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1300054
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1
The Canadian Mineralogist
Vol. 00, pp. 1-11 (2015)
DOI: 10.3749/canmin.1300054
AND
NICOLAE BUZGAR
Alexandru Ioan Cuza University of Iai, Faculty of Geography and Geology, Department of Geology, 20A Carol I Blv.,
700505 Iai, Romania
GHEORGHE DAMIAN
Alexandru Ioan Cuza University of Iai, Faculty of Geography and Geology, Department of Geology, 20A Carol I Blv.,
700505 Iai, Romania and
Tech Univ Cluj Napoca, North University Center of Baia Mare, 62A Dr. Victor Babe Street, 430083 Baia Mare, Romania
ANDREI BUZATU
Alexandru Ioan Cuza University of Iai, Faculty of Geography and Geology, Department of Geology, 20A Carol I Blv.,
700505 Iai, Romania
ABSTRACT
The Coranda-Hondol ore deposit (Certej, Romania) is a sulfide ore deposit that was mined primarily for gold, silver, lead,
and zinc. Secondary minerals were formed through a precipitation process from sulfate solutions with a high concentration of
dissolved metals (especially Fe). These sulfate solutions resulted from acid mine drainage. Fourteen waste samples were analyzed through Raman spectrometry, X-ray diffraction, and scanning electron microscopy. Fe3+-, Fe2+-, Cu-, Zn-, Ca-, Mg-, and
MnAl-hydrated sulfates were identified. All are unstable when exposed to the laser beam of the Raman spectrometer.
Coquimbite, copiapite, ferricopiapite, hydroniumjarosite, and gunningite turn into anhydrous forms or oxides, depending on the
laser power. Gypsum turns into bassanite, while apjohnite loses all water molecules at 53.6 mW laser power on the surface
of the sample. Rhomboclase, melanterite, rozenite, antlerite, and brochantite break down without forming new minerals.
Fe2+-sulfates do not change into hematite under laser irradiation. Epsomite and hexahydrite are stable at 53.6 mW laser power.
INTRODUCTION
Secondary minerals of supergene origin can be
found in various environments, especially in areas of
oxidation of metalliferous ore deposits containing sulfides. In some cases high and varied concentrations of
sulfosalts can form. These supergene alteration minerals
are mainly formed through oxidation of common sulfides (especially pyrite) and then through precipitation
from acid mine drainage (AMD) (Alpers et al. 2003).
Many previous studies have been undertaken by
Raman spectrometry to identify secondary sulfates,
especially those of Fe (Sasaki et al. 1998, Chio et al.
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MATERIALS
AND
METHODS
RESULTS
AND
DISCUSSION
(H3O)Fe3+(SO4)23H2O
Fe3
2 SO4 3 9H2 O
Fe2 Fe3
4 SO4 6 OH2 20H2 O
3
Fe3
2=3 Fe4 SO4 6 OH2 20H2 O
H3 OFe3
3 SO4 2 OH6
Fe2+SO47(H2O)
Fe2+SO44(H2O)
MgSO47(H2O)
MgSO46(H2O)
CaSO42(H2O)
MnAl2 (SO4)422(H2O)
Cu3(SO4) (OH)4
Cu4(SO4) (OH)6
(Zn, Mn)SO4H2O
Fe3+
Rhomboclase
Coquimbite
Copiapite
Ferricopiapite
Hydroniumjarosite
Fe2+
Melanterite
Rozenite
Hexahydrite
Gypsum
Apjohnite
Cu and Zn
Antlerite
Brochantite
Gunningite
Ideal formula
Mineral name
++/S
+/L
+/L
+++/S
++/S
++/S
+++/S
++/S
++/S
++/S
+++/S
++/S
+++/S
++/L
XRD, Raman
Raman, SEM
Raman
XRD, Raman
Raman, SEM
XRD, Raman
XRD, Raman
Raman
Methods
TABLE 1. MINERAL NAMES, IDEAL CHEMICAL FORMULAE, PRINCIPAL RAMAN BANDS, AND DISTRIBUTION AND METHODS OF IDENTIFICATION FOR
THE MINERALS IDENTIFIED IN THIS STUDY
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the raman study of weathering minerals from the coranda-hondol open pit
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FIG. 1. The Raman spectra of rhomboclase at 10.5 mW (a), coquimbite at 10.5 mW (b), mikasaite at 14 mW (c), copiapite
at 7.4 mW (d), ferricopiapite at 7.4 mW (e), intermediate phases between copiapite (ferricopiapite) and mikasaite (f, g),
and mikasaite at 18.4 mW (h).
