Miner Petrol (2015) 109:405–411
DOI 10.1007/s00710-015-0370-x

ORIGINAL PAPER

Parádsasvárite, a new member of the malachite-rosasite groupfrom Parádsasvár, Mátra Mountains, Hungary
Béla Fehér & Sándor Szakáll & Norbert Zajzon &Judith Mihály

Received: 22 July 2014 / Accepted: 6 February 2015 / Published online: 5 March 2015
# Springer-Verlag Wien 2015

Abstract Parádsasvárite (IMA No. 2012-077) was found in
the Nagy-Lápafő area, Parádsasvár, Mátra Mountains,
Hungary. It forms pale beige, globular aggregates up to
0.2 mm in diameter on calcite. Associated secondary minerals
are smithsonite, hemimorphite, hydrozincite, aurichalcite androsasite. The mineral was formed as an alteration product of
sphalerite and chalcopyrite in a carbonate-rich environment.
Parádsasvárite is translucent with a weakly vitreous, dull orsilky lustre and white streak. Its Mohs hardness is about 2–3,
cleavage and parting were not observed. It is brittle; the fracture
is finely fibrous. Average of nine electron-microprobe analyses
gave ZnO 58.08, CuO 12.60, PbO 1.27, CO2 (calc.) 19.50, H2O(calc.) 7.94, total 99.39 wt.%, corresponding to the empiricalformula (Zn0.62Cu0.36Pb0.01)Σ0.99Zn1.00(CO3)(OH)2. The sevenstrongest lines in the X-ray powder diffraction pattern are [dhklin Å (Iobs %, hkl)] 6.054 (67, 200), 5.085 (100, 210), 3.703 (87,
310 and 220), 3.021 (25, 400 and 130), 2.971 (25, −211 and001), 2.603 (62, −221) and 2.539 (36, 420). According to its Xray powder diffraction data and chemical formula, parádsasvárite
belongs to the malachite-rosasite group and it is isostructural withrosasite. It is monoclinic, space group P21/a, a = 12.92(1),Editorial handling: A. Beran
B. Fehér (*)
Department of Mineralogy, Herman Ottó Museum, Kossuth u. 13,3525 Miskolc, Hungary
e-mail: feherbela@upcmail.hu
S. Szakáll : N. Zajzon
Department of Mineralogy and Petrology, University of Miskolc,
3515 Miskolc-Egyetemváros, Hungary
J. Mihály
Institute of Materials and Environmental Chemistry, Research Center
for Natural Sciences, Hungarian Academy of Sciences, Pusztaszeri út
59-67, 1025 Budapest, Hungary

b = 9.372(7), c = 3.159(4) Å, β = 110.4(1)°, V = 358.5(5) Å3,
Z = 4.

Introduction
Rosasite, the zinc-rich member of the malachite-rosasite groupof minerals, has been known for a long time (Lovisato 1908).
In the literature its formula is given as (Cu, Zn)2(CO3)(OH)2(see e.g., Anthony et al. 2003); this formula indicates a disordered distribution of Cu and Zn, with the former as dominantcation. The zinc-dominant phase was described by Strunz(1959) from Tsumeb, Namibia, and named zincrosasite. Its
description is very short, since it consists of six sentences
and no figures or tables are presented. The author did not
produce a chemical analysis or empirical formula for the mineral; in fact, he indicated the Zn:Cu ratio only, which is equal
to 58.60:51.94 corresponding to a chemical formula(Zn1.06Cu0.94)(CO3)(OH)2. Present status of zincrosasite in
the most recent IMA list of mineral species (IMA 2014) is Q
(questionable), with chemical formula (Zn, Cu)2(CO3)(OH)2.
To date, several occurrences of zincrosasite have been described worldwide and the Mindat.org database lists 24
localities for it (http://www.mindat.org/min-4414.html).
Unfortunately, the available chemical analyses forzincrosasite are a very few. Pauliš et al. (2005) give the formula (Zn1.15Cu0.85)(CO3)(OH)2 for the sample of the mineralfound at Herlíkovice in the Czech Republic. The sample ofzincrosasite with the highest zinc content was described by
Fehér et al. (2008) from Rudabánya in Hungary with chemical
formula (Zn1.52Cu0.47Fe0.01)(CO3)(OH)2.
Following Perchiazzi and Merlino (2006), two distinct
structural types exist in the malachite-rosasite group, namely
a malachite structure type (Zigan et al. 1977) and a rosasite
structure type (Perchiazzi 2006). In both of the above structure

