www.elsevier.com/locate/chemgeo
Abstract
Several goethites were obtained through the hydrolysis at 60 °C of Fe(III) solutions containing variable amounts of Mn(II) ions.
The obtained samples were thermally treated at temperatures ranging from 180 to 310 °C until the complete phase transformation
to hematite was achieved. The effect of Mn in the dehydroxylation process was investigated using X-ray diffraction (XRD) and the
Rietveld refinement of XRD data together with scanning electron microscopy (SEM), differential thermogravimetric analysis
(DTA) and Fourier transform infrared spectroscopy (FTIR). In all cases, the formed hematites retained the acicular shape of the
precursor goethite. The dehydroxylation temperature increased with the increase of the Mn content in the parent goethite. The cell
parameters of both phases decreased with the thermal treatment, however the decrease in the goethite b-parameter was more
pronounced. This fact could be attributed to the distortion in the goethite structure by the presence of manganese. The band shifts in
the FT-IR spectra of the goethites with different Mn substitution were analysed. The intensities of the hydroxyl vibrations were
indicative of the degree of dehydroxylation.
The chemical reactivity of all the samples, before and after the thermal treatment, was also studied. The kinetic experiments
were carried out at 40 °C in 4 mol dm− 3 HCl. The acid dissolution of all Mn-goethites showed a congruent behavior indicative of a
homogeneous distribution of Mn in the goethite crystals, this trend was not observed in the formed hematites presenting a high Mn
content. The dissolution rate in goethites increased with the increase of Mn content, the opposite effect was observed in the
corresponding hematites. The activation energy in both phases was also obtained and indicated that the Mn substitution produces
an opposite effect on goethite- and hematite-phases. Different kinetic laws were applied in order to explain the dissolution behavior,
but the modified first-order Kabai equation described the dissolution data best.
© 2006 Elsevier B.V. All rights reserved.
whose properties depend on the temperature, treatment information regarding the distribution of the foreign
conditions, and the crystallinity of the goethite (Derie et metal within the structure of the iron oxide. If Fe and
al., 1976; Klissurski and Bluskov, 1980; Goñi-Elizalde associated metals dissolve at identical rates, then it is
and García-Clavel, 1988). Dehydration of goethite in- reasonable to assume that the metal is uniformly dis-
volves removal of hydrogen and one quarter of the tributed throughout the iron oxide crystals. Conversely,
oxygen, without disturbing the network of remaining if Fe and the metal show quite different patterns of
oxygen, and atomic rearrangement of Fe3+ to form dissolution, then it is unlikely that the two elements are
hematite: 2 α-FeOOH → α-Fe2O3 + H2O. Two different present in a single mineral of uniform composition
mechanisms have been suggested: direct dehydration of (Sidhu et al., 1981; Singh and Gilkes, 1992).
goethite to hematite without an intermediate phase The aim of this work is to provide information about
(Watari et al., 1983; Goss, 1987), and the formation of the effects of Mn substitution on the thermal transfor-
an intermediate product during dehydration where in the mation of goethite to hematite achieved at different
inhomogeneous dehydration process, the crystal devel- temperatures. For that, the structural changes of the two
ops separate ‘donor’ and ‘acceptor’ regions (Ball and phases are analysed using the Rietveld refinement of
Taylor, 1961; Lima-de-Faria, 1963). XRD powder data. The effect of the Mn incorporation
Although most work on the goethite dehydroxylation on the dissolution behavior in acidic media of all the
has focused on non-substituted goethite (Ruan et al., formed solids is also investigated.