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the raman study of weathering minerals from the coranda-hondol open pit
beam exposure may have two explanations: (1) at laser
power values above 18.4 mW, the ferricopiapite
and copiapite dehydrate into quasi-amorphous iron
hydroxide sulfate Fe(OH)SO4 (Lu & Wang 2012);
(2) these minerals turn into mikasaite via dehydration.
The second hypothesis is more plausible because the
Raman spectrum acquired (Fig. 1h) fits very well with
that of mikasaite (Fig.1c), much better than with that
of a quasi-amorphous phase.
Hydroniumjarosite is commonly associated with the
oxidation zones of sulfide deposits (Brophy & Sheridan
1965, Frost et al. 2006). The Raman spectral fingerprint
of this mineral can be clearly observed in Figure 2a.
The spectrum was acquired at 3.90 mW laser power.
Discrimination of Raman spectra of the members of the
jarosite-natrojarosite-hydroniumjarosite solid solution
series can be achieved using the following peaks:
3400 cm1, 1014 cm1, and 430 cm1 (Sasaki
et al. 1998, Frost et al. 2006, Lu & Wang, 2012).
When the laser power is increased above 14.3 mW
the spectrum of hydroniumjarosite changes into a
new spectrum (Fig. 2b) with the main Raman bands at
FIG. 2. The Raman spectra of hydroniumjarosite at 3.9 mW (a), hematite at 14.3 mW (b), melanterite at 5 mW (c), rozenite
at 5 mW (d), synthetic rozenite at 5 mW (e), szomolnokite obtained by heating of synthetic rozenite at 105 C for 30 min
(f), mikasaite obtained by heating of synthetic rozenite at 700 C for 30 min (g), and hematite obtained by heating of
synthetic rozenite at 800 C for 30 min (h); 3 magnication of the spectrum in a specic region is shown.
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FIG. 3. The Raman spectra of apjohnite at 22.9 mW (a), anhydrous form of apjohnite at 53.6 mW (b), gypsum at 14.3 mW
(c), bassanite at 35 mW (d), hexahydrite at 53.6 mW (e), and epsomite at 53.6 mW (f); 3, 4, and 5 magnication of
the spectrum in a specic region is shown.
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the raman study of weathering minerals from the coranda-hondol open pit
the v1 Raman mode trends to higher wavenumbers
with dehydration. For this reason it can be considered
that apjohnite turns into the anhydrous form.
Gypsum is widespread in waste samples from the
CHOP. It occurs as tabular monoclinic crystals up to
0.01 mm in length [Fig. S1a (Supporting Information)].
Its presence is due to calcite, one of main gangue minerals in the CHOP ore. Calcite breaks down and gypsum
appears in the acidic environment of the oxidation zones
of the sulfide deposits. Conversion of gypsum into bassanite as a function of temperature is irreversible and
well established (Sarma et al. 1998). Conversion of gypsum into bassanite under laser irradiation occurs after
increasing laser power above 35 mW (Fig. 3c, 3d).
In some cases gypsum turns into bassanite only at maximum laser power (53.6 mW). Crystal size certainly
influences the power required.
Hexahydrite and epsomite occur as very fine crystalline aggregates [Fig. S1f (Supporting Information)].
Raman spectra are shown in Figures 3e and 3f. The (v1)
symmetric stretching vibrations of both minerals appear
at 985 cm1. Taking into account our spectra and data
from the literature (Wang et al. 2006, Frezzotti et al.
