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T H E R E D U C T I V E D I S S O L U T I O N OF S Y N T H E T I C
GOETHITE AND HEMATITE IN DITHIONITE
J. T O R R E N T ,
U. S C H W E R T M A N N *
AND V. B A R R O N
Departamento de Cienciasy Recursos Agricolas, Escuela T~cnica Superior de Ingenieros Agr6nomos, Apdo.
3048, 14080 C6rdoba, Spain, and *InstitutJ~r Bodenkunde, Technische Universitiit Mi2nchen,8050 FreisingVVeihenstephan, Federal Republic of Germany.
(Received 30 July 1987)
Although thermodynamically extremely stable, goethite and hematite, the most frequent
Fe(III)-oxides in soils, may be completely redissolved under an anoxic environment if the
redox potential drops below about 0.15 V (at pH 7). This reductive dissolution is usually
caused by the anaerobic respiration of microorganisms which transfer an electron from the
metabolized organic compounds to the Fe(III)-oxides, as exemplified by the following
reaction:
FeOOH + 2H + + C H 2 0 - ~ Fe 2+ + CO2 + H20.
The dissolution of Fe(III)-oxides can be easily recognized in soils as the typical red or
yellow colours give way to the grey colours of the matrix minerals.
The ease with which the reduction takes place under fixed conditions with respect to Eh
and pH should depend on the type of Fe(III)-oxide, and its crystal properties such as crystal
size, morphology, disorder and chemistry (e.g. Al-for-Fe substitution).
Observations from red tropical soils containing hematite and goethite have led to the
conclusion that under anoxic conditions a yellowing, i.e. an apparent preferential dissolution
of hematite as opposed to goethite, occurs. Fey (1983) predicted this from thermodynamic
considerations based on an increasing stability of goethite if its AI substitution increases (see
also Yapp, 1983; Tardy & Nahon, 1985; Trolard & Tardy, 1987). However, because of the
variability of thermodynamic data for fine-grained minerals, which has resulted in a certain
arbitrariness of the selected solubility products (Trolard & Tardy, 1987), an experimental
investigation into the dissolution kinetics of fine-grained goethites and hematites appeared
desirable. This paper reports the results of a study in which the dissolution in Na-dithionite of
28 synthetic goethites and 24 hematites of widely varying crystallinity and Al-for-Fe
substitution was investigated. Dithionite was chosen because, under the conditions used, the
9 1987 The Mineralogical Society
330
J. Torrent et al.
rate of dissolution was high but still easy to follow analytically. In addition, dithionite is
widely used to extract Fe(III)-oxides from soils (Mehra & Jackson, 1960).
331
Goethite
Specific surface
calculated
(m2/g)
(m2/g)
Feo/F%
30
29
23
20
19
20
19
22
0'0
0.9
1'5
3.0
3.4
5.8
7"9
10.9
0'000
0.002
0"002
0.001
0.001
0-001
0.006
0-017
31
27
31
23
28
17
17
10
94
82
73
70
60
42
30
22
19
18
63
56
50
52
52
37
24
22
19
18
0'0
0-0
0"0
0.0
0.0
0-0
0.0
0"0
0.0
0"0
0'020
0-014
0.013
0.008
0.007
0.008
0.005
0.001
0.001
0"001
22
23
25
22
23
35
31
32
34
31
58
61
62
34
34
31
48
28
30
27
34
37
0.0
0.0
0.0
7.6
0-006
0.005
0.005
0.005
40
36
25
19
32
10
56
42
38
63
23
57
18.7
0.0
0.006
0-010
8
25
17
24
33
47
52
104
70
95
40
32
27
26
36
24
21
15
0"0
4.9
7'9
11'6
0"000
0-000
0"000
0'005
30
19
13
9
(nm)
34/0A
34/1
34/2
34/3
34/4
34/5
34/6
34/7
21
24
27
31
33
36
40
38
60
63
77
83
94
66
59
48
32
29
23
22
20
17
15
21
39'4
39'10
39r15
39'25
39'30
39'40
39'50
3~70
3980
9
10
11
11
11
16
26
29
36
38
38
43
53
43
45
54
71
80
80
80
GV1
GV2
GV3
GV4
21
24
17
20
GT2
GT4
35/0
35/3
35/4
35/5
39'60
hISS*
A1 substitution
(mol ~)
(nm)
no.
1 - 0-00228A
J. Torrent et al.
332
Hematite
no.
