105

The Canadian Mineralogist

Vol. 57, pp. 105-115 (2019)
DOI: 10.3749/canmin.1700074

MÖSSBAUER STUDY OF CHANGES IN OLIVINE AFTER HEATING IN AIR

MARIOLA KA˛DZIOŁKA-GAWEŁ§
Institute of Physics, University of Silesia, 75 Pułku Piechoty 1a, 41-500 Chorzow, Poland

ZDZISŁAW ADAMCZYK
Institute of Applied Geology, Silesian University of Technology, Akademicka 2, 44-100 Gliwice, Poland

LECH KALINOWSKI
Institute of Physics, University of Silesia, 75 Pułku Piechoty 1a, 41-500 Chorzow, Poland

ABSTRACT

The transformation mechanism of Fe2þ cations in two samples of natural olivine (Fe,Mg)2SiO4 after heat treatment in air in
the temperature range 400–1180 8C has been studied using 57Fe Mössbauer spectroscopy and XRD measurements. The
influence of heating duration (from one to 96 hr) on the behavior of Fe2þ ions in the olivine structure was investigated. Fe3þ ions
dominate as a primary product of the thermal treatment in air above 1000 8C. Heating at 1180 8C led to decomposition of the
olivine structure. The formation of ferriolivine as a result of low-temperature oxidation was also observed.

Keywords: olivine, thermal treatments, Mössbauer spectroscopy, X-ray diffraction.

INTRODUCTION of the olivine structure at various temperatures and the

Olivine (Fe,Mg)2SiO4 is an orthosilicate mineral
with an orthorhombic crystal structure that is charac-
terized by a distorted hexagonal close packing of
oxygen ions, Si at tetrahedral interstices, and Mg and
Fe ions at two octahedral sites (Birle et al. 1968, Dyar
et al. 2009), coordinated by a regular octahedron (M2)
and a distorted octahedron (M1). The Fe2þ and Mg2þ
ions have no particular preference for either site (Taran
& Koch-Müller 2006). Found primarily in iron- and
magnesium-rich igneous rocks, olivine is of particular
significance in understanding planetary geology in
differentiated bodies.
Although extensive studies have been conducted on
olivine over a range of compositions, temperatures,
and pressures (Ottonello et al. 1990, Khisina et al.
1993, Woodland & Angel 2000, Zhang et al. 2015)
using a variety of methods, there is still a need for data
on several aspects of the nature of olivine. The most
common investigations are connected with the stability
alteration products (Caroff et al. 2000, Redfern et al.
2000, Barcova et al. 2003). Also, very often there
appears a question about Fe3þ distribution in oxidized
olivine and the nature of these ions (Khisina et al.
1993, Khisina et al. 1995, Dyar et al. 1998, Zhe et al.
2001). Additionally, natural olivine has been found to
be a reactive material due to its catalytic activity,
which has been attributed to the presence of different
iron species (Świerczyński et al. 2006, Guan et al.
2014, Kaknics et al. 2015). The ordering of cations in
the olivine structure is strongly controlled by the
thermal history of the sample. Duration of thermal
treatment also influences the stability of the olivine
structure (Barcova et al. 2003).
The purpose of this work is to provide information
on the thermal transformation mechanism of Fe2þ
cations in the olivine structure and structural changes
in olivine after heat treatment, based on Mössbauer
and XRD analyses. Mössbauer spectroscopy was used
to evaluate the Fe2þ occupancies of the M1 and M2