2012), the distinction between hexahydrite and epsomite
can be done using the 3 bands of SO4 and the vibrational modes of H2O. The Raman bands at 1147 and
1084 cm1 are assigned to hexahydrite, while the (3)
antisymmetric stretching mode of epsomite appears at
1136, 1097, and 1062 cm1. The vibrational modes of
FIG. 4. The Raman spectra of brochantite at 5 mW (a), antlerite at 3.9 mW (b), and of both minerals after exposure under
intense laser beam at 53.6 mW (c); Raman band at 1591cm1 belongs to carbon.
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(785 nm) of 1 mW (Martens et al. 2003a). As previously noted, crystal size influences the laser power at
which these minerals break down. No new minerals
appear after the breakdown of these minerals (Fig. 4c).
The Raman line at 1591 cm1 belongs to carbon, which
comes from organic matter in the sample that is subjected to intense laser irradiation.
Gunningite was found on the surface of the sphalerite crystals, in particular. Goslarite (ZnSO47H2O) and
bianchite [(Zn,Fe2+)SO46H2O] are more widespread in
the oxidation zone of the metalliferous ore deposits containing sulfides (Chou et al. 2013) but at CHOP only
gunningite was identified. Its presence was confirmed
by XRD [Fig. S2 (Supporting Information)]. The
Raman spectrum of gunningite from CHOP (Fig. 5a)
fits very well with the Raman spectrum of synthetic
zinc sulfate monohydrate (Fig. 5b). A strong band
occurs at 1024 cm1 in both Raman spectra and is due
to (1). Two bands of the (3) antisymmetric stretching
mode are observed at 1192 and 1087 cm1. The bands
at 503 and 423 cm1 are assigned to the (2) bending
FIG. 5. The Raman spectrum of gunningite from CHOP at 7.37 mW (a); synthetic gunningite at 7.37 mW (b); gunningite
heated at 105 C for 30 min (c); synthetic gunningite heated at 800 C for 30 min (zinc oxysulfate) (d); synthetic gunningite heated at 900 C for 30 min (zinc oxide) (e); synthetic gunningite heated at 400 C for 30 min (zincosite) (f); photochemical degradation of gunningite (zincosite) at 35.8 mW (g); 3 magnication of the spectrum in a specic region
is shown.
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the raman study of weathering minerals from the coranda-hondol open pit
Triple degeneration of the stretching vibrations modes
suggests a large variation in SO4 tetrahedral distortion
(different OSO) due to lattice distortion which can
be attributed to the high temperature.
At high temperature, synthetic gunningite turns into
zinc oxysulfate (ZnO2ZnSO4) (Fig. 5d) and zinc
oxide (Fig. 5e) (Mu & Perlmutter 1981, Sharma &
Exarhos 1997, Siriwardane et al. 1999). These compounds do not form from photochemical degradation
of natural gunningite under laser beam exposure.
.
.
.
.
.
.
CONCLUSIONS
Pyrite is the main sulfide mineral from the Coranda
Hondol open pit which turns into secondary minerals
through oxidation and hydration. It is followed by
sphalerite with a low content of Fe (13% Fe, after
Udubaa et al. 1982) and chalcopyrite. Galena,
although widespread, did not lead to the formation of
secondary lead minerals (e.g., anglesite). This can be
explained by the fact that lead sulfates (especially
anglesite) have very high solubility in acidic waters,
and their precipitation is not possible under these
circumstances (Dove & Czank 1995).
Based on the main sulfides which generate oxidation
reactions, neutralization, hydration, and/or dehydration
and lead to the formation of supergene alteration, secondary minerals can be divided into the following categories (in order of abundance from most to least):
. Fe(III)-sulfates rhomboclase, copiapite, ferricopiapite, coquimbite, and hidroniumjarosite;
these are the most abundant secondary minerals,
Bassanite
anhydrous Apjohnite
x
x
Zincosite
Notes: * do not turn into a new mineral or break down at the maximum power of 53.6 mW;
x break down above the specified laser power threshold.
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ACKNOWLEDGMENTS
The authors gratefully acknowledge the staff of
S.C. DevaGold S.A. for access to the Coranda Hondol
open pit and their support at the sampling site. Thanks
are also extended to Prof. Dr. Essaid Bilal and to
anonymous reviewers for valuable suggestions and
comments to improve the quality of the paper.
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