Specific surface
measured calculated
(m2/g)
(mZ/g)
MCD a
(nm)
MCDc
(nm)
A2
A3
A4
A5
67
75
80
44
40
54
37
16
28
29
95
138
B1
B2
67
55
56
33
C1
C2
C3
C4
C5
44
69
47
68
55
D1
D2
D3
b/SS*
AI substitution
(mol %)
Feo/Fed
21
17
20
42
2.0
4-5
8.5
11-5
0.007
0-016
0.051
0.310
25
15
10
12
23
96
18
26
0.0
14.3
0.002
0.025
37
6
47
35
23
48
41
37
91
101
73
98
26
22
34
20
24
0.0
7.5
14.2
10-2
13.4
0.003
0.064
0.047
0-032
0.061
29
14
8
10
7
80
76
39
67
61
17
21
20
57
15
17
44
0-0
7.5
14.0
0-008
0.012
0.052
13
15
9
E1
E2
E3
94
88
77
88
85
56
11
6
23
13
13
17
4.1
7-8
12.6
0.005
0.002
0.022
17
21
11
M3
M4
40
40
13
12
93
100
49
53
12.6
12.8
0-194
0.189
9
9
MH22
MH27
MH41
MH47
90
80
37
28
81
42
42
27
11
12
43
67
13
19
29
42
1.7
12.5
0.0
8-2
0.019
0.006
0-012
0.005
36
32
50
14
S1
$2
$3
55
55
38
44
38
23
44
36
27
23
24
37
0.0
0.0
0.0
0.001
0.001
0-001
40
29
48
* As for Table 1.
AND
333
DISCUSSION
Goethites
For the goethites the plots of dissolved Fe against time were essentially linear for the first
30 min of reaction, when 9 ~ (for GT2) to 55~ (for 39/4) of the total Fe had dissolved.
Departure from linearity, when it occurred, was due to a small initial curvature of either
decreasing or increasing slope (Fig. 1), which is typical of first order and S-shaped curves,
respectively. Fitting straight lines to the 0-30 rain plots gave small positive or negative
intercepts ( < 2~ of total Fe). In several cases, positive intercepts corresponded to samples
having significant amounts of Feo, which would indicate some preferential, quick dissolution
of poorly-crystalline material. The slope, b, of these fitted lines is, obviously, a measure of the
initial dissolution rate which, in turn, can be taken as a measure of the 'reducibility' of the
goethites. The initial dissolution rate per unit of surface area can be obtained by dividing that
slope by the specific surfaces (SS). The resulting b/SS values (in nmol F e m -2 min-1), shown
in Table 1, are negatively correlated with A1 substitution (Fig. 2). Hence A1 appears to be a
major factor determining the dissolution rate.
For the unsubstituted goethites the initial rate of dissolution per surface area varied less if
referred to the calculated surface area than if referred to the surface area measured by H20 or
EGME adsorption. In fact, there was a negative correlation between the dissolution rate and
the difference SS~2o SScalc..For the series 39 this difference increased from zero for goethite
synthesised at 60~ to 31 m 2 g-1 for the goethite synthesised at 4~ As shown earlier by
electron microscopy (Schwertmann et al., 1985) this extra surface may be attributed to an
'internal' surface due to fissures and cracks between single domains. In contrast to the
-
5~
r~
bJ
/
/
_J
Q
or)
Or)
r-~
/,
4~
39/18
//
"~
w
b-r-
39/50
Z'
20
~
bJ
C~
/
f
10
.~J
,*
,-'~
- - -
39170
9 -"
t"
,.~"
_.
34/6
--m-
o ~/,P"
'
10
20
50
40
TIME
CMIN]
FIG. I. Dissolution-time curves for several goethites showing, in some cases, small initial
curvatures.
334
J. Torrent et al.
i
50J
"-7t..-
E
r
4~
E
LL
3g
o
y = 29-2x
E
t-
+ 0.05x 2
20
R=0.84
U3
m
12
16
2~
AI SUBSTITUTION
FIG.
2.
(MOLE
*/I,)
Relationship between dissolution rate per unit of surface area (b/SS) and Al substitution
in goethites.
dissolution by proton attack, it may be speculated that for reductive dissolution the electron
carrier, i.e. the dithionite anion, may not easily penetrate these fissures so that the main
dissolution process is more or less limited to the 'external' surface.
