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Characterization of Fayalite from Copper Slags

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 I. Mihailova,
Journal of the University of Chemical D. Mehandjiev
Technology and Metallurgy, 45, 3, 2010, 317-326

CHARACTERIZATION OF FAYALITE FROM COPPER SLAGS

I. Mihailova1, D. Mehandjiev2

1
University of Chemical Technology and Metallurgy Received 05 March 2010
8 Kl. Ohridski, Sofia 1756, Bulgaria Accepted 12 June 2010
E-mail: irena@uctm.edu
2
Institute of Catalysis, Bulgarian Academy of Sciences,
Acad. G. Bonchev St., Bldg. 11,Sofia 1113, Bulgaria

ABSTRACT

The aim of the present study was to characterize the fayalite crystal phases in two types of copper slag – flash
smelting furnace slag (FS) and converter (CS) slag, given their possible use in adsorption and catalytic processes. Two
typical slag compositions different in chemical composition and way of production were selected, in order to clarify how
these differences affect fayalite crystallization and composition. The main mineral phase found in copper slags is fayalite.
The samples of the slag were characterized using X-ray diffraction (XRD), Fourier transformation infrared spectroscopy
(FTIR), Light optical microscopy (LOM) in transmitted and reflected light.
Keywords: fayalite, copper slags, flash smelting furnace slag, converter slag.

INTRODUCTION is characterized by phases of the melilite group -

The chemical, phase and granulometric compo-
sition of metallurgical slags has always attracted a great
deal of interest in view of their reuse in the process of
production or use for other purposes, such as the ex-
traction of certain metals from them or for the produc-
tion of construction materials. Being a waste product,
the slag recovery or disposal in designated places is
closely related to the issue of environmental protec-
tion. During the cooling of the slag, crystallisation pro-
cesses occur in it and certain phases are formed. The
main phases formed during each crystallization process
are known, and they depend on the cooling conditions
of the metallurgical slag at certain stages in the produc-
tion process. Since slag-forming additives (fluxes) are
based on silicon, aluminium, calcium and magnesium,
compounds of mineral analogues are formed, a process
similar to the process of crystallization in natural sili-
cate melts - volcanic lava or magma. For example, the
slag from processing and production of ferrous metals
gehlenite and akermanite. Some studies, however, have
shown that these slags have adsorption properties for
heavy metals, such as lead, copper, etc., and the increased
content of these phases enhance the slag adsorption prop-
erties [1, 2]. In such cases, slag can be successfully used
as an adsorbent in purification of water containing heavy
metals [3]. It was also found that metals adsorbed on
the slag surface, for example copper, make it catalyti-
cally active in processes of complete oxidation and cata-
lytic removal of carbon monoxide and harmful organic
substances [4]. The flash smelting furnace slag and con-
verter slags in copper production contain mainly fayalite
due to the nature of the process of production.
Fayalite is a common member of the olivine
group of minerals. Olivine is a name for a series of
silicate minerals with the formula M2SiO4, where M is
most commonly Fe or Mg. Fayalite (Fe 2SiO4) and
forsterite (Mg2SiO4) form a substitutional solid solu-
tion where the iron and magnesium atoms can be sub-
stituted for each other without significantly changing