2001), natural goethite often contains appreciable quan-
tities of aluminum ion substituting Fe. This substitution 2. Materials and methods
may affect the dehydroxylation temperature (Jonas and
Solymar, 1970; Fey and Dixon, 1981; Ruan and Gilkes, Manganese goethites were synthesized from the
1995a). Others cations such as Cr, Ge, Ni, Co and Mn Fe(III)-system using a method described elsewhere
may also substitute Fe in natural goethite (Schwertmann (Sileo et al., 2001). Ferrihydrites were precipitated by
and Lathman, 1986; Bernstein and Waychunas, 1987; adding a 2 mol dm− 3 NaOH to different solutions
Trolard et al., 1995). containing variable quantities of Fe(III) and Mn(II)
Chemical dissolution of iron oxides has been studied nitrates. The final ratio OH− / (Fe + Mn) and the total
for a long time in analysis of natural and synthetic (Fe + Mn) concentration in all samples were 13.16 and
mixtures, material chemistry, and technology (Blesa et 0.53 mol dm− 3, respectively. The precipitates obtained,
al., 1994; Cornell and Schwertmann, 1996). In general, were washed twice with double-distilled water and
the solubility of iron oxides in pure water is extremely centrifuged. After this treatment, the samples were aged
low (Schwertmann, 1991); however, dissolution of Fe for 21 d at 60 °C in closed polyethylene flasks con-
oxides is promoted by strong acids and by reducing and taining 0.3 mol dm− 3 NaOH. Initial mole ratios
complexing agents. χMn = Mn / (Mn + Fe) were 0.00, 0.03, 0.07 and 0.10
Dissolution of iron oxides containing foreign ions (samples named S0_60 °C to S3_60 °C, respectively). After
that replace Fe has also received attention. The mech- aging, the materials were washed with double-distilled
anisms of dissolution of pure and Al-substituted, syn- water until the conductivity of the filtrated solution was
thetic and natural goethite in HCl solutions are well b 5 μS. The remaining solids were dried at 40 °C and
understood (Surana and Warren, 1969; Cornell et al., gently crushed. Then, the samples were oxalate-ex-
1974, 1975, 1976; Schwertmann, 1984a; Cornell and tracted in order to remove remaining ferrihydrite from
Schindler, 1987). Lim-Nuñez and Gilkes (1987) and their surfaces.
Alvarez et al. (2005) showed that transition metals- Sub-samples of Mn-substituted goethites were heated
substituted goethites dissolve in acidic media at rates in a glass furnace with temperature control within ± 2 °C
different from that of pure goethite. Wells et al. (2001) for 2 h at temperatures ranging from 180 to 310 °C
investigated the influence of metal substitution on the to evaluate the degree of transformation goethite →
dissolution rate and kinetics of dissolution in 1 mol dm− 3 hematite.
HCl of Al-, Mn- and Ni-susbtituted hematites. In all The level of Mn incorporation was calculated from
cases, dissolution kinetics have been used to interpret the composition of the oxalate-extracts. Metal contents
the release mechanism of cations included in goethite in the goethites were determined on 20 mg of each
and hematite; so, the acid dissolution provides evidence sample dissolved in 6 mol dm− 3 HCl at 60–80 °C, using
of the uniformity of incorporation of Fe and metals in a GBC Model B-932 flame atomic absorption spectrom-
these minerals. Iron and metal analysis of sequential eter. Differential thermal analyses (DTA) were carried
extracts during the dissolution of samples can provide out in a DTA-50 Shimadzu analyzer. Approximately
290 M. Alvarez et al. / Chemical Geology 231 (2006) 288–299
Fig. 1. DTA profiles for the samples Si_60 °C. Mn contents are indicated Fig. 2. XRD of samples (a) S0 and (b) S3 heated at different
in Table 1. temperatures.