§
Corresponding author e-mail address: mariola.kadziolka-gawel@us.edu.pl

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 106
sites in olivine crystals and in iron-bearing phases
which were created during the heating process.
Knowledge of the influence of the heating duration
in air atmosphere on the stability of Fe2þ ions in the
olivine structure is important for industrial applica-
tions. The results obtained give a basis for a better
understanding of the catalytic performance of olivine
in biomass gasification.
MATERIALS AND METHODS
Two natural samples of olivine were chosen for
detailed analysis. The first sample is from Cenozoic
volcanic rocks occurring in the Lower Silesia region
(Krzeniów, Pogórze Kaczawskie, SW Poland), which
forms the eastern part of the Central European
Volcanic Province. The second investigated sample
of olivine comes from the island of Lanzarote and
originated from mantle plume activity beneath the
Canary Islands.
Pulverized samples of olivine were heated in an
electric furnace in an air atmosphere under static
conditions to five temperatures: 400, 600, 800, 1000,
and 1180 8C. The duration of the heat treatment was
chosen based on the literature (Świerczyński et al.
2006, Barcova et al. 2003) and amounted to four
hours. To investigate the influence of heating duration
on the stability of Fe ions in the olivine structure, the
pulverized samples of olivine were also heated under
static conditions at two defined temperatures: 500 and
750 8C. The first temperature is somewhat lower than
that at which Fe3þ ions are observed for the first time.
The latter temperature is marginally lower than the one
at which magnetically ordered phases were observed
for the first time. The durations of the heat treatment of
each sample were one, two, 24, 48, and 96 hours. After
each heating treatment, Mössbauer measurements
were obtained at room temperature.
The chemical compositions of the two olivine
samples were determined using a Rigaku ZSX Primus
II X-ray fluorescence spectrometer. The spectrometer,
equipped with a 4 kW, 60 kV Rh anode and a
wavelength-dispersion detection system, allowed for
analysis of the elements from Be to U. No external
standards were necessary and only the internal
standards coupled with the fundamental-parameters
method (theoretical relationship between measured X-
ray intensities and the concentrations of elements in
the sample) were implemented.
We used X-ray powder diffraction (XRD) analysis
to confirm the olivine structure in the investigated
samples and identify other minerals in the samples
after heating. The X-ray diffraction data were
collected at room temperature using a Siemens
D5000 X-ray diffractometer and CoKa radiation for
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THE CANADIAN MINERALOGIST
the Krzeniów samples and CuKa for the Lanzarote
samples. Rietveld refinement was performed using the
Xpert High Score Plus system with the PDF-4
crystallography database from the International Center
for Diffraction Data.
Mössbauer spectroscopy was used to characterize
various iron-bearing minerals in the investigated
samples of olivine before and after the heating process
and also to investigate the oxidation state and
electronic configuration of Fe atoms in the minerals.
The initial samples were powdered in an agate ball
mill and then prepared in the shape of a thin disk
absorber. The 57Fe Mössbauer transmission spectra
were recorded at room temperature using a POLON
type spectrometer and a linear arrangement of the
source, a multichannel analyzer with 1024 channels
(before folding), the absorber, and a detector. A source
of about 15 mCi activity 57Co in rhodium matrix
(Cyclotron Co., Ltd., Obninsk) was used at room
temperature. An LND-45431 gas proportional counter
was used as a gamma-ray detector. A 2 mm plastic
filter was placed in the beam to absorb the ~6 keV
X-rays before they entered the detector. The 2 keV
escape peak and 14.4 keV gamma ray pulses were
selected with the multichannel analyzer. The spec-
trometer was calibrated at room temperature with a 30
lm-thick a-Fe foil. The time of Mössbauer spectrum
collection was typically from approximately one to
three days, and baseline counts ranged from ~35 to 80
million counts after Compton correction, as required to
obtain reasonable counting statistics. No influence of
the detector window on the spectrum was observed
during the period of the measurements.
Numerical analysis of the Mössbauer spectra was
performed with the use of the WMOSS program
(Prisecaru 2016). The obtained spectra were fitted with
a superposition of several doublets and sextets.
Mineralogical analysis of the spectra was based on
the Mössbauer Mineral Handbook (Stevens et al.
2005).
RESULTS
The chemical compositions of the investigated
olivine samples are given in Table 1. These compo-
sitions led to an average formula of olivine from
Krzeniów of (Mg0.87Fe0.13)2SiO4 and from Lanzarote
of (Mg0.89Fe0.11)2SiO4 (without taking into account the
minor elements Ni, Ca, Al, and Ca).
Figure 1 shows XRD patterns of the olivine
samples with values of interplanar spacing expressed
in Å. Orthorhombic lattice parameters (space group
Pbnm) determined using 266 reflections between 15
and 908 2-theta (2H) for the Krzeniów sample and 118
reflections between 10 and 658 (2H) for the Lanzarote
 CHANGES IN OLIVINE AFTER HEATING IN AIR: MÖSSBAUER STUDY 107