406

types, two hexacoordinated cation sites, named Me1 and Me2,
exist. The former displays a Jahn-Teller distorted 4 + 2 coordination, quite common in copper oxysalts (Eby and
Hawthorne 1993). Me2 site displays a more regular octahedral
coordination. Several mineral species are known in this group,
defined by the dominant cation on the Me sites and by theirstructural type (see Perchiazzi and Merlino 2006). In thissense, zincrosasite does not define a distinct mineral species,
because the dominant cations are copper in Me1 and zinc in
Me2, which is the same in the case of rosasite. The difference

Fig. 1 Geological map of thesurroundings of the type localityof parádsasvárite (after Rónai and
Pelikán 2005). Legend: 1: fluvial
sediments (Holocene); 2: Kékes
Andesite Formation (Miocene,
Badenian-Sarmatian); 3:
Nagyhársas Andesite Formation(Miocene, Badenian); 4: Tar
Dacite Tuff Formation (Miocene,
Carpathian); 5: Hasznos Andesite
Formation (Miocene,
Carpathian); 6: Fót Formation(Miocene, Carpathian); 7: Garáb
Schlier Formation (Miocene,
Carpathian); 8: Gyulakeszi
Rhyolite Tuff Formation(Miocene, Ottnangian); 9:
Zagyvapálfalva Formation(Miocene, Eggenburgian); 10:
Pétervására Sandstone Formation(Miocene, EgerianEggenburgian)Fehér B. et al.

between rosasite and zincrosasite is the total cation content(Me1 + Me2), which is not relevant in the nomenclature.
Here we describe the new mineral parádsasvárite, which
represents the Zn-dominant end-member of the malachiterosasite group, where zinc is the dominant cation in both
Me1 and Me2 sites. The mineral was approved by theCommission on New Minerals, Nomenclature andClassification of the International Mineralogical Association(IMA CNMNC) under IMA no. 2012-077. The holotype material is deposited in the collection of the Herman Ottó

Parádsasvárite, a new member of the malachite-rosasite group407

Museum, Miskolc, Hungary, under catalogue number
2012.23. Parádsasvárite was named after the type locality
Parádsasvár, in the Mátra Mountains of Hungary.

Geologic frameFig. 2 Globular parádsasvárite aggregates on calcite from Parádsasvár.
Short edge of the picture: 0.8 mm. Photo courtesy of László TóthFig. 3 Section of a globular parádsasvárite aggregate consisting of
bladed crystals; BSE-SEM image. Long edge of the picture: 380 μm

Fig. 4 Calculated X-ray powder
diffraction patterns for malachite
and rosasite. Atomic coordinates
used in the calculation are from
Zigan et al. (1977) for malachiteand from Perchiazzi (2006) for
rosasite. Diagnostic reflections
are indicated by asterisks

