory, as is well known, stem from the nonsteady
state of physical parameters. To determine the long-term effects of disposal,
it is also desirable to understand the physical, chemical, and biological
mechanisms of constituent removal.
This investigation includes an experimental method designed to determine
soil-waste interactions, plus a discussion of environmental problems that
could possibly result from the disposal of coal solid wastes. Also included
is a technique for the prediction of constituent migration distance. A
detailed discussion of the mechanisms that remove hazardous elements from soil
applied wastes has been omitted since it can be found elsewhere: in Fuller
(1977), Phillips and Nathwani (1976), and Braunstein, Copenhaver, and Pfuderer
(1977). We have included, however, a discussion of these removal mechanisms
as they apply to the wastes analyzed in this investigation.
DISPERSED SOIL METHODOLOGY
Soils are ideal media for waste disposal because their attenuating
behavior can render many of the hazardous properties harmless; then the wastes
can be eventually incorporated into the soil system (Phillips and Nathwani,
1976). Before disposal, however, it is desirable to have some idea of the
results of the soil-waste interaction, which will vary with wastes and soil
types.
In the past, column leaching studies have determined the results of soil-
waste interaction. There are two principal difficulties with column leaching
studies: the long period of time required, and the difficulty in simulating
59
-------
field flow patterns. For example, it may require up to a year to obtain the
necessary data for soils with high clay contents, and even sandy soils may
require several months.
Farquhar and Rovers (1976) and Rovers, Mooij, and Farquhar (1976) de-
signed a dispersed soil (batch reactor) methodology as an alternative tech-
nique. They conducted simultaneous experiments using dulpicate soils and
wastes to examine dispersed soil and column leaching techniques. For the
latter, they used both undisturbed and remolded soil samples. Their success
in comparing the use of these two types of soil samples enabled them to
develop the dispersed soil technique, which represents a remolded soil. Their
subsequent experimentation illustrated this, but not without the following
reservations and assumptions: (1) the effects of lateral dispersion cannot be
measured; (2) intergranular flow must be assumed; (3) no microbial activity is
assumed because of the short duration of the dispersal soil motluM; (-\] thf
remolded soil column must be leached in conjunction with the batch reactors to
determine the degree of attenuation caused by dilution by soil water; and
(5) it is difficult to accurately predict the attenuation of contaminants that
undergo retarded removal.
The first two factors are also true for column studies. The inability to
measure the effects of microbial activity as an attenuation factor is a trade
off for the short period of time needed for the dispersed soil experimentation.
The last two factors listed above, however, are the most critical. The need
for leaching a remolded soil column simultaneous to the batch reactors would
result in lengthening the experimentation time. An increase in the waste
solution to soil ratio in the batch reactors, however, would reduce the impor-
tance of dilution by soil water as an attenuation mechanism. Most waste
leachates are highly complex systems and certain elemental components will be
selectively removed prior to other elements. It is difficult to predict with
any certainty the degree of attenua-
tion of constituents that undergo
retarded removal, with a technique
that would not take an unreasonable
amount of time.
EXPERIMENTAL DESIGN
A modified version of the dis-
persed soil technique developed by
Farquhar and Rovers (1976) was used
to determine the behavior of con-
stituents in the aqueous super-
natant solutions from the coal
solid wastes.
Three sets of five 1-liter
linear polyethylene bottles were
used as reaction vessels (fig. 9);
each set was used to study one soil.
After the soils had been brought to
Addition of waste effluent followed
by slugs of desorption water
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Aliquots for chemical analysis
Figure 9. Schematic diagram of dispersed soil methodology.
60
-------
field capacity (moisture content), 700 ml or an equivalent volume of filtered
(0.45 ym Millipore) supernatant from the waste slurries were added. Then the
vessels were shaken using an EquipoiseR Heavy-Duty Shaker at a rate of 265
oscillations per minute. The shaking lasted for 1% hours, which was suffi-
cient time to develop equilibrium conditions (Rovers, Mooij, and Farquhar,
1976). The samples were then filtered through Whatman #45 filters, and 60 ml
of the filtrate was filtered again through MilliporeR .45 micron pore size
membrane filters. The 60 ml portion was withdrawn for chemical analysis, and
the remaining solution was transferred to the next reaction vessel in the
series. A 60 ml sample was collected from each of the post-contact solutions.
This procedure was repeated to determine the constituents that could be de-
sorbed from the soils after mixing with the leachates. This was accomplished
by passing distilled water through the reaction series.
Three Illinois soils—Ava silty clay loam (sicl), Bloomfield loamy sand
(Is), and Catlin silt loam (si 1)—with a broad range of physical and chemical
characteristics, were collected and characterized (table 20). Twelve waste
leachates were studied, including 10 of the 11 aerated natural (unadjusted)
pH supernatant solutions. The Lurgi gasification waste using the Illinois
No. 5 Coal did not possess sufficient sample volume for analysis. Also, both
of the acid-aerated liquefaction leachates, H-CoaU and SRCu, were studied to
assess the fate of their relatively high trace metal concentrations.
The filtrates collected from this study were analyzed for 10 constitu-
ents: Al, B, Ca, Fe, K, Mg, Mn, Na, SO.,, and Zn. These constituents were
chosen because they were the constituents present in the leachates in suffi-
cient concentrations to be potential pollution hazards after being leached
through soil. The filtrates collected from the two acid coal-liquefaction
leachates were also analyzed for: Be, Cd, Co, Cr, Cu, F, Ni, and Pb.
ATTENUATION RESULTS
It is difficult to make broad generalizations about varied, complex
systems such as the waste leachate-soil mixtures. One could say, however,
that the attenuation of constituents in each leachate was similar for each
soil type, although the degree of removal or elution of individual
TABLE 20. SOIL CHARACTERISTICS
Soil
Catlin
silt loam
Ava
silty clay loam
Bloomfield
loamy sand
Surface Organic
CEC area, Np carbon
pH (meq/100 g) (m2/g) (%)
7.1 18.1 . 10.1 4.73
4.5 13.1 28.3 1.18
5.7 0.8 1.7 0.21
Sand
m
11.6
2
82
Silt . Clay
(%> (%)
60.9 27.2
69.6 28.4
10 8
61
-------
TABLE 21.
SUMMARY 01" SOIL-ATTENUATION BEHAVIOR
OF CHEMICAL CONSTITUENTS IN LEACHATES
FROM SEVERAL" COAL SOLID WASTES
Elements
Al, B, Ca,
Total Fe,
Na*. SOi,, 7n
Additional trace metals
K*
Mg
Mn
Attenuated
Variable
Eluted
pH-dependent variability
*Eluted or steady at low concentrations (<10 ppm).
constituents varied with soil type
(table 21). Most of the constitu-
ents were attenuated through the
reactor series; however, because
of selective removal, some of the
constituents for certain wastes
were first eluted from the soils
before undergoing attenuation.
To illustrate the rate of
attenuation or elution, figures 10
through 16 were drawn to represent
typical examples of constituent
behavior. The figures depict the
constituent concentration vs. the
soil leachate ratio, which is the
grams of soil necessary to remove
or elute the indicated concentration of a constituent from one milliliter of
leachate. Also included is the original supernatant concentration and a
recommended water quality standard (U.S. EPA, 1972) for comparison. A figure
depicting the additional trace elements (Be, Cd, Co, Cr, F, Ni, and Pb) that
were determined for the two acid-aerated liquefaction wastes could not be
drawn because these elements were removed to less than detectable concentra-
tions in the first reaction vessel.
Iron and zinc were the two metals that were most often present in the
highest concentrations in the waste leachates. Figure 10 is a plot of the
zinc concentration through the leachate-soil mixtures for the natural pH
leachate (pH 4.12) from the fly ash with an original zinc concentration of
20 ppm. Figure 11 is a similar diagram for total iron for the most acidic
SRC liquefaction residue leachate (pH 3.5); in this case, the original total
iron concentration in the leachate was 2962 ppm.
Supernatant concentration
Fly ash3
Secondary drinking water standard
Bloomfield Is
^"~~ -^ Ava sicl
Soil leachate ratio, gm/mL
Figure 10. Zinc concentrations vs. soil/leachate ratio for fly ash3 (pH 4.12).
62
-------
Catlin soil proved to be the most efficient of the three soils tested in
removing metals from solution. This is probably due to its higher cation-
exchange capacity and its higher pH (7.1). The higher exchange capacity .of
the Catlin soil and its higher buffering ability enables it to neutralize
acidic leachates better than the other two soils, and in many cases,
precipitation of metal hydroxides will result. Probably adsorption as well
as precipitation are significant for the removal of metals in cases where the
metal concentrations are as high as those described above. Thus, the high
clay and organic content of the Catlin soil would make it a better medium for
adsorption than the other two soils. Figures 10 and 11 illustrate the "worst"
cases for two metals that are found throughout the supernatant solutions. In
the other leachate solutions, these metals were either present in concentra-
tions too low for detection, or they were attenuated during mixing in the
first reaction vessel to concentrations too low for detection. None of the
metals mentioned above displayed any degree of elution from the soils.
Because of their selective removal, the behavior of the other constit-
uents measured in the attenuation analysis was not as consistent or as easily
interpreted as that of the metals discussed above. From this investigation,
Mg and Mn emerge as having the most potential for pollution from land
disposal of the coal solid wastes. Both Mg and Mn undergo varipus degrees
of elution (negative attenuation), depending upon the particular waste
leachate-soil mixture.