317
 Journal of the University of Chemical Technology and Metallurgy, 45, 3, 2010
the crystal structure. The complete solid solution be-
tween these two elements is observed in olivine. Com-
positions in the Mg–Fe series commonly are identified
by the molar percentages of forsterite (Fo) and fayalite
(Fa) (e.g., Fo90Fa10), or in shortened form, by just their
forsterite number, where Fo# = Mg/(Mg+Fe)×100.
The crystal structure of Fe2SiO4 has been refined
using X-ray methods [5-7]. Olivine has an orthorhombic
structure. The structure consists of isolated SiO44- tetra-
hedra, which are held together by M cations occupying
two types of octahedral site (M1 and M2). The isolated
tetrahedra point alternately up and down along rows par-
allel to the z-axis. The magnetic spin structure has been
determined using powder neutron diffraction at 4 and 58
K by Santoro et al., who have also measured the powder
magnetic susceptibility between 4 and 300K [8].
Olivine with up to one formula unit of calcium
(CaMgSiO4) is referred to as monticellite. The iron ana-
logue, kirschsteinite (CaFeSiO4), is rare in nature. There
also is a manganese end member, tephroite (Mn2SiO4).
The metal cations occupy two positions in the crystal
structure, M1 and M2, which are defined by their sym-
metry; commonly, Fe2+ displays a preference for the
M1 site. The members of the olivine group are pre-
sented in Table 1. M. W. Schaefer has reported large
amounts of Fe3+ ions in fayalites (members of the olivine
group) from various localities. Such data are contrary to
the generally held belief that fayalite is incapable of ac-
commodating much Fe3+ ions in its crystal structure [9].
Members of the olivine group (olivines) are im-
portant rock-forming minerals in terrestrial, planetary,
Table 1. Olivine End-Members.
Mineral names Chemical
composition
Forsterite Mg2SiO4
Fayalite Fe2SiO4
Tephroite Mn2SiO4
Liebenbergite Ni2SiO4
Co-olivine Co2SiO4
Ca-olivine Ca2SiO4
Monticellite CaMgSiO4
Kirschsteinite CaFeSiO4
Glaucochroite CaMnSiO4
318
and astronomical geomaterials. Olivines are the major
component of Earth’s mantle, they are common to many
types of meteorites, and have been identified on the sur-
faces of planetary bodies and in the spectra of astronomical
targets. Olivine phases are indicators of low-silica envi-
ronments, they crystallize at high temperatures, and they
generally break down readily in the presence of weather-
ing agents such as water. As such, their identification and
characterization is a subject of considerable interest to a
wide variety of researchers [10]. Olivines are, quite liter-
ally, universally relevant minerals.
On Earth, olivine compositions in the forsterite–
fayalite series are common in mafic to ultramafic rocks,
in which their compositions typically range from about
Fo85–95. Compositions between Fo80 and Fo50 are typical
of gabbroic rocks. Olivine group minerals can be formed
in natural and in technological processes - in certain
mineral aggregates (rocks), in slags of the Blast furnace
and agglomerates [11]. Fayalite also has considerable
technological importance in copper metallurgical slags.
Ivanov et al. carried out interesting research on
phase composition and structure of copper slag from
Bulgarian plants [12-16].
Our previous research [17, 18] on the phase com-
position and structure of flash smelting furnace slag and
converter slag from copper production found that the
chemical compositions of fayalite included Al, Mg, Zn,
Cu, Al, Ca and other elements as isomorphic impuri-
ties. The phases in the samples were characterized by a
variable and non-stoichiometric composition. However,
the preference of the various elements contained in the
slag to the different crystalline or amorphous phases
was clearly manifested.
The aim of the present study was to characterize
the fayalite crystal phases in two types of copper slag –
flash smelting furnace slag and converter slag, given their
possible use in adsorption and catalytic processes. Two
typical slag compositions different in chemical compo-
sition and way of production were selected, in order to
clarify how these differences affect fayalite crystalliza-
tion and composition.
EXPERIMENTAL
Two kinds of copper slags were examined – slag
from flash-smelting furnace process and converter slag.
Samples were taken from the slag fields used for crys-
 I. Mihailova, D. Mehandjiev
tallization of the liquid slag by spraying with water. The
samples of copper flash smelting furnace slag and con-
verter slag are labeled as FS and CS respectively. The
samples of the slag were characterized using X-ray dif-
fraction (XRD), Fourier transformation infrared spec-
troscopy (FTIR), Light optical microscopy (LOM) in
transmitted and reflected light. Quantitative determi-
nation of elements in the samples was carried out by
Gravimetric analysis, Complexonometry, Atomic ab-
sorption spectrometry (AAS) and Inductively coupled
plasma (ICP-OES). The XRD characterization of the
different samples of slag was conducted using a DRON
3M X-ray diffractometer with a CoKá radiation (40
kV, 25 mA) as an X-ray source (λ = 0.17903 nm). The
samples were continuously scanned over an angular
range of 2è 8 – 90° using a step size of 0.05°. PowderCell
2.4 software [19] was used to determine the unit cell
parameters on the basis of experimental X-ray data.
FTIR spectroscopy has been applied. Infrared transmit-
tance spectra were recorded by using pressed pellet tech-
nique in KBr. The measurements were made with a FTIR
spectrophotometer Bruker EQUINOX 55 in the fre-
quency range from 4000 to 400 cm-1. In order to have a
good evaluation about the structures and textures in-
cluded of each sample as well as to make a comparison
Fig. 1. XRD patterns of samples of copper slags
between different samples, light optical microscopy in
transmitted and reflected light was used. In this study
we have used polarizing microscopes Laboval – pol – u
“Carl Zeiss” Jena.
RESULTS AND DISCUSSION
Chemical composition results
Table 2 shows the chemical composition of
samples of slag.
X-ray diffraction
Fig. 1 shows X-Ray diffraction data for samples
of slag.
Fayalite (Fe2SiO4) and magnetite (Fe3O4) are two
dominant phases in the samples. The two presented X-
ray diffraction patterns show amorphous halo at lower
values of 2è, associated with the presence of amorphous
phase. The converter slag sample contains larger amount
of magnetite in comparison with the sample of flash
smelting furnace slag. Divergence between experimen-
tal data and reference pattern data for the intensity of
diffraction peaks may be observed. The reflections of
the fayalite phase with the indices (120) (240) (020)
(130) have a higher intensity than expected. This is due
319
 Journal of the University of Chemical Technology and Metallurgy, 45, 3, 2010