Parádsasvárite was found in a near-surface epithermal ore
mineralization in the Nagy-Lápafő area, Parádsasvár, Mátra
Mountains, Hungary (Fig. 1) (47°54′26.50″N, 19°57′9.68″
E). This ore mineralization is connected with the Middle
Miocene andesitic volcanism (Nagyhársas Andesite
Formation) of the Mátra Mountains. During the constructionof a forest road, carbonate veins up to a few dm in thickness
were exposed in the andesite, and these were found to contain
disseminated sulphide minerals. Secondary minerals, formedby alteration of the sulphides, can be found in small cavities ofthe veins.
The main mineral of the carbonate veins, which are locatedin argillized and pyritized andesite, is calcite. The most abundant sulphide mineral is sphalerite, but several other sulphides
were also found here in lesser quantities: galena, pyrite, chalcopyrite, marcasite, hawleyite/greenockite, and tetrahedrite.
Beside calcite, the other gangue minerals in the veins are fluorite, palygorskite, quartz, dolomite, and anatase. At the contactof the andesite and carbonate veins there are clay minerals,
such as montmorillonite, illite and kaolinite, as well as gibbsite;these were observed as hydrothermal alteration products (Kiss
1960, 1964; Koch 1966). To date, the following secondary
minerals have been detected, and here they are given in theirorder of decreasing abundance: smithsonite, hydrozincite,hemimorphite, aurichalcite, rosasite, malachite, chalcophanite,azurite, cerussite, anglesite, devilline, and linarite.

408
Table 1

Fehér B. et al.
X-ray powder diffraction data for parádsasvárite

Table 2

Irel (%)

dmeas (Å)

dcalc (Å)

h

k

l

11
67
100
14
87

7.431
6.054
5.085
4.678
3.703

7.411
6.054
5.085
4.686
3.707
3.706
3.027
3.025
2.964
2.960
2.881
2.776
2.599
2.543
2.503
2.480
2.470

1
2
2
0
3
2
4
1
−2
0
4
2
−2
4
0
−3
3

1
0
1
2
1
2
0
3
1
0
1
3
2
2
2
2
3

0
0
0
0
0
0
0
0
1
1
0
0
1
0
1
1
0

2.355
2.345
2.343
2.209
2.151
2.149
2.019
1.983
1.973
1.914
1.858
1.791
1.789
1.747
1.702
1.661
1.594
1.570
1.541

2
5
0
−2
5
0
3
−6
6
5
−5
2
4
−4
−6
2
5
−2
−4

0
1
4
3
2
3
1
1
1
3
3
5
1
4
3
4
1
0
1

1
0
0
1
0
1
1
1
0
0
1
0
1
1
1
1
1
2
2

1.512
1.482
1.412
1.410
1.388

2
5
0
−9
4

6
5
2
1
6

0
0
2
1
0

25

3.021

25

2.971

10
7
62
36
23
15

2.880
2.773
2.603
2.539
2.498
2.478

20

2.346

5
19

2.212
2.150

12
5

2.016
1.975

4
6
7

1.910
1.852
1.785

8
6
7
7
10
9

1.748
1.699
1.656
1.589
1.568
1.544

5
4
3

1.510
1.479
1.410

4

1.385

Sample material and experimental
Parádasasvárite occurs as pale beige, globular aggregates up
to 0.2 mm in diameter and consists of bladed crystals in aradial arrangement on calcite (Figs. 2 and 3). The individual
bladed crystals are up to 80 × 5 μm. The colour on the surface