TABLE 1. CHEMICAL COMPOSITIONS OF THE
INVESTIGATED INITIAL OLIVINE SAMPLES
Element Mg Fe Si Ni Ca
Krzeniów
(wt.%) 21.89 7.36 17.95 0.33 0.10 1.23 0.29
Lanzarote
(wt.%) 25.45 7.60 17.89 0.36 0.99 0.83 0.09
material are listed in Table 2. Table 2 also shows the
unit-cell volumes obtained for the investigated olivine
samples before and after heating at different temper-
atures. Patterns for initial samples of the investigated
olivines show diffraction lines that are associated with
the olivine structure (Merli et al. 2001). The calculated
values for the initial samples are close to those
reported for olivine rich in magnesium (Aikawa et al.
1985, Zha et al. 1998, Świerczyński et al. 2006). Heat
treatment of the investigated minerals at 400 and 600
8C did not lead to any significant changes in the
diffraction patterns. However, decreases in cell
volumes are observed for these temperatures, which
can indicate the formation of ferriolivine as a result of
low-temperature oxidation in olivine (Khisina et al.
1992). These decreases are due to the smaller ionic
radius of Fe3þ in comparison to Fe2þ. Increasing the
heating temperature from 800 to 1180 8C leads to a
small decrease in the unit-cell volume. As we know,
the ionic radii for sixfold coordination are 0.65 Å for
Mg2þ (Kaufman Katz et al. 1996) and 0.77 Å for Fe2þ
(Price et al. 1976). For this reason a decrease in the
unit-cell volume should be observed after the depar-
ture of iron from the olivine structure. Annealing at
800 8C leads to the appearance of a low-intensity line
with an interplanar spacing volume equal to 2.70 Å
(for the olivine sample from Krzeniów) due to the new
crystalline phase a-Fe2O3 (hematite). The presence of
iron oxides can be explained by the rejection of iron
from the olivine structure caused by the oxidation of
Fe2þ to Fe3þ. High-temperature treatment (above 1000
8C) results in diffraction lines arising from a-Fe2O3,
MgSiO3 (enstatite) and MgFe2O4 appearing in X-ray
patterns for both olivine samples. These lines, and
Al Na
crystal phases connected to them, indicated decompo-
sition of the olivine structure after heating at
temperatures higher than 1000 8C.
Figure 2 shows room-temperature Mössbauer
spectra of the investigated olivine samples before
and after heating at 1180 8C, while the relative areas
of fitted subspectra obtained after heating at high
temperatures are presented in Figure 3. Table 3 sums
up the hyperfine parameters obtained for all sub-
spectra for the initial and heated olivines. Selected
Mössbauer spectra obtained for the olivine samples
after heating at temperatures of 500 and 750 8C for
the above time periods are presented in Figure 4. The
abundances of Fe in the olivine structure and in iron
oxides after the heating over a given time are shown
in Figure 5.
The Mössbauer spectra of the unheated olivines
contain three doublets. Two dominant doublets
originate with Fe2þ ions at the octahedral positions in
the olivine structure. The values of the hyperfine
parameters for the olivine from Krzeniów are 1.13 and
1.15 mm/s (isomer shift, Is) and 2.86 and 3.02 mm/s
(quadrupole splitting, Qs), respectively. For the olivine
from Lanzarote the isomer shifts were 1.14 and 1.16
mm/s, and the quadrupole splittings were 2.91 and
3.09 mm/s, respectively. The doublets with smaller
quadrupole splitting, i.e., more distorted octahedra, can
be assigned to Fe at M2 and those with the larger
quadrupole splitting can be assigned to Fe at M1
(Zhiganova et al. 2007, Oshtrakh et al. 2008, 2013).
As seen in Figure 3, the M1 sites contain a higher
amount of Fe. In the Mössbauer spectra of both initial
samples of olivine there is a doublet with an isomer
shift of 0.19 mm/s and a quadrupole splitting value of
about 0.42 mm/s. This doublet corresponds to Fe3þ
ions that can be incorporated at the tetrahedral position
of the original olivine structure. The results show that