Figures 12 and 13 are plots of the elution of Mn through the reactor
series for two of the liquefaction residue leachates. Overall, the greatest
elution of Mn occurred in the liquefaction residue leachate-soil mixtures.
In a typical example (fig. 12), an initial flush of Mn from the soil is
followed by adsorption or reverse exchange out of solution. The trend is
generally that the more acid the leachate-soil mixture, the higher the
3000 H
I
2 2000-
1000-
Supernatant concentration
SRC.,
(Secondary drinking water standard, 0.3 ppm)
•_ Bl,
Catlin sil
I
Soil leachate ratio, (|ni/ml_
Figure 11. Total Fe concentration vs. soil/leachate ratio for SRC4 (pH 3.5).
63
-------
(Secondary drinking water standard, 0.05 ppm)
2 3
Soil leachate ratio, gm/mL
Figure 12. Manganese concentration vs. soil/leachate ratio for SRC (pH 4.69).
Ill
12-
10-
E
a
a
c*
O p _
to .
c
03
1 >
at
O>
c
(O
01
5 4-
s
2-
n-
s
•r
/
/
/
/
/
K
/
/
f (Secondary drinking water standard.
/
1
/
j
I
1
;^
II *-—•»-. ^
// "~"^ -^-I'El
//'
i/'.*..
•' ''-^ • Catlin sil
*^-- Supernatant concentration
0.05 ppm)
• ^
•
234567
Soil leachate ratio, gm/mL 15051979
Figure 13. Manganese concentration «s. soil/leachate ratio for H-Coal (pH 3.10).
64
-------
concentration of Mn initially eluted. A mixture of the acid H-Coal leachate
with the Bloomfield soil, however, resulted in a greater elution of Mn than
when the leachate contacted the other two soils (fig. 13). A similar
example is the acid SRC.,, where the initial leachate Mn concentration is
5.4 ppm and the final Bloomfield elution was 108.2 ppm Mn. The recommended
water quality level for Mn is 0.05 ppm (U.S. EPA), 1972). The other mixtures
exhibit a pattern similar to that of figure 12, but the initial eluted Mn
concentrations are in the range of 0.5 to 4.0 ppm.
An elution of Mg is observed for all the leachate-soil mixtures with the
exception of the Bloomfield mixture (fig. 14). In several cases, the increase
in Mg concentration is as high as 300 ppm. These flushes of Mg are thought to
be caused by cation-exchange reaction in the soil. The flushes of minerals
have been found to cause increases in the hardness of groundwaters around
waste disposal sites similar to those envisioned for the disposal of coal con-
version wastes (Griffin and Shimp, 1978).
The fate of boron in the coal wastes is of interest because it was found
to exceed the recommended water quality levels for irrigation water in all of
the waste leachates, except for the water-quenched slag. Boron's concentra-
tion ranges from 5 ppm to as high as 65 ppm (Lurgi Ash, Rosebud Seam Coal) in
the leachates. Catlin soil, followed by Ava and Bloomfield respectively, was
the most efficient at removing boron (fig. 15). Other researchers have shown
that boron is readily adsorbed by illite (Harder, 1961; and Couch and Grim,
1968), and that adsorption increases with increasing pH (Sims and Bingham,
1967). Both of these factors favor higher retention of boron by Catlin soil
than the Ava and Bloomfield soils.
2 3
Soil leachate ratio, gm/mL
Figure 14. Mg concentration vs. soil/leachate ratio tor SRC IpH 3.5).
65
-------
In almost all of the natural pH supernatant solutions, calcium and sul-
fate are the dominant cation and anion in solution. Over the pH range stud-
ied, S04~2 is the dominant sulfur species in solution (Garrels and Christ,
1965; Stumm and Morgan, 1970). Because of the high concentrations of both
calcium and sulfate and the rate at which they are removed from solution, the
precipitation of gypsum (CaSO^-ZHzO) and/or anhydrite (CaSOO would seem to be
an important attenuation mechanism. Figure 16 plots the typical case for sul-.
fate attenuation with the trend of Ava > Catlin > Bloomfield. Adsorption of
sulfate could also be occurring with the acid leachate-Ava mixture, although,
because of the amount of sulfate being removed (Bolt and Bruggenwert, 1976),
it is unlikely that this is the only mechanism.
Figures 17 and 18 are combined plots of calcium and sulfate behavior
through the reactor series. The figures have been normalized by using C/Co
(the constituent concentration in each reaction vessel/the original leachate
concentration) for the vertical axis. The first plot indicates there is a
definite relationship between the removal of calcium and sulfate, which sup-
ports an interpretation that precipitation of gypsum is the dominant attenua-
tion mechanism. The second graph, however, gives the more normal case where
both constituents are removed similarly in the Ava mixtures, but calcium is at
least initially eluted, whereas sulfate is attenuated for the Catlin and
Bloomfield mixtures. These samples indicate that in some situations, adsorp-
tion of sulfate by soil appears to be the dominant attenuation mechanism. It
is difficult to account for precipitation of CaSOij for the last two leachate-
soil mixtures because it was impossible to account for the available Ca from
the soils themselves.
30-
LURGI Rosebud,
-Supernatant concentration
Ava sicl
Irrigation water, recommended standard (0.75 ppm)
—( , - r • -
234
Soil leachate ratio, gm/mL
Figure 15. Boron concentration vs. soil/leachate ratio for Lurgi-Rosebud (pH 8.4).
66
-------
• Supernatant concentration
Fly ash.
Secondary drinking water standard
~\ 1 1 r
2345
Soil leachate ratio, gm/mL
Figure 16. Sulfate concentration vs. soil/leachate ratio for fly ash (pH 4.12).
I.O-
0.5-
S(V_8loomfie/d / Ca-Bloomfield
S04-Catlin
Ca-Catlin
2 3
Soil leachate ratio, gm/mL
4
ISGS 1979
Figure 17. Ratio of concentration of Ca or SO4 in leachate after reaction with soil to the initial concentration vs. soil/leachate ratio.
67
-------
1.5-1
1.0-
o
u
0.5
SOj-Catlin
S
-------
and the soil bulk density. From this data, the migration distance per unit
time can be computed.
If it is assumed that: soil bulk density = 1.50 gm/cm3, leachate volume
6 in./yr (15.24 ml/cm2 yr), and landfill life = 30 years, then the migration
distance is computed to be:
(0.75 gm/mL(15.24 ml/cm2 yr)(30 years)
— = 228 cm or 7.5 ft in 30 years
1.50 gm/cm3
This calculation does not account for dilution by soil water or waters
of infiltration, and interactions occurring in the soil profile prior to the
subsequent waste additions reaching the leachate front.
69
-------
SECTION 9
BIOASSAYS OF LEACHATES FROM COAL SOLID WASTES
INTRODUCTION
The environmental data acquisition for a complete environmental assess-
ment of coal-based energy technology includes physical, chemical, and bio-
logical analyses (Hangebrauck, 1978). The preceding sections have comprised
the physical and chemical analyses of this investigation; this section com-
prises the biological analysis investigation of the potential pollution
hazard of coal solid wastes.
If coal conversion processes are developed on a commercial scale, they
will generate an enormous amount of solid waste (Braunstein, Copenhaver, and
Pfuderer, 1977). The solid wastes from coal conversion plants will probably
be deposited in landfills and ponds (Talty, 1978). Landfills are subject to
leaching; ponds could be contaminated and thus serve as potential sources of
pollution to other water resources such as groundwater and nearby streams.
Since the impact of coal solid wastes on aquatic biota has not been adequately
assessed, toxicity tests of the leachates generated from these wastes were
conducted with fathead minnow fry (Pimephales promelas].
The purposes of toxicity tests were to determine: (1) if the leachates
from three Lurgi gasification ashes, an H-Coal liquefaction residue, an SRC
liquefaction residue, two chars, a fly ash, a water-quenched slag, and two
gob samples were acutely toxic to young fathead minnows; (2) how much dilution
was necessary to eliminate mortality caused by toxic leachates on a short-term
basis; (3) if the acute toxicity of leachates equilibrated under anaerobic
conditions differed significantly from similar leachates equilibrated under
aerobic conditions; and (4) which water-soluble constituents leached from
these coal solid wastes were responsible for the toxicity.
MATERIALS AND METHODS USED FOR BIOASSAYS
Ninety-six hour static bioassays of the leachates were conducted with
1- to 6-day-old fathead minnow fry, Pimephales pvomelas. The fish were propa-
gated in the laboratory and in outdoor ponds at the Illinois Natural History
Survey in Urbana, Illinois. The leachates were obtained from the same vessels
used in the solubility and attenuation studies; they were filtered through a
0.45 ym pore size membrane filter prior to the bioassays.
The toxicity tests were divided into two phases: the screening procedure
and the LC-50 determination. During the screening procedure, the young
70
-------
fathead minnows were exposed to the "full-strength" leachates. During the
LC-50 determinations, the minnows were exposed to "full-strength" leachates
diluted with soft reconstituted water that was prepared according to sugges-
tions in "Methods for Acute Toxicity Tests with Fish, Macro-invertebrates and
Amphibians" (Committee on Methods for Toxicity Tests with Aquatic Organisms,
1975). The screening procedure enabled us to determine LC-50 values more
efficiently, since LC-50 determinations were not needed for leachates that
did not cause 50 percent mortality in the screening procedure. Procedures
outlined in Litchfield and Wilcoxon (1949) were used for the LC-50 deter-
minations.