M. Alvarez et al. / Chemical Geology 231 (2006) 288–299 291
Table 3
Unit cell parameters for the samples
Sample Goethite Hematite
3
a (nm) b (nm) c (nm) Vol (nm ) a = b (nm) c (nm) Vol (nm3)
S0_60 °C 0.46172(5) 0.99548(10) 0.30242(3) 0.13901(2) – – –
S1_60 °C 0.46113(2) 0.99573(5) 0.30217(1) 0.13875(1) – – –
S2_60 °C 0.46051(1) 0.99698(2) 0.30197(1) 0.13864(1) – – –
S3_60 °C 0.45990(1) 0.99837(1) 0.30165(1) 0.13851(1) – – –
S0_220 °C 0.46114(9) 0.99774(7) 0.30051(4) 0.13827(4) 0.50519(63) 1.37576(262) 0.30408(99)
S1_220 °C 0.46060(10) 0.99791(12) 0.29902(5) 0.13744(3) 0.50553(20) 1.37905(70) 0.30521(16)
S2_220 °C 0.46066(9) 0.99686(12) 0.29819(5) 0.13693(3) 0.50632(11) 1.37893(179) 0.30615(39)
S3_220 °C 0.45945(5) 0.99540(8) 0.29762(2) 0.13611(2) 0.50481(25) 1.38673(72) 0.30604(24)
S0_260 °C – – – – 0.50390(2) 1.37624(13) 0.30263(3)
S1_260 °C – – – – 0.50373(5) 1.37583(20) 0.30233(7)
S2_260 °C 0.45588(18) 0.99546(38) 0.29418(13) 0.13350(5) 0.50467(5) 1.37375(37) 0.30300(8)
S3_260 °C 0.45832(10) 0.99559(18) 0.29465(4) 0.13444(4) 0.50312(4) 1.37499(21) 0.30142(5)
S2_310 °C – – – – 0.50333(2) 1.37537(18) 0.30176(4)
S3_310 °C – – – – 0.50308(4) 1.37535(16) 0.30145(6)
M. Alvarez et al. / Chemical Geology 231 (2006) 288–299 293
Fig. 5. Cell parameters vs. temperature for S2 (○) and S3 (■): (a), (b), (c) goethite phase, and (d), (e) hematite phase.
al. (1999) found a Mn zoning in goethite, which may 3.4. FT-IR spectra
partly explain inhomogeneous transformation of ferri-
hydrite to goethite. This behavior could also occur in the In the FT-IR spectra (Fig. 6) structural OH of
topotatic goethite–hematite phase transformation in the goethite causes the absorption at 3140 cm− 1, the
presence of Mn. hydroxyl stretching region, and the two bands at
The a and c parameters of hematite decrease as the ∼890 and 795 cm− 1 correspond to OH deformation
temperature of the treatment is raised from 220 to and water bending modes (Cambier, 1986). The
intensity of the band at 3140 cm− decreased as the
1
260 °C. Similar trends were reported for pure hematites
and Al-hematites obtained from thermal transformation Mn content increased shifting to lower energy values and
of the corresponding goethites (Ruan and Gilkes, 1995a; disappeared in all the samples after heating at 260 °C.
Ruan et al., 2001). The same trend in intensity is found in the bands
294 M. Alvarez et al. / Chemical Geology 231 (2006) 288–299
Fig. 6. Infrared spectra of samples (a) S0, (b) S1, (c) S2 and (d) S3, and its dehydroxylated products obtained from heating goethite between 180 and
310 °C for 2 h.
corresponding to the OH deformation and water bending Dissolution curves for goethite show nearly linear
modes. shapes in the range of time studied in this work
After heating at 220 °C all samples show a band at (Fig. 7a), whereas the curves for the samples S0_260 °C,
∼3400 cm− 1, together with the weak absorption at S1_260 °C, S2_310 °C and S3_310 °C, where the unique
∼1620 cm− 1, attributed to ‘loosely bound water’, which phase is hematite, show deceleratory shapes (Fig. 7b).
are indicative of hydroxyl in hematite. The spectra show As shown in the Fig. 7, dissolution rates are similar for
that the hematites, formed by thermal dehydroxylation S0_60 °C and S1_60 °C and then increase with Mn content
of goethite, inherited some structural OH expressed by (S0_60 °C ≈ S1_60 °C b S2_60 °C b S3_60 °C), whereas the
Fe2−x / 3(OH)xO3−x. Wolska and Szajda (1985) reported opposite effect was observed with the increase of Mn
the bands near 3400, 950 and 630 cm− 1 as OH unit substitution in the hematite samples. These latter re-
vibrations in “hydrohematite”. sults agreed with those presented by Wells et al. (2001).
The presence of goethite detected by XRD in The dissolution rate per gram of oxide was calculated
samples S2 and S3 only could be supported by FT-IR from the initial nearly linear region of the dissolution
spectra of S2. In samples S2_310 °C and S3_310 °C, the curves (Table 4).
spectra show characteristic bands of “hydrohematite”, The initial dissolution rates in Table 4 indicate that
and no bands of goethite are detected. These results non-substituted hematite (S0_260 °C) dissolved about 90
agree with XRD patterns. times faster than the corresponding goethite (S0_60 °C).