TABLE 2. LATTICE PARAMETERS AND CELL VOLUMES OBTAINED FOR THE INVESTIGATED OLIVINES
BEFORE AND AFTER HEATING AT DIFFERENT TEMPERATURES

Krzeniów Lanzarote
a (Å) b (Å) c (Å) V (Å3) a (Å) b (Å) c (Å) V (Å3)
RT 5.9866(8) 10.2140(2) 4.7387(6) 289.7579(2) 6.0061(7) 10.2302(1) 4.7470(6) 291.6727(8)
400 8C 5.9895(2) 10.2197(3) 4.7538(3) 286.6419(3) 6.0001(3) 10.2259(2) 4.7458(3) 291.1853(1)
600 8C 5.9868(2) 10.2177(6) 4.7539(2) 290.8024(7) 5.9985(1) 10.2286(2) 4.7464(8) 291.2213(4)
800 8C 5.9830(2) 10.2290(4) 4.7520(2) 290.8229(1) 6.0012(1) 10.2281(1) 4.7514(7) 291.6540(8)
1000 8C 5.9890(2) 10.2175(4) 4.7521(3) 290.7421(6) 6.0003(2) 10.2200(2) 4.7603(1) 291.9161(9)
1180 8C 5.9897(3) 10.2160(7) 4.7549(2) 290.9560(2) 6.0011(1) 10.1821(3) 4.7740(9) 291.7095(4)

RT – room temperature

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 108 THE CANADIAN MINERALOGIST

FIG. 1. Room-temperature diffraction patterns obtained for the olivine samples from Krzeniów and Lanzarote after heating at
selected temperatures. Mineral abbreviations: Ol – olivine, Hem – hematite, Mfr – magnesioferrite, En – enstatite.

their area remains almost constant during thermal between the two octahedral sites. This effect is
treatment. especially visible for the sample from Krzeniów, and
Heating olivine samples at temperatures of 400 and it is confirmed by the change in interplanar spacing in
600 8C leads to a change in distribution of iron ions XRD patterns. Additionally, there appears to be a new

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 CHANGES IN OLIVINE AFTER HEATING IN AIR: MÖSSBAUER STUDY 109

FIG. 2. Room-temperature Mössbauer spectra of the olivine samples from Krzeniów and Lanzarote obtained for untreated
samples and after heating at 1180 8C. Fitted subspectra are visible on the spectra. Ol – olivine M1, M2 – Fe2þ in octahedral
sites, FOL – ferriolivine, Fe3þ(Si4þ) – Fe in tetrahedral site, Hem – hematite, Mfr – magnesioferrite.

non-magnetic component which is a doublet attributed
to Fe3þ ions in octahedral coordination. The appear-
ance of this component confirms the formation of
ferriolivine. The hyperfine parameters of Fe2þ at the
M1 and M2 positions in the olivine structure did not
change during the formation of this phase. A small
amount of this phase is indicated even after heating at
1180 8C.
The main effects seen after annealing the samples
at temperatures ranging from 600 to 800 8C are the air-
oxidation of Fe2þ ions, the formation of superpara-
magnetic nanoparticles of Fe2O3*, and a magnetically
ordered phase of hematite (after heating at 800 8C).
The Fe2O3* fraction is represented in the Mössbauer
spectra by doublets with hyperfine parameters Is ¼
0.37–0.40 mm/s and QS ¼ 0.84–0.92 mm/s (Brown et
al. 1998, Barcova et al. 2003, Rivas- Sánchez et al.
2009). The contribution of the superparamagnetic
doublets increases significantly after heating at a
temperature of 800 8C. Formation of these Fe3þ ions
leads to visible changes in the hyperfine parameters of
Fe2þ at octahedral positions in olivine. This shows that
the decomposition of the olivine structure starts in this
temperature range. The Fe2O3* fraction is not visible
in the X-ray diffraction patterns because this method is
useful for crystalline phases and less so for short-
ordered phases. The thermally unstable nanoparticles
of Fe2O3* undergo isochemical structural change to
hematite a-Fe2O3 above 800 8C, as demonstrated by
the increase in relative area of this component in the
Mössbauer spectra. The high abundance of the
component connected with hematite at this tempera-
ture is also the result of the direct oxidation process of
Fe2þ from olivine to Fe3þ in Fe2O3. In addition,