•Ten young fathead minnows were placed into glass fingerbowls (115 x
45 mm) containing 200 mL of "full-strength" or diluted leachate. Each bio-
assay was replicated. Fish mortality data were collected at 24, 48, 72, and
96 hours after the bioassays were begun. The test organisms were not fed and
the solutions were not aerated during the bioassays. Since one-half of the
leachates were equilibrated under anaerobic conditions, all solutions were
aerated before the fish were added. The bioassays were conducted at a con-
stant temperature (21 ± 1°C) and with a constant photo-period (16L-8D) in an
environmental chamber. At the beginning and end of all bioassays, pH and
dissolved oxygen were measured with a Beckman pH meter and a YSI dissolved
oxygen meter. Specific conductance was measured at the beginning of each
bioassay with a YSI portable conductivity meter.
RESULTS OF BIOASSAY STUDY
The screening procedures were conducted to determine if the "full-
strength" leachates were acutely toxic. To test the effect of pH on the
mortality of fathead minnows, bioassays were conducted utilizing buffered re-
constituted water ranging in pH from 4.9 to 11.0. The results of the pH
experiment were similar to those of the screening procedures (figs. 19 to 23).
Many of the leachates and the reconstituted water were not acutely toxic to
young fathead minnows if the pH of the solutions was between 6.2 and 9.0.
Low mortality (5 to 20 percent) occurred, however, in 37.5 percent of the
neutral leachates, and mortality was greater than 20 percent in a Lurgi Ash
(111-5-6, pH = 7.1), H-Coal (HC-5, pH = 8.8), solvent-refined coal (SRC-6,
pH = 7.3), and a low-sulfur gob (LSR-2, pH = 6.9). Total mortality occurred
in those solutions with pH values less than 6.0, and mortality was 50 percent
or higher in solutions with pH values greater than 10.0.
The mortalities that occurred during the screening procedures of the
natural pH leachates are listed in table 22. The natural pH leachates from
the Lurgi gasification process were not acutely toxic. The aerobic natural
pH leachate generated from H-Coal liquefaction residue was relatively non-
toxic on a short-term basis; however, HC-5, the natural pH leachate equili-
brated under anaerobic conditions, was relatively alkaline (pH = 8.8), and
35 percent mortality occurred. Total mortality occurred in the aerobic
natural pH leachate from SRC dry mineral residue; this leachate was acidic
(pH = 5.6). The natural pH leachate of SRC equilibrated under anaerobic con-
ditions (SRC-6) was a neutral solution (pH = 7.1); however, 40 percent
mortality occurred during the screening procedure. The natural pH leachates
71
-------
100
80-
>• 60
e
o
40
20-,
•ana o
• Illinois 5 -Air
O Illinois 5-Argon
• Illinois 6 - Air
D Illinois 6 Argon
A RtWfltM.'. A,'
A Rosebud—Argon
X Reconstituted water
2.0
—i—
3.0
4.0
11.0
Figure 19. Percentages of mortality of 1- to 6-day-old fathead minnow fry (Pimephales promelas) resulting from 96-hour exposures
to 24 leachates of different pHs generated from three Lurgi gasification ashes and 7 buffered solutions of reconstituted
water.
100
o
80-
60-
40-
20
§• m
• H-Coal-Air
O H-Coal-Argon
• SRC-Air
O SRC-Argon
X Reconstituted water
2.0
3.0
4.0
5.0
9.0
10.0
11.0
pH
Figure 20. Percentages of mortality of 1- to 6-day-old fathead minnow fry (Pimephales promelas) resulting from 96-hour exposures
to 16 leachates of different pHs generated from SRC and H-Coal liquefaction residue and 7 buffered solutions of recon-
stituted water.
72
-------
100
80-
60-
o
40
20
-B-
-e—e*.
2.0
• Bottom slag-Air
O Bottom slag-Argon
• Fly ash-Air
D Fly ash-Argon
X Reconstituted water
3.0
4.0
5.0
10.0
I 1.0
Figure 21. Percentages of mortality of 1-to 6-day-old fathead minnow fry (Pimephales promelas) resulting from 96-hour exposures
to 16 leachates of different pHs generated from a water-quenched slag and a fly ash and 7 buffered solutions of reconsti-
tuted water.
IOO
80-
> 60'
o
40-
20-
-BH
2.0
• HTC-Air
O HTC-Argon
• LTC-Air
D LTC-Argon
X Reconstituted water
3.0
4.0
9.0
10.0
II.O
Figure 22. Percentages of mortality of 1-to 6-dayold fathead minnow fry {Pimephales promelas) resulting from 96-hour exposures
to 16 leachates of different pHs generated from high- and low-temperature chars and 7 buffered solutions of reconsti-
tuted water.
73
-------
TABLE 22. PERCENTAGES OF MORTALITY OF 1-TO-6-DAY-OLD FATHF.AD MINNOW FRY (i'lUKrHALZC ':~EC;-ZLAz)
RESULTING FROM 96-110UU EXPOSURES TO THE NATURAL pH LF.ACHATFS OF .1.1 COAT. SOLID WASTES
Sample
BS-1
BS-5
ILL-5-1
ILL-5-5
ILL-6-1
ILL-6-5
HC-1
HC-5
SRC-2
SRC-6
KS-3
KS-7
FA-3
FA- 7
HSR-2
HSR- 6
LSR-1
LSR-5
HTC-1
HTC-5
LTC-2
LTC-6
Type
Gasification ash
Gasification ash
Gasification ash
Gasification ash
Gasification ash
Gasification asli
Liquefaction residue
Liquefaction residue
Liquefaction residue
Liquefaction residue
Water-quenched sing
Water-quenched slag
Fly ash
Fly ash
High-sulfur gob
High-sulfur gob
Low-sulfur gob
Low-sulfur gob
High-temperature char
High-temperature char
Low-temperature char
Low-temperature char
Atmosphere
Aerobic
Anaerobic
Aerobic
Anerobic
Aerobic
Anaerobic
Aerobic
Anaerobic
Aerobic
Anaerobic
Aerobic
Anaerobic
Aerobic
Anaerobic
Aerobic
Anaerobic
Aerobic
Anaerobic
Aerobic
Anaerobic
Aerobic
Anaerobic
P
7.
8.
7.
7.
7.
7.
8.
8.
5.
7.
3.
5.
4.
4.
7.
8.
8.
8.
7.
7.
6.
8.
H
8
0
1
3
1
5
3
8
6
3
7
8
0
3
7
0
8
9
2
6
8
1
Mortality
0
0
0
0
0
0
15
100
100
40
100
100
100
100
5
0
15
15
0
0
5
0
from the water-quenched slag and the fly ash from a coal-fired power plant
were acidic (pH <5.8), and total mortality occurred in all four leachates.
Low mortality (<5 percent) occurred in the natural pH leachates generated
from the high-sulfur gob. Both natural pH leachates generated from the low-
sulfur gob were relatively alkaline (pH values of 8.8 and 8.9), and low
mortality (15 percent) occurred in these solutions. Low mortality (<5 per-
cent) occurred in natural pH leachates generated from the high- and low-
temperature chars.
Attempts were made to decrease the mortality rate caused by low pH by
neutralizing some of the acidic leachate solutions with sodium hydroxide.
Total mortality occurred in all neutralized solutions. Since all the neu-
tralized solutions had specific conductance values greater than 7.00 mmhos/cm,
it was postulated that the exposures to relatively large total ion concentra-
tions resulted in "ionic shock." To test this hypothesis, several solutions of
reconstituted water of differing specific conductances were prepared using
NaCl; the results of 96-hour static bioassays of these solutions are shown in
figure 24. Total mortality occurred in solutions with a specific conductance
74
-------
100-
80-
60-
o
40.
20-
• HSR-Air
O HSR-Argon
• LSR-Air
D LSR-Argon
X Reconstituted water
2.0
3.0
4.0
9.0
10.0
11.0
Figure 23. Percentages of mortality of 1- to 6-day-old fathead minnow fry (Pimephales promelas) resulting from 96-hour exposures
to 16 leachates of different pHs generated from a high-sulfur gob sample and a low-sulfur gob sample and 7 buffered
solutions of reconstituted water.
345
Specific conductance (mmhos/cm)
Figure 24. Percentages of mortality of 1 - to 6-day-old fathead minnow fry (Pimephales promelas) resulting from 96-hour exposures
to 7 buffered solutions of reconstituted water of different specific conductances adjusted with NaCI.
75
-------
greater than 6.10 mrnhos/cm. The high total ion concentrations were probably
responsible for the total mortality that occurred in the neutralized acidic
leachates.
The LC-50 values were determined to investigate the relative toxicities
of the leachates and how much dilution was necessary to ensure their survival
during 96-hour static bioassays. The LC-50 values, their 95 percent confidence
intervals, and the dilutions necessary to ensure survival of the minnows are
listed in tables 23 to 27. The pH values listed are those of the "full-strength"
leachates after aeration and prior to dilution with reconstituted water. The
TABLE 23. THE LC-50 VALUES, THEIR 95 PERCENT CONFIDENCE INTERVALS, AND THE AMOUNT OF DILUTION
NECESSARY TO ELIMINATF, MORTALITY FOR THREE LURCT GASIFICATION ASH LEACHATES OBTAINED
IN 96-HOUR STATIC BIOASSAYS USING 1-TO-6-DAY-OLD FATHEAD MINNOW FRY C/'./'«£.'V//1WS
PROI-1ELAS).