Table 2. Chemical composition of slag samples. ing furnace slag sample and 31.0 ° 2è (d = 3.34) in the
Elements/ Content, %mass XRD pattern of converter slag sample are an exception.
Oxides Flash Converter Their presence is likely due to copper sulphide phases.
smelting Slag (CS) The cell parameters of fayalite and magnetite
furnace found in slag were calculated using the program Pow-
slag (FS) der Cell 2.4. They are given in Table 3.
SiO2 25.56 22.45
As seen in Table 3, the values of the unit cell
CaO 5.94 1.52
parameters of fayalite and magnetite in copper slags are
MgO 1.59 0.48
K2O 0.78 0.44 very close to literature values for pure phases.
Na2O 0.76 0.62
Fe 46.63 47.71 FTIR analysis
Cu 1.14 5.07 Fayalite is an especially important phase for dif-
Pb 0.06 0.66 ferent types of spectroscopy because, by definition, it
Zn 0.33 1.05 contains an equal distri­bution of Fe2+ cations between
Ni 0.017 0.036 the M1 and M2 octahedral sites. Thus, features associ-
Co 0.043 0.160
ated with each of the two sites must represent equal
As 0.02 0.02
numbers of Fe2+ cations, removing the uncertainties
Sb 0.021 0.064
Bi 0.020 0.007 associated with assumptions about order/disorder of Fe2+
Cd 0.016 0.002 and other cations [24].
Cr 0.004 0.043 Thermal infrared band assignments for Mg–Fe
S 0.18 0.74 olivines were determined early on [25-26] from trans-
Ó 83.111 81.072 mission spectra and many studies have resulted in re-
fined and extended assignments. Symmetry analysis in-
to textures in the samples related to fayalite crystals dicates that there are a total of 84 normal modes of
morphology. The presence of additional crystalline vibration [27], 35 of which are infrared active (but which
phases could not be ascertained from the presented XRD may not be individually observable in unpolarized spec-
patterns. Peaks with negligible intensity remain after tra, or may be too weak to be observed). These modes
juxtaposing diffraction maxima with the reference pat- represent internal stretching and bending modes as well
terns for fayalite and magnetite. Diffraction maxima at as lattice modes (cation translations and rigid rotation–
34.8 ° 2è (d = 3.00) in the XRD pattern of flash smelt- translation) of the SiO4 tetrahedra. In spectra of ran-