Electron microprobe data for parádsasvárite

Constituent

Mean wt.%(n = 9)Range in wt.%

σ

ZnO

58.08

55.00–63.08

2.70

CuO

12.60

8.76–15.18

2.17

PbO

1.27

0.55–1.65

0.29

CO2a

19.50

H2Oa

7.94

Total

99.39

a

Calculated from the stoichiometryof the aggregates is pale beige, while sections of the globular
aggregates are white, sometimes with a weak bluish tint. Its
lustre is weakly vitreous or dull on the surface of the aggregates and silky in cross-sections. The streak is white and theMohs hardness is about 2–3. The mineral does not show any
discernible fluorescence under long-, or short-wave ultraviolet
radiation. Tenacity is rather brittle. Cleavage and parting were
not observed. Fracture of the aggregates is finely fibrous.
Density could not be measured directly due to the very
limited amount of type material available as well as the factthat the expected density >4.1 g/cm3. Moreover, an accurate
value of measured density cannot be expected because of theporous nature of the aggregates (see Fig. 3). Parádsasvárite
has a calculated density of 4.175 g/cm3, as determined using
the empirical chemical formula.
Optical properties could not be determined (except for pleochroism) due to the very small sizes of the crystals. The
pleochroism is very weak and is colourless to very pale green.
Mean refractive index calculated from the Gladstone-Daleequation (see Mandarino 1981) using the measured composition and the calculated density is n = 1.764.
Because of its microcrystalline habit, single-crystal X-ray
studies could not be carried out on parádsasvárite. X-ray powder diffraction data were collected using Ni-filtered CuKα
radiation and a 114.6 mm diameter Gandolfi camera.
Operating conditions were as follows: accelerating voltage
40 kV, tube current 40 mA, and exposition time 47 h.
Synthetic silicon powder (NIST SRM 640) was used as theinternal standard for film shrinkage. The Gandolfi film wasscanned using a UMAX PowerLook 3000 scanner with aresolution of 3000 dpi; it was processed by QSpectr software(Zelensky et al. 2009).
Nine quantitative point analyses were performed using a
JEOL JXA-8600 electron microprobe operated inwavelength-dispersive mode. Operating conditions were as
follows: accelerating voltage 20 kV, probe current 20 nA, a
final beam diameter of 10 μm, the peak count-times were 20 s
and the background count-times were 10 s. The standards
employed were: pure Zn (Zn), pure Cu (Cu) and PbS (Pb).
Raw intensity data were corrected using a PAP matrix correction (Pouchou and Pichoir 1984).

Parádsasvárite, a new member of the malachite-rosasite group409

Fig. 5 The IR spectrum of
parádsasvárite (* = sapphire head)An aggregate of parádsasvárite was investigated using a
Varian 2000 FTIR spectrometer with a single reflection diamond ATR accessory and an MCT detector with a 4 cm−1
resolution, and 128 scans. The IR spectrum is limited by the
cut-off point at 550 cm−1 of the broad band MCT detector. The
region 2000–2300 cm−1 cannot be evaluated due to the strong
absorption of the diamond ATR cell.

Results and discussion
X-ray crystallography
Apart from malachite (Zigan et al. 1977) and rosasite (Roberts
et al. 1986), single-crystal studies are missing for the membersof the malachite-rosasite group; this is mainly because of theirmicrocrystalline, fibrous habit. The symmetry and cell parameters of all the other members (see Table 3) were mainly deduced from powder pattern indexing (Perchiazzi 2006).
As reported by Perchiazzi (2006), two structure types canbe distinguished in the malachite-rosasite group – namely, amalachite-like and a rosasite-like structure. The difference between them was treated in detail by Perchiazzi and Merlino(2006). According to the structural investigations performedon the members of the group, only malachite belongs to themalachite-type structure. All the other members which haveso far undergone crystal structure determination (rosasite,
mcguinnessite – Perchiazzi 2006; glaukosphaerite,
pokrovskite – Perchiazzi and Merlino 2006; chukanovite –Pekov et al. 2007) have a rosasite-type structure.
Although malachite- and rosasite-type structures have very
similar X-ray powder diffraction patterns, they can be distinguished clearly (on the basis of their respective peak intensities)
in the region of 30–40° 2θ (CuKα radiation). As shown in
Fig. 4, there are two strong reflections at 31.3° (100 %,2.856 Å) and 32.2° (43 %, 2.778 Å) on the calculated patternof malachite (relative intensities and d-values are in brackets),
while on the same positions only low intensity peaks (9 and 8 %,respectively) can be found in the case of rosasite. Conversely,
the strong reflection on the rosasite pattern at 34.46° (100 %,2.600 Å) has no counterpart on the malachite pattern.
According to its X-ray powder diffraction pattern (Table 1),
parádsasvárite is structurally analogous to rosasite. Leastsquares refinement of the powder diffraction data using the
program UnitCell (Holland and Redfern 1997) and 31 indexedlines leads to a = 12.92(1), b = 9.372(7), c = 3.159(4) Å, β =110.4(1)°, V = 358.5(5) Å3, and Z = 4. Unit cell parameters
and the cell volume of parádsasvárite are very close to thatreported for rosasite by Perchiazzi (2006) (see Table 3).
The crystal structure data of rosasite determined by
Perchiazzi (2006) was used for calculating the X-ray powder
pattern of parádsasvárite, where the Me1 site is occupied by
0.63Zn + 0.36Cu + 0.01Pb and the Me2 site is occupied entirely by Zn. For the calculation the PowderCell 2.4 software(Kraus and Nolze 1996) was applied.
Chemical composition
In Table 2 the mean values and ranges of chemical analyses arelisted alongside the standard deviations. H2O and CO2 were notdetermined because of the very limited amount of type material
available. The presence of OH and CO3 groups was confirmed
by FTIR spectroscopy. H2O and CO2 contents were calculated
from the stoichiometry. Due to the lack of data concerning the
crystal structure of parádsasvárite, the cation distribution between Me1 and Me2 sites is unknown. In order to give a structural formula for parádsasvárite, a full occupancy by zinc for theMe2 position was assumed. This is because zinc tends to occupy the smaller, more regular Me2 octahedron (Perchiazzi 2006).
For the Me1 site a mixed occupancy Zn0.62Cu0.36Pb0.01 was410