"" - .- ' ._.--.-__!_ . . _™_ -r- ._.___.___._, • . i. -!-._-. . , -i _. -r -M. ._.-.— r i "• ' l •
Sample
1*
2
3
4
5*
6
7
8
1*
2
3
4
5*
6
7
8
1*
2
3
4
5*
6
7
8
Atmosphere
Aerobic
Aerobic
Aerobic
Aerobic
Anaerobic
Anaerobic
Anaerobic
Anaerobic
Aerobic
Aerobic
Aerobic
Aerobic
Anaerobic
Anaerobic
Anaerobic
Anaerobic
Aerobic
Aerobic
Aerobic
Aerobic
Anaerobic
Anaerobic
Anaerobic
Anaerobic
pH
Rosebud
7.8
7.6
5.4
3.3
8.0
7.6
4.7
3.7
Illinois No.
7.1
7.0
6.1
3.0
7.3
7.1
6.0
4.4
Illinois No.
7.1
4.1
3.9
2.6
7.5
7.1
. 4.9
3.8
LC-50
(ml./ 100 mL)
>.100
>100
18.00 < 2.70
0.50 ' 0.13
>.100
>100
2. .10 :' 0.76
0.78 -.1. 0.16
5
>100
>100
11.00 ± 3.85
1.80 :' 0.61
>100
>100
40.00 ± 16.40
1.00 + 0.09
6
>100
8.60 ± 2.92
5.20 ± 0.99
6.40 i 0.90
>100
>100
10.00 ± 2.60
0.38 i- 0.01
Dilution for
0% mortality
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
:1
:1
:100
:769
:1
:1
:200
:250
:1
:1
:50
:166
:1
:1
:50
:200
:1
:43
:38
:1000
:1
:1
:26
:1000
*Natural 'pH solutions
76
-------
LC-50 value is the statistically determined concentration of leachate at
which 50 percent mortality occurs. There is an inverse relationship between
toxicity and the LC-50 value; for example, the LC-50 values for Rosebud-3
(BS3) and BSi, are 18.00 and 0.50, respectively (table 23). Eighteen milli-
liters of 883 diluted with 82 mL of reconstituted water was as toxic as
0.50 mL of BSi, diluted with 99.5 mL of reconstituted water. Leachates exhib-
iting greater toxicity, therefore, have lower LC-50 values than less toxic
leachates. If, in the "full-strength" leachates, less than 50 percent mor-
tality occurred, the LC-50 is reported as greater than 100 mL/100 mL.
Generally, all leachates were acutely toxic when acidic (pH <6.2). With
increasing acidity, toxicity also increased and the LC-50 value decreased.
The LC-50 values of leachates equilibrated under aerobic atmospheres were not
significantly different from LC-50 values of similar leachates equilibrated
under anaerobic atmospheres (p >.05, paired t-test).
Natural pH leachates generated from Lurgi gasification ashes were not
acutely toxic; therefore, their LC-50 values were greater than 100 mL/100 mL,
and no dilution was necessary to achieve 0 percent mortality (table 23).
TABLE 24. LC-50 VALUES, THEIR 95 PERCENT CONFIDENCE INTERVALS, AND THE AMOUNT OF DILUTION
NECESSARY TO ELIMINATE MORTALITY FOR H-COAL AND SRC LIQUEFACTION LEACHATES OBTAINED
IN 96-HOUR STATIC BIOASSAYS USING 1-TO-6-DAY-OLD FATHEAD MINNOW FRY (PIMEPHALES
PROMELAS).
Sample
1*
2
3
4
5*
6
7
8
1
2*
3
4
5
6*
7
8
Atmosphere
Aerobic
Aerobic
Aerobic
Aerobic
Anaerobic
Anaerobic
Anaerobic
Anaerobic
Aerobic
Aerobic
Aerobic
Aerobic
Anaerobic
Anaerobic
Anaerobic
Anaerobic
pH
H-Coal
8.3
7.7
5.9
3.3
8.8
7.6
7.6
3.1
SRC-I
7.7
5.6
3.6
3.1
6.6
7.3
5.5
3.7
LC-50
(mL/100 mL)
>100
>100
39.00 ± 4.80
29.50 •': 8.85
>100
>100
>100
7.90 i 1.66
>100
21.00 :'. 3.36
16.00 i 2.72
0.36 ± 0.10
74.00 ± 6.22
>100
25.00 ± 2.75
0.26 ± 0.07
Dilution for
0% mortality
1:1
1:1
1:5
1:21
1:6
1:1
1:1
1:46
1:1
1:10
1:10
1:1000
1:2
1:1
1:7
1:2000
*Natural pH solutions
77
-------
TABLE 25. LC-50 VALUES, THEIR 95 PERCENT CONFIDENCE INTERVALS, AND THE AMOUNT OF DILUTION
NECESSARY TO ELIMINATE MORTALITY FOR LEACHATES GENERATED FROM BOTTOM SLAG AND FLY ASH
OBTAINED IN 96-HOUR STATIC HIOASSAYS USING l-TO-f)-!)AY-O!.n KATIIKAD MINNOW FRY
' (PIMEPHALES PROMELAS).
Sample
1
2
3*
4
5
6
7*
8
1
2
3*
4
5
6
7*
8
Atmosphere
Aerobic
Aerobic
Aerobic
Aerobic
Anaerobic
Anaerobic.
Anaerobic
Anaerobic
Aerobic
Aerobic
Aerobic
Aerobic
Anaerobic
Anaerobic
Anaerobic
Anaerobic
PH
Slag
8.0
7.6
3.7
3.3
7.7
7.1
.. 5.8
3.8
Fly ash
8.7
8.0
4.0
2.7
9.6
7.9
4.3
2.4
LC-50
(mL/100 ml.)
>100
>100
22.50 ± 4.28
8.00 ± 1.68
MOO
MOO
37.00 i 3.89
3.90 ! 0.55
>100
>100
9.00 ' 2.70
0.64 •' 0.08
80.00 :' 7.20
MOO
3.15 :>: 0.72
0.68 :' 0.12
Dilution for
0% mortality-
1
1
1
1
1
1
L
1
1
1
1
1
1
1
1
1
:1
:l
:28
:20
:1
:1
:5
:100
,
:l
:1
:100
:2000
:3
:1
:1000
:333
*Natural pH solutions
The aerobic natural pH leachate generated from H-Coal liquefaction resi-
due was not acutely toxic and therefore required no dilution for 0 percent
mortality. During the screening procedure, total mortality occurred in the
anaerobic natural pH H-Coal leachate (table 22). During the LC-50 determina-
tion, however, 40 percent mortality occurred in the full-strength leachate,
and 30 percent mortality occurred in a solution of 180 ml of HC-5 and 20 ml
of reconstituted water. The LC-50 determination was made 9 months after the
screening procedure was performed, and apparently the leachate had not
reached equilibrium at the time of the screening procedure. The LC-50 value
for HC-5, therefore, was greater than 100 mL/100 mL, even though total mor-
tality occurred during the screening procedure (table 24). The aerobic nat-
ural pH leachate generated from the SRC liquefaction residue had a pH of 5.6,
was acutely toxic, and required a 1:10 dilution to eliminate mortality. In
addition, we estimate that 50 percent mortality would occur in a solution of
21 mL SRC-2 and 79 ml reconstituted water (table 24). The anaerobic natural
pH SRC leachate had an LC-50 value greater than 100 mL/100 mL, and required
less than a 1:1.5 dilution to eliminate mortality.
The natural pH leachate generated from the water-quenched slag and equil-
ibrated under aerobic conditions was relatively toxic (LC-50 = 22.50 ± 4.28)
and required a moderate amount of dilution (1:28) to negate its toxicity. The
78
-------
TABLE 26. LC-50 VALUES, THEIR 95 PERCENT CONFIDENCE INTERVALS, AND THE AMOUNT OF DILUTION
NECESSARY TO ELIMINATE MORTALITY FOR HIGH-SULFUR AND LOW-SULFUR GOB LEACHATES
OBTAINED DURING 96-HOUR STATIC BIOASSAYS USING 1-TO-6-DAY-OLD FATHEAD MINNOW FRY
(PIMEPHALES PROMELAS).
Sample
Atmosphere
PH
LC-50
(mL/100 mL)
Dilution for
0% mortality
1*
2
3
4
5*
6
7
Aerobic
Aerobic
Aerobic
Aerobic
Anaerobic
Anaerobic
Anaerobic
Anaerobic
LSR
7.9
5.4
3.8
8.9
7.7
6.6
>100
>100
57.00 •'; 2.28
3.80 .'• 0.4V
>100
>100
96.00 ± 0.83
2.1.5 ± 0.16
HSR
1:1
1:1
1:3
1:50
1:1
1:1
1:1
1:100
1
2*
3
4
5
6*
7
8
Aerobic
Aerobic
Aerobic
Aerobic
Anaerobic
Anaerobic
Anaerobic
Anaerobic
8.
7.
3.
2.
8.
8.
3.
2.
1
7
5
7
0
0
9
6
>100 '
>100
41.00 ±
3.00 ±
>100
>100
56.00 ±
2.30 ±
2.
0.
2.
0.
87
62
52
14
1
1
1
1
1
1
1
1
:1
:1
:4
:67
:1
:1
:2
:67
*Natural pH solutions
natural pH slag leachate equilibrated under anaerobic conditions was less
toxic (LC-50 = 37.00 ± 3.89) and less acidic than the aerobic leachate. Both
natural pH leachates generated from the fly ash were relatively toxic
(LC-50 <11.70) and required a dilution of 1:100 or greater to ensure survival
during the bioassay. The natural pH leachates of the two gob and two char
samples were not sufficiently toxic on a short-term basis to establish LC-50
values and required little dilution (<1:1.5) to eliminate mortality
(tables 26 and 27).