Table 3. Cell parameters of the crystalline phases in the slags. Comparison with literary data.

Sample Cell parameter of Cell parameters of fayalite (orthorhombic)

magnetite (cubic)
= = > ?
Flash smelting 8.385 4.824 10.477 6.089
furnace slag (FS)
Converter slag 8.412 4.825 10.502 6.120
(CS)
Magnetite 8.3958
[20]
Magnetite 8.3965
[21]
Magnetite 8.3970
[22]
Fayalite 4.818 10.471 6.086
[5]
Fayalite 4.818 10.470 6.086
[23]

320
 I. Mihailova, D. Mehandjiev

Fig. 2. FTIR spectra of the samples of copper slags

domly oriented samples, the three principal bands be-
tween : 1000 and 850 cm-1 are the result of splitting of
degenerate Si–O asymmetric stretching vibrations of the
í3 mode in SiO4. A feature near 825 cm-1 results from
the í1 mode (symmetric stretch), and three or four fea-
tures in the 610–460 cm-1 region can be attributed to split-
ting of the degenerate í4 asymmetric bending vibration.
Features in the 500–200 cm-1 region are attributable to
the í2 symmetric bending mode, rotations and translation
of the SiO4 tetrahedron, and translations of one of the
divalent cations. In the far infrared (200–85 cm-1), addi-
tional translational modes and combinations of SiO4
and cation translations are observed [10].
Fig. 2 shows FTIR spectra of samples.
As can be seen the presented spectra are mainly
due to the fayalite phase in the samples.
The vibrational modes in olivine series minerals
vary slightly as a function of solid solution composi-
tion, leading to shifts in band position and changes in
band strength, including the presence or absence of some
features. Regardless of whether the measured olivines
are natural or synthetic, their infrared spectra exhibit a

Table 4. Olivine transmittance band positions, cm-1.

Sample / Fo# Band Band Band Band Band Band Band Band
1 2 3 4 5 6 7 8
FS (this study) 948 914 874 826 562 502 472 425
CS (this study) 947 911 873 826 564 504 475 413
Fo31 956 927 883 833 582 516 482 (417)
Fo29 955 926 878 831 573 513 482 411
Fo18 951 918 874 829 567 511 480 411
Fo14 950 920 883 831 570 506 479 (407)
Fo11 947 920 874 829 563 507 476 409
Fo9 949 920 876 831 570 506 478 (413)
Fo1 945 916 874 828 563 505 475 (419)
Fo0 945 917 875 830 566 507 478 –
Fo0 946 917 879 830 569 505 479 (418)