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 110 THE CANADIAN MINERALOGIST

FIG. 3. Relative area of fitted Mössbauer subspectra obtained after heating at high temperatures for the olivines from Krzeniów
and Lanzarote.

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 CHANGES IN OLIVINE AFTER HEATING IN AIR: MÖSSBAUER STUDY 111

FIG. 4. Room-temperature Mössbauer spectra of the olivine samples from Lanzarote obtained after heating for one and 96 hr at
temperature of 500 and 750 8C.

heating at 800 8C leads to the minor incorporation of
Fe and Mg ions in the spinel structure of MgFe2O4.
The contribution of magnetically ordered phases of
hematite and magnesioferrite in samples heated at 800
8C is too small to be detected using the XRD method.
Hematite makes up more than 50% of all of the
iron-bearing phases in the investigated samples of
olivine heated at 1000 8C. This was the heating
temperature where contribution of these iron-oxides
was the highest. The high-temperature treatment (1180
8C) resulted in partial decomposition of the olivine
structure, mainly connected with the transfer of Fe and
Mg ions from olivine to MgFe2O4.
The stability of iron in the olivine structure is
influenced not only by heating at high temperatures but
also by the duration of heating. As can be seen in Figures
4 and 5, heating for less than two hours led mostly to
migration of Fe and Mg atoms inside the olivine
structure. After heating for two hours, an additional Fe3þ
doublet with a small contribution is visible. Isomer shift
of this component is in the range 0.38–0.45 mm/s and
quadrupole splatting in the range 0.30–0.44 mm/s. These
hyperfine parameters indicate the formation of ferrioli-
vine, which confirms the measurements made by
Khisina (Khisina et al. 1992, 1995). After two and 24
hr of heating, oxidation of Fe2þ to Fe3þ ions at octahedral
positions becomes dominant. Also, Fe3þ in superpar-
amagnetic iron oxides appear. Together with the
increase in temperature and time of heating, a
magnetically ordered phase of hematite and a small
amount of magnesioferrite appear. At higher tempera-
ture (750 8C) the above-mentioned processes were more
intensive. Heating of olivine at high temperature over
times longer than 48 hr did not create new phases but did
cause ordering of the phases present in the sample.

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 112 THE CANADIAN MINERALOGIST

FIG. 5. Concentrations of iron in olivine and in Fe-oxides after heating at 500 and 750 8C for 1, 2, 24, 48, and 96 hr.