Hematites
Many of the hematites used in this study had significant amounts of oxalate-soluble Fe
(Table 2). In three cases (A5, M3, M4) the Feo/Fed ratio was > 0.1 (Table 2) although the
products had been washed for 2 h with acid NH4-oxalate in amounts higher than those
required for the stoichiometric removal of noncrystalline Fe-oxides. The presence of this
noncrystalline Fe can explain, in part, why the measured specific surfaces were often much
higher than the calculated ones, since noncrystalline Fe-oxides show high specific surfaces of
about 400 mZ/g (Schwertmann & Fischer, 1973; Borggaard, 1984). However, for several
samples having a Feo/F% ratio of < 0.05 (and, consequently, a specific surface attributable to
noncrystalline oxides of < 400 x 0.05 = 20 m: g-l) the differences between calculated and
measured specific surfaces were much higher than 20 m: g-1 (see e.g. A4, B2 and C3). This
fact suggests that either the morphology of the particle is markedly different from the ideal
plate assumed here, or that the particle is platy but the surface is irregular, or that the crystals
have micropores to produce a marked increase in the specific surface (Schwertmann &
K/~mpf, 1985). Irregular, grainy hematite crystals have been described specifically for
hematites prepared in oxalate (Fischer & Schwertmann, 1975 ; Schwertmann, 1987) and this,
indeed, is the case for some of the hematites of the present investigation, as for instance B2
and C3.
335
50.
.",4
173
Lid
Jl"
41~
A5
--- .,,"
/,
,/
J
0"3
0'3
,J
30
t")
20
.,~/
H-
~ --C2
CI2
fl
T"
1.'/
.-~-
-..1,_..,r
~4
--"-
~-
,
10
MH 27
,
20
TIME
,
$0
~
4~
CMINI
FIG. 3. Dissolution-time curves for hematites A5, M3, C2 and MH-27. The first two are
curvilinear and the last two essentially rectilinear.
Most of the plots of dissolved Fe against time for the hematites were, after a few (0-5) rain
close to linearity (Fig. 3) until, at least, the first 30 min, and similar, therefore, to those of the
goethites. A few samples with high Feo/F% ratios (C3, B2, M3, M4 and A5) showed curved
dissolution curves with a decreasing slope and no sharp breaks (Fig. 3), suggesting that
noncrystalline oxides and hematite have not dissimilar dissolution rates (because in the
opposite case sharp breaks close to the Feo values would have been observed).
As for the goethites, the initial rates of dissolution per unit surface area of the hematites
(hISS) were also negatively correlated with the A1 substitution (Fig. 4). Comparison of Fig. 2
with Fig. 4 shows that the fitted quadratic curves are similar, i.e. the rate of dissolution per
unit of surface of the two minerals is similar at similar A1 substitution.
Unsubstituted hematites showed markedly different values of b/SS. None of the
mineralogical characteristics studied here were able to explain these differences. Particle
morphology might affect dissolution. This would be in line with the anisotropy shown by
hematites being etched by acids (Warren et al., 1969) although no proofs can be offered here.
CONCLUSIONS
Under the conditions of the present investigation, synthetic goethites and hematites having
similar specific surfaces and A1 substitution showed similar dissolution rates in dithionite.
Although this observation may not be valid in toto for natural goethites and hematites present
in soils or sediments it suggests, nevertheless, that the apparent preferential dissolution of
hematite in natural environments is due either to its smaller size (higher specific surface) or to
336
J. Torrent et al.
"7"( -
50,
0__
[]
E
o
LL
'%.
%
38
Y = 3 5 - 3.5 x+ 0.14 x 2
,% /
[]
,%
,%
R =0.79
,%
%.
U3
(J3
[]
,%
[]
"t ~..
[]
18-
12
16
AL SUBSTITUTION (MOLE %)
FIG. 4. Relationship between b/SS and A1 substitution in hematites.
its lower level of A1 substitution, or both. Although it has been frequently reported that
hematite has larger crystal size than goethite (Schwertmann, 1987) this is not always true
(Pefia & Torrent, 1984). As a consequence, particle size cannot be invoked as the main cause
for preferential dissolution of hematite. In contrast, in natural environments A1 substitution
is lower in hematite than in the coexisting goethite (Torrent et al., 1980; Pefia & Torrent,
1984; Schwertmann, 1985). This could be then the main reason for the preferential reductive
dissolution of hematite in soil materials or sediments which have changed from red to yellow,
and when only the pigmenting effect of the goethite remains.
ACKNOWLEDGMENT
This work was supported, in part, by the Comisi6n Asesora de Investigaci6n Cientifica y T6cnica (Spain)
under Project No. 2010/83.
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