Fehér B. et al.

Table 3 Members of the malachite-rosasite group. Cations dominatingin Me1 and Me2 sites are reported for each phase
Name

Me1 Me2 Space
group

Malachite

Cu

Cu

Rosasite

Cu

Zn

Parádsasvárite

Zn

Zn

Mcguinnessite

Cu

Mg

Glaukosphaerite Cu

Ni

Kolwezite

Cu

Co.

Nullaginite

Ni

Ni

Pokrovskite

Mg

Mg

Chukanovite

Fe2+ Fe2+

a

P21/a

Latticeparameters

a = 9.502
b = 11.974
c = 3.240 Å
β = 98.75°
V = 364.34 Å3
P21/a
a = 12.8976(3)b = 9.3705(1)c = 3.1623(1) Å
β = 110.262(3)°V = 358.54(2)Å3
P21/aa = 12.92(1)b = 9.372(7)c = 3.159(4) Å
β = 110.4(1)°V = 358.5(5) Å3
P21/aa = 12.9181(4)b = 9.3923(2)c = 3.1622(1) Å
β = 111.233(3)°V = 357.63(2)Å3
P21/aa = 12.0613(4)b = 9.3653(4)c = 3.1361(1) Å
β = 98.085(5)°V = a350.73 Å3
P-1 ora = 9.50
P1
b = 12.15
c = 3.189 Å
α = 93.32°
β = 90.74°
γ = 91.47°
V = a367.31 Å3
P21/m or a = 9.236(3)P21
b = 12.001(6)c = 3.091(2) Å
β = 90.48(7)°V = 342.6 Å3
P21/aa = 12.2396(4)b = 9.3506(4)c = 3.1578(1) Å
β = 96.445(5)°V = a359.12 Å3
P21/a
a = 12.396(1)b = 9.407(1)c = 3.2152(3) Å
β = 97.78(2)°V = a371.47 Å3

Reference

Zigan et al. (1977)

Perchiazzi (2006)

This work

Perchiazzi (2006)

Perchiazzi andMerlino (2006)

Deliens and Piret(1980)

Nickel and Berry(1981)

Perchiazzi andMerlino (2006)

Pekov et al. (2007)