321
 Journal of the University of Chemical Technology and Metallurgy, 45, 3, 2010

generally linear decrease in the wavenumber position
of each band as the molar proportion of Fe increases,
and this trend is attributed to the increasing radius and
mass of the cation linking the SiO4 tetrahedra. The lin-
earity of band positions as a function of composition in
the forsterite – fayalite series indicates a nearly random
distribution of Mg2+ and Fe2+ in the M1 and M2 sites
and that any significant deviation from linearity would
indicate ordering of the Mg2+ and Fe2+ ions [10].
In Table 4, experimental data for fayalite in cop-
per slag is compared to literature data [10] for olivines
with a forsterite number (Fo#) in the range of 31-0.
There is a good correspondence between experimental
data and literature data for olivines with Fo# below 11.
Due to the low content of magnesium in slag, the
forsterite number of the fayalite phase formed in slag
should be small. It is interesting to make a theoretical
estimate of the expected forsterite number on the basis
of the available data for the content of the main com-
ponents involved in fayalite structure formation. Mag-
nesium, iron and silicon content in FS and CS samples
are given in Table 1.
On the basis of these data using the formula
Fo# = a.100/a + 0,435.b, where a and b denote respec-
tively the percentage content of magnesium and iron,
the forsterite number Fo# was calculated, assuming that
all magnesium and iron participate in the fayalite phase
formation in both slags. The calculated values are as fol-
lows: Fo# = 4.5 (FS) and Fo# = 1.4 (CS). The forsterite
number value of fayalite in flash smelting furnace slag is
higher than that in converter slag, which should be ex-
pected given the higher content of magnesium in the phase.
Experimental values for the forsterite number of
fayalite phases may also be calculated using the linear
relationship between the band position and the forsterite
number. In Fig. 3 is shown the dependence of position
of the band 1 at : 950 cm-1 on the forsterite number,
according to literature data [28, 29].
In Fig. 3 with straight horizontal lines are also
given the values derived by us for the same band of the
fayalite phase in both slags. The intersection points of
these lines with the straight line give the forsterite num-
ber value. Thus the calculated value for FS sample is 8.3,

956

954

952
-1
Band cm

950

948 FS
CS
946

944
0 5 10 15 20 25 30 35

Fo#
Fig. 3. The dependence of position of the band 1 at ~ 950
cm-1 on the forsterite number (The equation of the straight
line is: Y= 945.088 + 0.34776 X. Then Fo# = 8.3 for the sample
of flash smelting furnace slag (FS) and Fo# = 5.5 for the
sample of converter slag (CS).
Fig. 4. Microstructure of sample of flash smelting furnace
slag. Elongate aggregates of fayalite and black magnetite
crystals in a groundmass of glass. 120x optical magnification.
Plane polarized (a) and cross polarized (b) transmitted light
photomicrographs.

322
 I. Mihailova, D. Mehandjiev
Fig. 5. Typical morphology of fayalite crystals in the sample
of flash smelting furnace slag. 120x optical magnification.
Plane polarized (a) and cross polarized (b) transmitted light
and that for CS sample is 5.5. There are certain differ-
ences between calculated and found values of the forsterite
number, though the theoretical estimate suggesting a
higher forsterite number of flash smelting furnace slag
compared to that of converter slag was confirmed.
However, it should be kept in mind that silicon
also plays a determining role. Calculations based on its
content show that fayalite formation phase, in which all
magnesium and iron participate can not be expected.
Taking into consideration the above limitation in the
calculation of the forsterite number, forsterite number
values obtained are 4.7 for flash smelting furnace slag
and 1.6 for converter slag. The calculation assumes that
all the magnesium participates as well as some iron,
inasmuch as allowed by the presence of silicon. From
this follows that the excess iron should form a new phase
and presence of magnetite in both slags was actually
Fig. 6. Inclusions of magnetite and silicate glass in the
fayalite crystals from flash smelting furnace slag. 120x optical
magnification. Plane polarized (a) and cross polarized (b)
transmitted light photomicrographs.
observed. Since magnetite is clearly distinguished under
X-rays as a separate phase, it appears that there is less
iron participating in the fayalite phase. At the same time
silicon-containing phases are additionally found that could
increase the value of the forsterite number, which was
actually observed. Some deviations from data for the iso-
morphic series forsterite - fayalite are inevitable and may
be also due to possible inclusion in the olivine crystal
structure of other cations present in the slag.
Light optical microscopy
Olivine group minerals crystallize in the same
system, both in rocks and in slags, but their morpholo-
gies are different. The most frequently occurring forms
of olivine in rocks have been analyzed by optical mi-
croscopy. These forms are crystal and rounded. Olivine
group minerals from slags show skeletoidal or crystal
323
 Journal of the University of Chemical Technology and Metallurgy, 45, 3, 2010