DISCUSSION OF BIOASSAY RESULTS
The potential hazard that coal solid wastes pose to the aquatic environ-
ment lies in the relatively large concentrations of accessory elements in the
waste and the possibility of acid formation. Accessory elements could be
leached from the solid wastes by water in a slag pond or water percolating
through a landfill. Pyritic minerals in these solid wastes produce acid when
exposed to air and water, and acid could lower the pH of the pond or the pH
of the water passing through a landfill. Lowering the pH could increase the
leaching of potentially hazardous chemical constituents or directly harm
organisms in the affected area.
79
-------
TABLE 27. LC-50 VALUES, THEIR 95 PERCENT CONFIDENCE INTERVALS, AND THE AMOUNT OF DILUTION
NECESSARY TO ELIMINATE MORTALITY FOR HIGH-TEMPERATURE AND LOW-TEMPERATURE CHAR
LEACHATES OBTAINED DURING 96-HOUR STATIC BIOASSAYS USING 1-TO-6-DAY-OLD FATHEAD
MINNOW FRY (I'lMKI'HAW.
Sample
1
2*
3
4
5
6*
7
Atmosphere
Aerobic
Aerobic
Aerobic
Aerobic
Anaerobic
Anaerobic
Anaerobic
Anaerobic
LC-50
(mL/100 mL)
LTC
9.2
(,.8
4.2
4.0
8.8
8.1
4.6
3.8
HTC
>100
>10()
12.00 ' 1.30
3.48 ± 0.48
98.00 i 2.00
>100
17.40 :'. 1.22
1.03 ± 0.11
1*
2
3
4
5*
6
7
8
Aerobic
Aerobic
Aerobic
Aerobic
Anaerobic
Anaerobic
Anaerobic
Anaerobic
7
6
5
3
7
7
5
4
.2
.5
.4
.9
.6
.8
.4
.3
>100
>100
5.40 i
O.HO '
>100
>100
14.00 :>•
3.20 :'.
0.92
0. 1.8
1.54
0.20
Dilution for
0% mortality
1:1
1: .1.
1:20
1:50
1:1
1:1
1:8
1:200
1:1
1:1
1:100
1:333
1:1
1:1
1:13
1:50
*Natural pH solutions
Three of the 11 natural pH leachates that were equilibrated under aero-
bic atmospheres (SRC liquefaction residue, water-quenched slag, and fly ash)
were acidic (pH <6.2). Total mortality occurred during the screening proce-
dures of these acidic leachates (table 22). These acidic leachates were
relatively toxic (LC-50 <25.00 ml/100 ml) and at least a 1:10 dilution was
necessary to ensure survival during a bioassay (tables 24 and 25).
Many factors probably contributed to the acute toxicity of the acidic
leachates. It has been demonstrated (Griffin et al., 1978) that total mor-
tality occurs when fathead minnow fry are exposed to acidic reconstituted
water (pH <5.9) for 96 hours. Since the test organisms were propagated.and
held in water having a pH of approximately 7.4 and then experienced a rapid
change in pH, the mortality was partially due to "ionic shock." A rapid
lowering of the pH disrupts the Na+/H+ exchange system of fish and results
in a loss of sodium that can cause death (Giles and Vanstone, 1976). Some
of the acidic leachates also contained concentrations of Al, Cr, Cu, Mg, Ni,
and Zn, which under laboratory conditions have been shown to be acutely toxic
to fish (Brown, 1968; Doudoroff and Katz, 1953; Eaton, 1973; McCarty, Henry,
and Houston, 1978; Pickering, 1974; and-Pickering and Cast, 1972).
80
-------
The natural pH leachates generated from the H-Coal liquefaction residue
and the low-sulfur gob were relatively alkaline (pH >8.3) and acutely toxic
during the screening procedure (table 22). The organisms were propagated
and held in water having a pH of approximately 7.4; they experienced a rapid
change in pH during the bioassays. Thus the mortality might partially be
caused by the rapid rise in pH, since 5 percent and 50 percent mortality
occurred in bioassays of reconstituted water with pH's of 9.2 and 10.0,
respectively. The short-term acute toxicity of three of these four natural
pH leachates, however, was eliminated with little dilution (<1:1.5), and
HC-5 required a 1:6 dilution to ensure survival during a 96-hour bioassay.
Because of the complex chemical composition of the leachates and the
unknown synergistic and antagonistic effects of the chemical constituents
composing the leachates, it is not possible from these experiments to deter-
mine specifically which chemical constituents were directly responsible for
the observed mortality. This point is illustrated dramatically by the
anaerobic leachates generated from SRC liquefaction residue. The pH of the
leachate during the screening procedure was 7.3, yet 40 percent mortality
occurred. In addition, none of the chemical constituents were present in
concentrations exceeding known acute LC-50 values.
To determine more precisely which chemical constituents are responsible
for the toxicity of coal solid waste leachates, it is necessary to perform
additional chemical and biological analyses. Such analyses would include
the determination of organic compounds found in the wastes and leachates, as
well as bioassays of particular chemical constituents and mixtures of chemi-
cal constituents found in those leachates generated from coal solid wastes,
such as Al, Cd, Cu, Mg, and Ni.
When coal solid wastes are disposed of in landfills, it is important to
investigate how the waste leachates interact with earth materials; the
results of our investigation of soil-leachate interactions were discussed
earlier in this report. Unfortunately, because of the small amount of leach-
ate used in the attenuation study, we were not able to conduct bioassays of
the filtrates; however, Al, Fe, K, Mg, and Zn were present in large enough
concentrations to pose a hazard. For example, the filtrates produced from
the acidified SRC leachate often contained zinc in amounts higher than
0.87 mg/L, which was the LC-50 value for zinc using fathead minnows in soft
water, determined by Pickering and Henderson (1966).
Filtrates from the two chars, the low-sulfur gob, the SRC liquefaction
residue, and the two Lurgi ashes tested often contained more than 5 mg/L of
potassium. Although potassium is not acutely toxic to fathead minnows at
this concentration, it is acutely toxic to other aquatic organisms such as
freshwater mussels (Imlay, 1973). Even though several elements in the leach-
ates are attenuated by the soil, some are not affected; they may even be
eluted from the soil and could become a hazard to the aquatic environment.
The soil characteristics of a proposed disposal site for coal solid wastes,
therefore, and the location and access to nearby water resources should be
studied before the site is chosen.
81
-------
This limited biological analysis of the potential hazard of coal solid
wastes consisted of acute static bioassays of the waste leachates using fat-
head minnow fry. It is considered very important to increase the scope of this
investigation to assess the environmental impact of coal solid wastes.
Several types of aquatic organisms should be tested in addition to fish,
although recommended safe levels for selected test fish such as the fathead
minnow, Pimephales promelas, quite often provide protection to other aquatic
animals and plants (U.S. EPA, 1972).
Patrick, Cairns, and Scheier (1968) made a comparative study of the
effects of 20 pollutants on fish, snails, and diatoms and found that no
single kind of organism was most sensitive in all situations. A literature
review by Braunstein, Copenhaver, and Pfuderer (1977) indicated that crusta-
ceans (such as Daphnia magna} and phytoplankton may be appreciably more sen-
sitive to trace elements than are insects and fish. Preliminary experiments
with Daphnia magna demonstrate that this zooplankter is more sensitive to SRC
liquefaction leachate than the fathead minnow fry. A complete environmental
assessment of coal solid wastes should therefore include acute ecological
bioassays utilizing fish, zooplankton, phytoplankton, and possibly a detrito-
vore—suggestions that have also been made in a recent EPA publication (EPA,
1977).
Besides conducting acute bioassays with several types of organisms,
representing all major trophic levels, it is also essential to conduct
chronic bioassays to assess the chronic effects of coal solid wastes. Long-
lived organisms such as fish might be harmed by long-term exposure (directly
or through the organism's food supply) to chemical constituents leached from
coal solid wastes. Reduced reproduction, malformation, disease,'reduced
growth, or generally decreased ability to compete with other organisms could
result from long-term sublethal exposure to potentially hazardous chemical
constituents found in coal solid wastes. It is important, therefore, to in-
vestigate the accumulation and concentration of potentially hazardous chemi-
cal constituents found in coal solid wastes by lower trophic levels, as well
as to investigate the chronic toxicity of coal solid wastes to long-lived
aquatic organisms.
Finally, a battery of health effects tests must be conducted on coal
solid wastes and leachates. The EPA has recommended (for a level 1 assess-
ment) that the wastes be tested for the presence of microbial mutagenicity,
rodent acute toxicity, and cytotoxicity. The specific tests include the Ames
Test, the Rabbit Alveolar Macrophage (RAM) assay, the Human Lung Fibroblast
(WI-38) Assays, and acute toxicity bioassays with rats. The tests detect a
broad spectrum of potential health effects, are not as costly as long-term
animal bioassays, and are relatively reliable (Smith, 1978). With these tests
it is possible to screen wastes, including coal solid wastes and their leach-
ates, for potential carcinogenicity, cytotoxicity, and other detrimental
health effects.