In the case of substituted samples, hematite with higher
3.5. Dissolution curves Mn content (S3_310 °C) dissolved only about 5 times
faster than the corresponding Mn-goethite (S3_60 °C).
The representative plots of Fe released at 40 °C in Then, Mn substitution reduced the dissolution rate of
4 mol dm− 3 HCl vs. time for the prepared Mn-goethites hematite, but increased the dissolution rate of goethite.
and the totally thermal transformed Mn-hematites are The increase in k0 values detected in the mixed
shown in Fig. 7. goethite–hematite samples compared to that of pure
M. Alvarez et al. / Chemical Geology 231 (2006) 288–299 295
Table 5
Coefficients for the Kabai equation for samples dissolved at 40 °C
Sample Mol% Mn Hm (1) Linear part n α k (min− 1 × 103) R2
Hm þ Gt
S0_60 °C 0 0 – 7 1.217 1.98 0.994
S0_180 °C 0 – 9 1.282 1.70 0.996
S0_220 °C 0.414 I 11 0.298 0.11 0.997
II 5 0.772 1.61 0.996
S0_260 °C 1 – 9 1.130 81.36 0.991
S1_60 °C 2.5 0 – 7 1.617 3.63 0.999
S1_180 °C 0 – 6 1.189 3.86 0.997
S1_220 °C 0.386 I 8 0.412 7.71 0.989
II 4 1.351 7.80 0.991
S1_260 °C 1 – 10 0.867 54.57 0.999
S2_60 °C 6.7 0 – 9 1.395 2.42 0.997
S2_180 °C 0 I 6 1.139 1.75 0.997
II 3 1.955 2.15 0.978
S2_220 °C 0.319 I 8 0.388 6.42 0.995
II 4 1.064 7.96 0.997
S2_260 °C 0.696 – 12 0.759 23.30 0.997
S2_310 °C 1 – 10 0.926 31.37 0.992
S3_60 °C 8.3 0 – 9 1.016 3.63 0.993
S3_180 °C 0 I 5 0.822 1.53 0.995
II 5 1.722 3.76 0.998
S3_220 °C 0.286 I 7 0.533 8.24 0.993
II 4 1.032 7.30 0.994
S3_260 °C 0.641 – 12 0.784 14.56 0.998
S3_310 °C 1 – 10 1.156 14.37 0.992
(1)
Hm: hematite; Gt: goethite.
from Kabai equation is 1.98×103 min− 1 for pure goethite thermically treated at different temperatures. The degree
(S0_60 °C), and 8.14 × 104 min− 1 for pure hematite of transformation could be evaluated in function of
(S0_260 °C), while for S3_60 °C k value is 3.63×103 and changes in the cell parameters of all samples, and their
1.44 × 104 min− 1 for S3_310 °C. These results are in chemical reactivity in an acidic media.
accordance with k0 values observed in Table 4. Crystals of Mn-substituted goethite retain the acicular
shape after transformation to hematite at 310 °C. The
4. Conclusions temperature of transformation decreases as the Mn con-
tent increases. In the same way, the Mn substitution in
A series of goethites with increasing Mn content were goethite raises the dehydroxylation temperature.
synthesized by forced hydrolysis with base addition, and The cell parameters of both goethite and hematite
decrease with the thermal treatment. However, the be-
havior of the b parameter in Mn-goethite is more erratic.
In agreement with XRD results, IR spectra support
the assumption that Mn retards the dehydroxylation of
goethite solid phase to form hematite.
The results of this study confirm that Mn-substituted
goethite is thermally more stable than non-substituted
goethite. The same effect was observed in Al-goethite.
The acid dissolution of all Mn-goethites is congruent,
but not for all Mn-hematites. The major diversion from
this tendency is observed in hematites with higher Mn
content.
The increasing Mn substitution in goethite raises the
dissolution rate, while the opposite effect was observed
Fig. 9. FTIR spectra from samples S0_180 °C to S3_180 °C in the region of for the corresponding Mn-hematites obtained from heat-
the water bending bands (1600–1900 cm− 1). ing goethite.
298 M. Alvarez et al. / Chemical Geology 231 (2006) 288–299
Mn substitution produces opposite effects in activa- Derie, R., Ghodsi, M., Calvo-Roche, C., 1976. DTA study of the
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