Calculated here

assumed. A structural study of parádsasvárite should possibly
confirm this assumption. The empirical formula (based on 5 O
apfu) is (Zn0.62Cu0.36Pb0.01)Σ0.99Zn1.00(CO3)(OH)2, withrounding errors. The end-member formula is Zn2(CO3)(OH)2,
which requires ZnO 72.40, CO2 19.58 and H2O 8.02 wt.%.
Infrared spectroscopy
The IR spectrum of parádsasvárite is shown in Fig. 5. The
curve is similar to that of other members of the malachite-rosasite group reported by Frost et al. (2007a, b).
Interpretation of the bands was carried out according to
Frost et al. (2007a, b). The two bands observed at 661 and738 cm−1 were assigned to the ν4 bending modes of the CO32−
ions. A band at 792 cm−1 could possibly be assigned to the ν2
bending mode of CO32−, although its intensity is rather high.
The band at 993 cm−1 can probably be ascribed to the δOH
deformation mode. The CO32− ν1 band of rosasite group minerals should not be infrared active. However, because of symmetry reduction of the carbonate anion the band is observed at1097 cm−1. Two intense bands at 1379 and 1514 cm−1 were
attributed to ν3 antisymmetric CO32− stretching modes. The
low intensity band at 1637 cm−1 was ascribed to the water
bending mode. Its appearance suggests that water molecules
were adsorbed on the parádsasvárite surface. The presence ofmolecular water has been noted for other members of themalachite-rosasite group, i.e. for nullaginite (Nickel andBerry 1981) and for pokrovskite (Ivanov et al. 1984;
Perchiazzi and Merlino 2006). In the IR spectrum of
parádsasvárite two bands were observed at 3272 and3473 cm−1. These were ascribed to the stretching vibrationsof hydroxyl groups. The weak, but well-separated band at
3647 cm−1 could be assigned to the adsorbed H2O, weaklyhydrogen-bonded to the surface. However, it is also possiblethat this OH band is caused by a contamination of submicroscopic mica-group minerals. The very weak bands between 3000 and 2800 cm−1 are due to organic impurities arising from the uncompensated background of the instrument(also taking into account the very small amount of the sample
investigated), although the peak at around 3000 cm−1 could be
a combination band.
Libowitzky (1999) gave the correlation function of O-H
stretching frequencies versus O-H···O hydrogen bond lengths
in the form ν = 3592 – 304 × 109 × exp.[−d(O···O)/0,1321],
where ν is the stretching frequency in cm−1 and d(O···O) is the
O···O hydrogen bond length in Å. In the structure of rosasite
the two OH− groups are denoted as O4 and O5. The corresponding acceptor oxygen atoms are O3 and O1 (Perchiazzi2006). By using our determined cell parameters ofparádsasvárite and the structure model of rosasite (Perchiazzi2006), the calculated O4···O3 and O5···O1 bond lengths are
2.722 and 2.793 Å, respectively. Substituting these values into
the above equation, the obtained stretching frequencies are3250 and 3392 cm−1, respectively. These wavenumbers are
relative close to the measured ones, i.e. 3272 and 3473 cm−1(see Fig. 5).
Classification
Parádsasvárite is the zinc-dominant member of the malachiterosasite group, now including nine members (Table 3), being
no. 5.BA.10 in the Strunz classification (Strunz and Nickel2001). Although Strunz and Nickel (2001) used the nameParádsasvárite, a new member of the malachite-rosasite groupmalachite group for these minerals, here the term malachiterosasite group is preferred. This implies the existence in thegroup of two different, but closely related, malachite-like androsasite-like crystal structures. As already noticed,
parádsasvárite is defined by zinc dominancy in both the Me1
and Me2 octahedrally coordinated cation sites.
May be worth now to take into account the relationships
between rosasite, zincrosasite and parádsasvárite. On the basisof their chemical data and of the features of their powder
pattern, one can properly speak of a solid solution between
rosasite, with Cu > Zn in Me1 and Zn > Cu in Me2, andparádsasvárite, with Zn dominant in both Me1 and Me2
sites. Regarding the zincrosasite occurrences reported inliterature, both the type zincrosasite described by Strunz(1959) and the one described by Pauliš et al. (2005) can actually be referred to rosasite. The phase studied by Fehér et al.
(2008) can instead be referred to parádsasvárite.
Acknowledgments We thank Sándor Klaj (Pécs) for providing of theholotype sample and László Tóth (Velence) for the high quality photomicrograph of parádsasvárite. We also acknowledge Philip Rawlinson (Corvinus University, Budapest) for the English text revision. Finally, theauthors would like to thank the two anonymous reviewers, as well as
the Associate Editor Anton Beran for their valuable comments and suggestions to improve the manuscript.

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