82
-------
SECTION 10
POTENTIAL POLLUTION HAZARD FROM COAL SOLID WASTES
Evaluating the potential pollution hazard of coal solid wastes involves
comparing the quantities of the wastes and their constituents with standards
for acceptable levels of these constituents in the environment. Unfortu-
nately, no established standards exist that delineate which specific chemical
or mineralogical compositions of coal solid wastes pose potential hazards.
Similarly, no established standards exist that specify which concentrations
of chemical constituents in aqueous effluents from coal solid wastes will
cause significant environmental damage. This section addresses this problem
by comparing the chemical analyses of the solid wastes and leachates and the
bioassay data, with the Multimedia Environmental Goals (MEGs) (Cleland and
Kingsbury, 1977) and the toxicant extraction procedure criteria (U.S. EPA,
1978) for hazardous wastes. Both MEGs and the toxicant extraction procedure
were sponsored or proposed by the U.S. EPA.
MATE VALUES FOR SOLID WASTES
The effluent guidelines proposed in the MEGs are known as Maximum Acute
Toxicity Effluents (MATE). A MATE value is a theoretical value calculated to
predict the maximum concentration of a constituent that will not have adverse
health or ecological effects after short-term exposure. MATE is now a
defunct term that will be replaced by DMEG (Discharge MEG) in future publica-
tions (D. Kingsbury, 1980, personal communication). MATELEi values were cal-
culated using equation 52 of MEGs Volume 1 (Cleland and Kingsbury, 1977,
p. 112). They were based on ecological effects using the LC-50 data from
Section 9 of this report.
Table 28 lists the MATE values for 50 inorganic constituents of solid
wastes disposed of on land. Each constituent has two values: one based on
predicted adverse effects to health, the other based on predicted adverse
effects to soil ecosystems. The table also lists the concentrations of those
constituents that were found to exceed their respective MATE values. Also
listed are the MATELE1 values, representing the MATE values measured for the
solid wastes as a whole.
The MATELE1 values indicated that eight of the 11 wastes were not acutely
toxic. The remaining three had MATELEi values that indicated relatively low
toxicity. On the other hand, the MATE values for the individual chemical con-
stituents of the waste indicated that 20 of the 50 constitutents were present
in greater concentrations than their MATE values. This implies that these 20
elements are potential pollution hazards—a statistic that does not agree well
83
-------
TABLE 28. CONSTITUENTS IN COAL UTILIZATION SOLID WASTES EXCEEDING HEALTH- OR ECOLOGY-BASED MATE VALUES FOR INDIVIDUAL PARAMETERS
AND MATELE1 VALUES FOR LAND DISPOSAL ACTUALLY DETERMINED FOR THE SOLID WASTE
CO
MATE*
Parameter
Ag
Al
Au
As
B
Ba
Be
Br
Ca
Cd
Ce
Cl
Cr
Co
Cu
F
Fe
Ga
Ge
Hf
Hg
K
La
Li
Mg
Mn
Mo
Na
Ni
Pb
Health
(mg/kg)
. 50
16,000
N
50
9,300
1,000
6
N
48,000
10
250,000
260,000
50
150
1,000
7,500
300
15,000
1,700
150
2
N
340,000
70
18,000
50
15,000
160,000
45
50
Ecology
(mg/kg)
10
200
N
10
5,000
500
11
N
3,200
0.2
N
N
50
50
10
.N
50
N
N
N
50
4,600
N
75
17,000
20
1,400
N
2
10
Lurgi
111. No. 5
95,506
11
760
15
22,571
1.6
171
50
151,016
12,867
2,014
195
182
Lurgi
111. No. 6
108,121
950
12
16,652
1.6
212
57
143,780
14,611
1,859
89
45
Lurgi
Rosebud H-Coal
101,188 17,253
22
3,900
60,106 7,862
1.6 0.4
55
49 14
60,059 23,662
5,230
21,531
929 77
5 21
38 32
SRC
67,529
74
11
7,933
1.3
100
100
135,169
8,717
155
14
59
Fly ash
73,600
46
16
26,100
1.9
130
140
134,400
20,900
380
160
110
Bottom
ash
(slag)
84,571
500
43,668
2
100
40
137,267
13,365
465
57
20
High- Medium-
temp, temp. High-S
char char refuse
17,147 13,601 56,522
13
4,574 6,075 28,159
0.5 0.4 1.4
14 11 29
23,951 5,860 86,157
9,962
77 57 310
20 12 48
12 55
Low-S
refuse
97,008
63
-. ' •
21, -227
1.8
78
36
24,813
17,102
310
55
55
-------
TABLE 28. Continued.
MATE* BnV-l-nm Uinh. Moftinm-
Parameter
P
Rb
s
Total
Sb
Sc
Se
Si
Sm
Sn
Sr
5 Ta
Te
Th
Ti
Tl
U
V
W
Zn
Zr
Health
3,000
360,000
N
1,500
160,000
10
30,000
160,000
N
9,200
15,000
300
130
18,000
300
12,000
500
3,000
5,000
1,500
Ecology Lurgi Lurgi Lurgi ash temp. temp. High-S Low-S
(mg/kg) 111. No. 5 111. No. 6 Rosebud H-Coal SRC Fly ash (slag) char char refuse refuse
0.1 218 87 2,095 44 1,004 873 786 87 87 829 1,397
N
N
40
N
5 . 16
N 245,653 229,946 225,739 39,641 110,930 194,300 222,934 40,015 50,490 145,490 261,380
N
N
N
N
N
N
160 6,415 6,295 6,475 1,019 1,799 5,100 4,436 959 4,318 4,668 8,298
N
100
30 172 184 30.8 33 112 230 56 35.3 39.8
N
20 1,500 400 31 71 560 62 48 42 300 500
N
MATE
LEI
values measured for solid waste (mg waste/kg soil) are as follows: Lurgi No. 5: >2 x 106 (nontoxic); Lurgi No. 6: >2 x 106
(nontoxic); Lurgi Rosebud: >2 x 106 (nontoxic); H-Coal: >2 x 106 (nontoxic); SRC: 42,000; fly ash: 18,000; bottom ash: 45,000; high-
temp, char: >2 x 106 (nontoxic); medium-temp, char: >2 x 106 (nontoxic); high-S refuse: >2 x 10s (nontoxic); low-S refuse: >2 x 106
(nontoxic).
N = none.
*From ApjJehdix C
model changes.
Cleland and Kingsbury, 1977; values listed here are 100 times those listed in Appendix C to reflect January 1978
fMATELE1 (yg/g) = 0.002 x MATE^ (yg/L); MATE^ (yg/L) = 100 x LC5o(mg/L).
-------
TABLE 29. DISCHARGE SEVERITIES FOR CONSTITUENTS IN COAL UTILIZATION SOLID WASTES EXCEEDING
HEALTH- OR ECOLOGY-BASED SOLID WASTE MATE VALUES
MATE
Param-
eter
Ag
Al
Au
As
6
Ba
Be
Br
Ca
Cd
Ce
Cl
Cr
Co
Cu
F
Fe
Ga
Ge
Hf
Hg
K
La
Li
Mg
Mn
Mo
Na
Ni
Pb
P
Rb
s£otal
Sc •
Se
Si
Sm
Sn
Sr
Ta
Te
Th
Ti
Tl
U
V
W
Zn
Zr
Total
Health
(mg/kg)
50
16,000
N
50
9,300
1,000
6
N
48,000
10
250,000
260,000
50
150
1,000
7,500
300
15,000
1,700
150
2
N
340,000
70
18,000
50
15,000
160,000
45
50
3,000
360,000
N
1,500
160,000
10
30,000
160,000
N
9,200
15,000
300
130
18,000
300
12,000
500
3,000
5,000
1,500
Ecology
(mg/kg)
10
200
N
10
5,000
500
11
N
3,200
0.2
N
N
50
50
10
N
50
N
N
N
50
4,600
N
75
17,000
20
1,400
N
2
10
0.1
N
N
40
N
5
N
N
N
N
N
N
N
160
N
100
30
N
20
N
Lurgi
No. 5
478
1
2
2
7
8
3
5
3,020
• 3
101
97
18
2,180
8
40
6
75
Lurgi
No. 6
541
2
2
5
8
4
6
2,876
3
93
44
4
870
8
39
6
20
Lurgi
Rose-
bud H-Coal
506 86
2
8
19 2
8 2
1
5 1
1,201 473
1
1
46 4
2 10
4 3
20,950 440
8 1
40 6
1 1
2 4
Bottom High- Medium-
SRC Fly ash
338 368
7 5
2 3
2 8
6 9
2 3
10 14
2,703 2,688
2 5
8 19
7 80
6 11
10,040 8,730
3
4 6
11 32
4 8
28
ash temp. temp.
(slag) char char
423 86 68
1
14 1 2
10 2 2
2
4 1 1
2,745 479 117
3
23 4 3
28 10 6
2 1
7,860 870 870
7 1 2
28 6 27
2
3 2 2
High-S
refuse
283
1
t
9
7
3
1,723
2
15
24
5
8,290
5
29
1
15
Low-S
refuse
485
7
7
9
2
4
496
4
15
27
5
13,970
9
52
1
25
discharge
severity
6,054
4,531
22,805 1,033
13,152 12,020
11,155 1,463 1,100
10,412
15,118
Discharge severity = concentration/MATE
86
-------
with the results generated by the MATELE1 values for the wastes (that eight
were not acutely toxic). It seems, therefore, that the MATE values for solid
waste disposal on land are perhaps conservative when applied to coal solid
wastes.