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 CHANGES IN OLIVINE AFTER HEATING IN AIR: MÖSSBAUER STUDY 113

TABLE 3. MÖSSBAUER HYPERFINE PARAMETERS OF COMPONENTS PRESENT ON THE OBTAINED

MÖSSBAUER SPECTRA FOR INITIAL SAMPLES OF OLIVINE AND AFTER HEATING AT DIFFERENT
TEMPERATURES

Krzeniów Lanzarote
G Is Qs H A G Is Qs H A Compound
RT 0.29 1.15 3.02 - 56 0.30 1.16 3.09 - 50 Ol M1
1.13 2.86 - 26 1.14 2.91 - 41 Ol M2
0.19 0.40 - 18 0.19 0.38 - 9 Fe3þ(Si4þ)
400 8C 0.29 1.15 3.10 - 41 0.30 1.15 2.97 - 56 Ol M1
1.14 2.85 - 39 1.07 2.94 - 37 Ol M2
0.16 0.43 - 16 0.16 0.42 - 7 Fe3þ(Si4þ)
0.45 0.51 - 4 - - - - FOl
600 8C 0.30 1.15 3.09 - 24 0.34 1.15 2.63 - 20 Ol M1
- - - - 1.15 3.18 - 28
1.13 2.88 - 26 1.12 2.93 - 36 Ol M2
0.15 0.46 - 15 0.16 0.40 - 6 Fe3þ(Si4þ)
0.41 0.55 - 15 0.38 0.58 - 4 FOl
0.40 0.90 - 20 0.37 0.91 - 6 Fe2O3*
800 8C 0.32 1.15 3.11 - 6 0.34 1.16 3.07 - 48 Ol M1
1.13 3.00 - 13 1.12 2.81 - 19 Ol M2
0.16 0.46 - 15 0.14 0.50 - 2 Fe3þ(Si4þ)
0.41 0.34 - 9 0.39 0.52 - 6 FOl
0.39 0.84 - 23 0.39 0.92 - 16 Fe2O3*
0.39 –0.13 51.9 18 0.38 –0.14 51.9 4 Hem
0.23 –0.05 48.7 9 0.69 0.03 48.6 2 Mfr
0.72 –0.00 47.0 7 0.21 –0.05 46.9 3
1000 8C 0.30 1.15 3.03 - 4 0.32 1.16 3.04 - 28 Ol M1
1.13 2.98 - 2 1.13 2.89 - 8 Ol M2
0.16 0.40 - 9 0.13 0.50 - 2 Fe3þ(Si4þ)
0.38 0.29 - 2 0.45 0.57 - 1 FOl
0.37 –0.18 51.6 78 0.37 –0.18 51.3 52 Hem
0.34 0.04 47.5 3 0.29 –0.05 47.6 4 (Mg,Fe)3O4
0.70 0.05 47.0 2 0.65 –0.01 47.0 5
1180 8C 0.31 1.15 3.18 - 2 0.32 1.16 3.10 - 10 Ol M1
1.13 3.00 - 8 1.12 2.94 - 7 Ol M2
0.16 0.41 - 12 - - - Fe3þ(Si4þ)
0.37 0.34 - 3 0.45 0.57 - 3 FOl
0.37 –0.18 51.6 51 0.37 –0.17 51.4 50 Hem
0.28 0.00 48.8 14 0.21 –0.03 47.6 16 Mfr
0.27 0.00 47.2 10 0.54 0.06 47.0 14

G (mm/s) – full line width at half maximum; Is (mm/s) – isomer shift; Qs (mm/s) – quadrupole splitting; H (T) –
hyperfine magnetic field; A (%) – abundance of component. RT – room temperature.
Ol – olivine M1, M2; FOL – ferriolivine, Fe3þ(Si4þ); Hem – hematite; Mfr – magnesioferrite.

CONCLUSIONS formation of reducible iron oxides dispersed in the

Fe3þ ions in iron oxides dominate as a primary
product of the thermal treatment in air at 1180 8C of
natural samples of olivine from Krzeniów (Poland)
and Lanzarote (Canary Islands). Mössbauer spectros-
copy results show that the oxidation of iron-bearing
olivines starts after heating at 600 8C and leads to the
iron-depleted olivine matrix. Additionally, the forma-
tion of ferriolivine as a result of low-temperature
oxidation in the olivine structure was also observed. At
a temperature of 800 8C decomposition of the olivine
structure occurs, with incorporation of Fe and Mg ions
from olivine in magnetically ordered phases of
hematite and magnesioferrite. After heating at 1000

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 114 THE CANADIAN MINERALOGIST
8C, the highest abundance of iron oxides was observed,
which is useful information for using olivine in
biomass gasification. However, Mössbauer spectros-
copy results show that after heating olivine at this
temperature for four hours more than 20% of the iron
stays in the initial olivine structure. Therefore, the way
to obtain more iron from olivine while preserving the
structure of the mineral is to increase the heating time,
but to no more than 24 hr; more than this and the
process is unproductive.
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Received October 23, 2017. Revised manuscript accepted
November 15, 2018.