Fig. 7. Allotriomorphic fayalite crystal in the converter slag. 120x optical magnification. lane polarized (a) and cross polarized
(b) transmitted light photomicrographs

Fig. 8. Fayalite displaying skeletal crystal form in the converter slag. 120x optical magnification. Plane polarized (a) and cross
polarized (b) transmitted light photomicrographs

Fig. 9. Typical morphology of fayalite crystals in the sample of converter slag. 120x optical magnification. Plane polarized (a) and
cross polarized (b) transmitted light photomicrographs.

324
 I. Mihailova, D. Mehandjiev
Fig. 10. Fayalite (1), magnetite (2), sulphide inclusions (3)
and copper (4) in silicate glass a) and b) – sample of flash
smelting furnace slag; c) – sample of converter slag. 120x
optical magnification. Reflected light photomicrographs.
form under microscope. Morphology of olivine crystal
forms in slags differs from those in natural aggregates
(rocks) [11].
Fayalite crystals occurring in experimentally ob-
tained copper converter slags with variable SiO2 con-
tents are described [15]. The crystals differ in the de-
gree of skeletal growth which is explained in terms of
hindrances in heat transfer brought about by the in-
creasing viscosity of the melt upon increase of the SiO2
content. The formation of tubular inclusions in crystals
elongated along the b-axis is related to the influence of
sulphide droplets at the surface of the crystals [15].
In Figs. 4-10 are given the typical structural re-
lationships between phases present in the examined
samples of slag. It was confirmed that fayalite is the
dominant crystal phase, followed by magnetite and cop-
per sulphide inclusions, with the glass phase present
as a main mass. Fayalite crystals when viewed in trans-
mitted light were pleochroit with shades ranging from
green to pink. For FS sample were typical dendritic
growth and subparallel orientation in space as well as
not fully formed skeletal crystals. The relations be-
tween fayalite and the magnetite phase in the samples
differed. In fayalite crystals themselves there were small
grains of magnetite inclusions. In some cases the lat-
ter formed elongated zones in skeletal fayalite crystals
and showed simultaneous crystallization of both phases.
Heterogeneous xenomorphic crystals were typical
for CS sample. They included many impurities of crys-
talline phases and glass within their boundaries (Fig. 9).
Specific skeletal forms were also observed. The magne-
tite content was definitely higher compared to that in
FS sample and the amorphous phase was more hetero-
geneous.
CONCLUSIONS
From the present study of fayalite crystal phases
in two types of copper slag - flash smelting furnace slag
and converter slag the following conclusions can be
drawn:
• Despite the complex composition of metallur-
gical slag and the possibility of inclusion of other ele-
ments as isomorphic impurities in the fayalite phase
Fe2SiO4, the latter’s crystal lattice was not substantially
altered, according to XRD data. The values of the unit
cell parameters of fayalite and magnetite in copper slags
were very close to literature values for pure phases. This
may have been due to isomorphic substitutions of Fe2+,
325
 Journal of the University of Chemical Technology and Metallurgy, 45, 3, 2010
both by cations with smaller ionic radii, such as Mg2+,
and by cations with larger ionic radii.
• The obtained FTIR spectra of copper slag
samples corresponded almost entirely to the spectrum
of the fayalite phase. This made possible the use of FTIR
to determine the composition of fayalite through the
established dependency of spectrum bands positions on
fayalite composition.
• Dendritic growth as well as not fully formed
skeletal crystals were common features relevant to the
morphology of fayalite in the examined samples of cop-
per slag. Fayalite crystals included many impurities of
crystalline phases and glass within their boundaries. Spe-
cific crystal forms were observed in both types of slag.
• On the base of presented data the copper slags
may be used as adsorbents and support for catalysts.
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