The discrepancy between the estimated hazard based on MATE values for
individual chemical constituents and the measured toxicity of the leachates
seems to originate in the assumption (during the derivation of the MATE value)
that the solid waste is highly soluble in water. Coal solid wastes are gen-
erally made up of materials of relatively low water solubility, this contra-
dicts the assumption and may be the reason for the overestimation of the
hazard for these particular wastes.
Another method to further evaluate the toxicity of the constituents is
comparing their discharge severities (concentration/MATE value). After doing
so (table 29), it is clear that Al, Fe, and P are predicted to have the most
potential for exceeding discharge limits and posing environmental problems.
MATE VALUES FOR LEACHATES
The MATE values for water quality of the chemical constituents measured
in the leachates from the coal wastes are given in tables 30 and 31. The
tables also provide a listing of those constituents in the leachates that ex-
ceeded their MATE values for individual parameters (appendix C in Cleland and
Kingsbury, 1977), along with a listing of MATEWE values (Cleland and Kings-
bury, 1977, eq. 50, p. Ill), which are based on ecological effects and acute
bioassay data that were obtained using the leachates from the wastes (Sec-
tion 9).
TABLE 30. MATEWE VALUES MEASURED FOR LEACHATES, BASED ON ECOLOGICAL EFFECTS AND BIOASSAY DATA
Leachate
Lurgi No. 5
Lurgi No. 6
Lurgi Rosebud
H-Coal
SRC
Fly ash
Bottom ash (slag)
High-temp, char
Medium- temp, char
High-S refuse
Low-S refuse
MATEWE value*
(yg/L)
>109
>109
>109
>109
2.1 x 10'
9 x 106
2.25 x 107
>109
>109
>109
>109
LC50 96-hr
(ppm)
>107
>107
>107
>107
210,000
90,000
225,000
>107
>107
>107
>107
Mortality, full
strength leachate
(«)
0
0
0
15
100
100
100
0
5
5
15
Dilution for,
no mortality
None
None
None
1:1
1:10
1:100
1:28
None
1:1 .
1:1
1:1
*MATEWE (pg/L) = 100 x LC50(mg/L)
No mortality during 96-hour bioassay.
87
-------
TABLE 31. CONSTITUENTS IN LEACHATES EXCEEDING HEALTH- OR ECOLOGY-BASED WATER MATE VALUES FOR INDIVIDUAL PARAMETERS
MATE*
Parameter
Al
As
B
Ba
Be
Ca
Cd
Cl
Cr
Co
Cu
F
Fe
Hg
K
oo Li
oo Mg
Mn
Mo
Na
NH,,+
Ni
Pb
P
s-2
SO,
Sb
Se
Si
Sn
Sr
Te
Ti
Tl
V
Zn
Health
(mg/L)
80
0.25
47
5
0.03
240
0.05
1,300
0.25
0.75
5.0
7.0
1.5
0.25
N
0.33
90
0.25
75
800
N
0.23
0.25
15
N
1,250
7.5
0.05
150
N
46
1.5
90
1.5
2.5
25
Ecology Lurgi Lurgi Lurgi
(mg/L) 111. No. 5 111. No. 6 Rosebud H-Coal
1 3.0
0.05
25 26.9
2.5
0.055
16 470 290 210 110
0.001 0.02 0.02
N
0.25
0.25
0.05
N 8.0
0.25
0.22
23 30 42
0.38 1.00 1.8
87
0.10 0.45
7
N
N
0.01 0.03 0.03
0.05 0.1 0.1
0.0005
N
N
0.2 0.4
0.25
. N
N
N
N
0.82
N
0.15
0.1 0.12
SRC Fly ash
62.6
58
415 508
0.39
0.31
0.20
1.0 13.5
0.53
0.93 9.14
1.31
0.15
2,350
20
Bottom High- Medium-
ash temp. . temp. High-S Low-S
(slag) char char refuse refuse
5.5
17.5 93 207 480 568
0.20
0.60 1.08
0.78 0.28 0.57 1.83 0.59
0.13
0.20 0.15
0.04
1,600
0.18
*From Appendix C (Cleland and Kingsbury, 1977).
-------
The MATEwE values, which are the measured values of the leachates, were
computed from the LC-50 values for the aerobic natural pH leachates, (see
Section 9, this report). Eight of the 11 leachates produced a low mortality
percentage (<15 percent), whereas three of the leachates were highly toxic.
The toxicity of the leachates from the fly ash and bottom ash was mainly
caused by their acidity.
Comparing the MATE^ values of the leachates to the table of constituents
exceeding individual MATE values and to the discharge severities (table 32),
TABLE 32. DISCHARGE SEVERITIES FOR CONSTITUENTS IN LEACHATES FROM COAL SOLID WASTES EXCEEDING
HEALTH- OR ECOLOGY-BASED WATER MATE VALUES
Param-
eter
Al
As
B
Ba
Be
Ca
Cd
Cl
Cr
Co
Cu
F
Fe
Hg
K
Li
Mg
Mn
Mo
Na
NH,/
Ni
Pb
P
S'2
SO,,
Sb
Se
Si
Sn
Sr
Te
Ti
Tl
V
Zn
MATE
LurQ1
Health Ecology Lurgi Lurgi Rose-
(mg/L) (mg/L) No. 5 No. 6 bud H-Coal
80 1 3
0.25 0.05
47 25 1
5 2.5
0.03 0.055
240 16 29 18 13 7
.05 .001 20 20
1,300 N
0.25 0.25
0.75 0.25
5.0 0.05
7.0 N 1
1.5 0.25
0.25 0.22
N 23 12
0.33 0.38 3 5
90 87
0.25 0.10 4
75 7
800 N
N N
0.23 0.01 3 3
0.25 0.05 2 2
15 0.0005
N N
1,250 N
7.5 0.2 2
0.05 0.25
150 N
N N
46 N
1.5 N
90 0.82
1.5 N
2.5 0.15
25 0.1 1
Bottom
ash
SRC Fly ash (slag)
63 5
2
26 32 1
390
1
4 4
4 54 2
2
9 91 8
131 13
3
2
200 2
High- Medium-
temp, temp. High-S Low-S
char char refuse refuse
6 13 30 35
4
3 6 18 6
4 3
1
Total discharge
severity
38 55
37
10
39
975
35
19
53
48
89
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TABLE 33. CONSTITUENTS IN LEACHATES FROM COAL UTILIZATION SOLID WASTES
Parameter
Maximum
allowable
leachate
(mg/L)
Lurgi No. 5
Nat. pH Adj. pH
8.25 6.05
Lurgi No. 6
' Nat. pH Adj. pH
7.55 5.10
Lurqi Rosebud
Nat. pH Adj. pH
8.44 4.95
H-Coal
Nat. pH Adj. pH
8.83 5.01
Primary drinking water
Arsenic 0.5
Barium 10.0
Cadmium 0.1
Chromium (VI) 0.5
Fluoride 14.0
Lead 0.5
Mercury 0.02
Nitrate 100.0
Selenium 0.1
.Silver 0.5
Secondary drinking water
Chloride 2,500.0
Copper 10.0
Hydrogen
sulfide 0.5
Iron 3.0 14.0
Manganese 0.5 4.2 1.94 16.2 1.67
Sulfate 2,500.0
Total
dissolved
solids 5,000.0
Zinc 50.0
pH (units) 5.5-9.5
Irrigation water
Aluminum 20.0
Beryllium 0.5
Boron 2.0 5.0 6.8 4.0 4.5 26.9 29.9 11.0 11.6
Cobalt 5.0
Molybdenum .05 0.4
Nickel 2.0
Nat. = Natural
Adj. = Adjusted
reveals that only Ca and Mn consistently exceed their MATE values for most of
the wastes. Fly ash leachate contains the most constituents that exceed MATE
values, 13, compared to only two each for the H-Coal and the two char leach-
ates; The measured MATE^ values for the leachates represent acute toxicity,
whereas those elements exceeding listed MATE values represent potential
chronic toxicity problems. More data need to be collected and evaluated in
order to validate the proposed MATE values and the use of discharge severi-
ties and acute toxicity data as a basis for predicting long-term environ-
mental effects.
Another basis for evaluating the potential hazard posed by coal solid
wastes is to compare the concentrations of constituents in the leachates from
this study with the proposed U.S. EPA hazardous waste criteria (U.S. EPA,
1978). Before evaluating results, however, the two extraction procedures
must be compared.
90
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EXCEEDING PROPOSED U.S. EPA TOXICANT EXTRACTION PROCEDURE STANDARDS
Bottomash High-temp. Medium-temp. High-sulfur Low-sulfur
_ SRC Fly ash (slag) char char refuse refuse
Nat. pH Adj.pH Nat. pH Nat. pH Nat. pH Adj.pH Nat. pH Adj. pH Nat. pH Adj. pH Nat. pH Adj.pH
6.35 4.69 4.08 3.81 8.05 4.33 7.19 3.81 7.45 3.43 7.79 3.50
0.39
31.2 13.5 250.0 4.75 10.0
0.93 1.38 9.14 ' 4.45 0.57 3.20 1.83 14.7 0.59 12.6
4.08 3.81
62.6
4.0 4.0 58.0 2.8 2.5 10.0 9.1
The procedure proposed by the EPA calls for screening through a 3/8-inch
sieve, which can be compared to the 45-mesh sieve that was used in this study.
The solid is then shaken in a volume of water that is 16 times its weight; in
this study, the volume of water is nine times the solid's weight. In the EPA ,
procedure, the sample is adjusted to pH 5.0 ± .1 with acetic acid; in this
study, the pH was adjusted with nitric acid to several values, many of which
were close to 5.0. The EPA procedure calls for a 24-hour shaking period; this
study used a 6-month equilibration.
Clearly, the intent and the methods used for the two extraction proce-
dures were quite similar; however, they cannot be directly compared. The
effects of using acetic acid compared to using nitric acid, the effects of the
differences in equilibration times, and the consequences of differences in
final volumes is difficult to assess. Nevertheless, the results obtained by
the two methods should be similar. Table 33 presents a tabulation of
91
-------
constituents of the leachates from this study that exceeded the proposed
U.S. EPA maximum allowable effluent levels for primary and secondary drinking
water parameters and for irrigation water standards for short-term (less than
20 years) application.
These results indicate that only Cd in the fly ash leachate exceeds the
primary leachate standard (10 times drinking water) and would thus be classed
as a hazardous waste by the proposed U.S. EPA criteria. It is useful to com-
pare the secondary drinking water parameters and note that Mn and Fe fre-
quently exceed 10 times the drinking water standard level. This occurs mainly
in the acidified leachates as compared to the natural pH leachates. When
making these comparisons, the differences between our procedure and the EPA
procedure should be kept in mind, particularly the two differences in final
volume and in pH.
Interestingly, boron exceeds the irrigation water standard in the leach-
ates from nearly all the coal wastes and at all pH levels. This is a poten-
tially serious problem in the western states, where high levels of boron in
irrigation waters are a problem because of the toxicity of boron to plants.
This illustrates that the ecologically based MATE value for boron may need to
be lowered to be more consistent with irrigation water standards.
Of the leachates obtained from the 11 coal solid wastes at their natural
pH level, only the fly ash leachate contained a significant level of acute
toxicity. Whereas the acute toxicity of most coal ash leachates was low,
however, they were measured with only one species of organism, and the poten-
tial for long-term pollution that could cause chronic toxicities is unknown.
The elements in the leachates that exceeded the MATE values for water quality
and irrigation water standards may be a guide to potential long-term pollution
problems.
The thermochemical modeling indicated several of the leachates were in a
mqtastable equilibrium. For example, the pyrites and pyrrhotites in the coal-
cleaning and liquefaction residues will eventually oxidize to form an acidic
leachate, which would have a much higher acute toxicity than was measured at
its natural pH in this study. The toxicity to be expected upon oxidation of
the metastable minerals would be more closely estimated from the bioassay and
chemical data from the acidified leachates. Thus, all these chemical,
mineralogical, biological, and soil attenuation factors must be integrated
when assessing the environmental impact of land disposal of the solid wastes
from coal utilization processes.
92
-------
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development program report, Research Triangle Park, NC.
United States Environmental Protection Agency, 1978, Hazardous waste: Pro-
posed guidelines and regulations and proposal on identification and
listing: Federal Register, v. 43, no. 243.58946-59028.
van Meter, W. P., and R. E. Erickson, 1975, Environments effects from
leaching of coal conversion by-products, Int. Rept., Energy Research
Development Administration, Fe-2019-1, Washington, D.C.
Wewerka, E. M., J. M. Williams, N. E. Vanderborgh, A. W. Harmon, P. Wagner,
P. 0. Wanek, and J. D. Olsen, 1978, Trace element characterization of
coal wastes—Second annual progress report: Intra-agency Energy-
Environment Research and Development program report, DOE LA-7360-PR,
EPA-600/7-78-028a, Research Triangle Park, NC.
White, P. C., and R. L. Zahradnik, 1976, Coal liquefaction: Energy Research
and Development Administration, ERDA 76-95/2, Washington, D.C.
98
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APPENDIX
LIST OF PUBLICATIONS
Griffin, R. A., R. M. Schuller, S. J. Russell, and N. F. Shimp, 1979, Chemi-
cal analysis and leaching of coal conversion solid wastes, in
F. A. Ayer [ed.h Environmental aspects of fuel conversion technology
IV: U.S. Environmental Protection Agency, EPA-600/7-79-217, Research
Triangle Park, NC.
Griffin, R. A., R. M. Schuller, J. J. Suloway, S. J. Russell, W. F. Childers,
and N. F. Shimp, 1978, Solubility and toxicity of potential pollutants
in solid coal wastes, in F. A. Ayer [ed.], Environmental aspects of
fuel conversion technology III: U.S. Environmental Protection Agency,
EPA-600/7-78-063, Research Triangle Park, NC.
Hinckley, C. C., G. V. Smith, H. Twardowska, M. Saporoschenko, R. H. Shi ley,.
and R. A. Griffin, 1980, Mossbauer studies of iron in Lurgi gasification
ashes and power plant fly.and bottom ash: Fuel, v. 59, p. 161-165.
Saporoschenko, M., C. C. Hinckley, G. V. Smith, H. Twardowska, R. H. Shiley,
R. A. Griffin, and S. J. Russell, 1980, Mb'ssbauer spectroscopic studies
of the mineralogical changes in coal as a function of cleaning, pyroly-
.sis, combustion, and coal conversion processes: Fuel, v. 59, p. 567-574.
.Schuller, R. M., R. A. Griffin, J. J. Suloway, 1979, Chemical and biological
characterization of leachate from coal cleaning wastes, in J. D. Kil-
groe ted.], Coal cleaning to achieve energy and environmental goals:
U.S. Environmental Protection Agency, EPA-600/7-79-098a, Research Tri-
angle Park, NC.
Schuller, R. M., J. J. Suloway, R. A. Griffin, S. J. Russell, and W. F.
Childers, 1979, Identification of potential pollutants from coal con-
version wastes, in Elements in coal and potential environmental con-
cerns arising from these elements: .Mini Symposium Series No. 79-06,
Society of Mining Engineers of AIME, Littleton, CO.
Shiley, R. H., S. J. Russell, D. R. Dickerson, C. C. Hinckley, G. V. Smith,
H. Twardowska, and M. Saporoschenko, 1979, Calibration standard for
x-ray diffraction analyses of coal liquefaction residues: MDssbauer
spectra of synthetic pyrrhotite: Fuel, v. 58, p. 687-688.
Smith, Gerard V., Juei-Ho Liu, Mykola Saporoschenko, and Richard Shiley,
1978, MBssbauer spectroscopic investigation of iron species in coal:
Fuel, v. 57, p. 41-45.
99
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TECHNICAL REPORT DATA
(Please read Instructions on the reverse before completing}
1. REPORT NO.
EPA-600/7-80-039
2.
3. RECIPIENT'S ACCESSION NO.
4. TITLE AND SUBTITLE
Chemical and Biological Characterization of Leachates
from Coal Solid Wastes
5. REPORT DATE
March 1980
6. PERFORMING ORGANIZATION CODE
7. AUTHOR(S)
R. A. Griffin, R. M.Schuller, J.J.Suloway,
N.F.Shimp, and W.F.Childers
8. PERFORMING ORGANIZATION REPORT NO.
9. PERFORMING ORGANIZATION NAME AND ADDRESS
Illinois State Geological Survey
Natural Resources Building
Urbana, Illinois 61801
10. PROGRAM ELEMENT NO.
EHE623A
11. CONTRACT/GRANT NO.
68-02-2130
12. SPONSORING AGENCY NAME AND ADDRESS
EPA, Office of Research and Development
Industrial Environmental Research Laboratory
Research Triangle Park, NC 27711
PERIOD COVEREO
14. SPONSORING AGENCY CODE
EPA/600/13
is. SUPPLEMENTARY NOTES IERL_RTP project officer is N. Dean Smith, Mail Drop 61, 919/
541-2708.
16. ABSTRACT ,
The report gives results of the chemical and mineralogical characterization
of coal solid wastes. The wastes included three Lurgi gasification ashes, mineral
residues from the SRC-I and H-Coal liquefaction processes, two chars, two coal-
cleaning residues, and a fly-ash-and-water-quenched bottom ash (slag) from a coal-
fired power plant. Leachates generated from the solid wastes at eight pH levels and
under two different gas atmospheres were analyzed for more than 40 chemical con-
stituents. Thermodynamic speciation of inorganic ions and complexes in solution
were modeled. The modeling demonstrated that similar mineral phases controlled
the aqueous solubility of the major ionic species for all wastes. Adsorption and co-
precipitation of trace metals with iron, manganese, and aluminum oxides and hy-
droxides were thought to be the likely controls on trace metal concentrations in the
leachates. A high degree of attenuation of the leachate constituents by soils was ob-
served. Soil properties controlled the degree of attenuation to a greater extent than
did the chemical concentrations of the leachates. Results of acute 96-hour static
bioassays using fathead minnows identified mortality as being caused by the com-
bined effect of pH arid total ionic strength of the leachate.
17.
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
b.lDENTIFIERS/OPEN ENDED TERMS
c. COSATI Field/Group
Pollution Bioassay
Wastes Ashes
Coal Coal Gasification
Combustion Coal Preparation
Chemical Properties Fly Ash
Minerals Slags
Pollution Control
Stationary Sources
Biological Properties
Chars
Coal Cleaning
13B
2 ID
21B
07D
08G
06A1
13H
11B
07A
18. DISTRIBUTION STATEMENT
Release to Public
19. SECURITY CLASS (TMi Report)
Unclassified
21. NO. OF PAGES
110
20. SECURITY CLASS (Thispage)
Unclassified
22. PRICE
EPA Form 2220-1 (9-73)
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