Journal of Archaeological Science 40 (2013) 2128e2135

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Journal of Archaeological Science

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Focus

Characterization and source of Cucuteni black pigment (Romania):

vibrational spectrometry and XRD study
Nicolae Buzgar*, Andrei Ionut Apopei, Andrei Buzatu
Alexandru Ioan Cuza University of Iasi, Department of Geology, Archaeoinvest Platform, Bulevardul Carol I 20A, 700505 Iasi, Romania

a r t i c l e i n f o

a b s t r a c t

Article history:
Received 6 December 2011
Received in revised form
27 December 2012
Accepted 28 December 2012

A multi-technique characterization and a provenance study of the black pigment used in Cucuteni
pottery painting (Neolithic age, Romania) were carried out. 127 Cucuteni shards were analyzed by Raman
spectrometry. The main components of this pigment are pyrolusite and/or jacobsite. Hematite and quartz
are frequent minor components and Ti oxides were seldom found. The manganiferous corpuscles discovered at Neamt county (eastern part of Romania) were the raw material of the Cucuteni black pigment.
The Mn corpuscles were studied using XRD, Raman, FT-IR and Atomic Absorption Spectrometry. The
main components are birnessite, goethite and frequently, quartz. Raw material was subjected to a temperature of 750
C for 6 h and,once cooled, analyzed through Raman and FT-IR spectrometry. Pyrolusite,
hematite and quartz were found in the heated powder sample.
2013 Elsevier Ltd. All rights reserved.

Keywords:
Cucuteni culture
Black pigment source
Birnessite
Goethite
Pyrolusite
Jacobsite

1. Introduction
Around 6500 years ago, Neolithic people living in Eastern
Europe crafted beautiful monochrome and/or trichrome painted
pottery. This last great calcholithic civilization of Europe known as
the CucutenieAriusdeTripolye cultural complex spread across
350,000 km2, from the south-east of Transylvania (Romania,
CucutenieAriusd culture) to the Dnieper River (Ukraine, Tripolye
culture). Based on the painted decoration of the pottery, the
Cucuteni culture was divided into three phases: Cucuteni A (4525/
4500e4050 B.C.), AeB (4100e3800/3700 B.C.) and B (3800/3700e
3500/3350 B.C.) (Mantu, 2000; Buzgar et al., in press).
The ornamentation of the Cucuteni phase A pottery is characterized by polychrome painting, with varied spiral and meander
motifs in red or white and black borderlines covering the entire
surface of the pot, in a so-called horror vacui style (Mantu, 2000).
In the next evolutionary phase, AeB, the three colors gain equal
importance. During the nal phase of the Cucuteni culture, the
decoration of the pots becomes more sophisticated. The meander
almost disappears, while the spiraled decorative motifs are oversimplied. Zoomorphic and anthropomorphic representations
become more frequent and the three colors e red, black and

* Corresponding author. Tel./fax: 40 232201462.

E-mail address: nicolae.buzgar@uaic.ro (N. Buzgar).
0305-4403/$ e see front matter 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.jas.2012.12.034

white e have continuously changing proportions (Mantu, 2000;

Buzgar et al., in press).
A small number of studies were conducted on pigments to
discover the nature of the materials. Stos-Gale and Rook (1981) and
Niculescu et al. (1982) pointed out that jacobsite is the chromatophorous mineral of the dark brown pigments found on a number of
Cucuteni-Tripolye shards. Burghelea et al. (2003) conducted an XRD
study on polychrome ceramic shards belonging to the Cucuteni A
phase. They identied a-quartz, plagioclase feldspar, calcite, magnetite, and hausmannite in the black pigment. Through X-Ray
Fluorescence (XRF) and Synchroton Radiation X-ray Diffraction (SRXRD) measurements, Constantinescu et al. (2007) analyzed a series
of painted (redewhiteeblack) Cucuteni shards belonging to the
Cucuteni A phase. They found jacobsite (Mg-jacobsite), pyroxmangite and magnetite (quartz) in the black pigment. The XRF
measurements indicated that the main chemical elements in the
black pigment (dark brown or chocolate black) are Mn and Fe.
Using Raman spectrometry, Buzgar et al. (2010a; 2010b) analyzed
the black pigment of certain Cucuteni shards from eastern Romania.
They found pyrolusite, jacobsite, quartz and very rare anatase,
rutile and carbon.
Two hypotheses were proposed for the origin of the raw
material used for black pigment. First, based on the mineralogical
composition and the high values of the Mn/Fe ratio of the black
pigment, Constantinescu et al. (2007) suggested that raw material
used for black pigment was metamorphosed Mn ore from Iacobeni,
a settlement situated in the Suceava county, NE region of Romania.

N. Buzgar et al. / Journal of Archaeological Science 40 (2013) 2128e2135

Fig. 1. Manganiferous corpuscles collected from the Calu riverbed (right tributary of
the Bistrita river).

The second hypothesis was put forth in Buzgar et al. (2010b) and
based on the Raman, XRD and mineralogical studies on the
spherical or oblate black corpuscles discovered in a Cucuteni pot at
Fetesti e La Schit (Suceava county). It pointed out that the black
pigment consists of Mn  Fe oxihydroxides and quartz. Neither Mn
carbonates nor Mn silicates were identied. Thus it concluded that
the raw materials used for black pigment were of sedimentary
genesis and could not have originated from Iacobeni. At the time
the paper was published, the only known larger sedimentary Mn
accumulation was that of Nikopol (Ukraine) and as such it was
considered a possible source for raw material.
This paper indicates for the rst time the presence of accumulations of manganiferous corpuscles in Quaternary detrital
deposits, situated in the Neamt county (north eastern part of
Romania). These manganiferous corpuscles (Fig. 1) were initially
discovered in the riverbed of a right side tributary of the Bistrita
river (Fig. 2).

2129

Further eld investigations led to the discovery of a horizon of

Mn  Fe corpuscles in the Quaternary clastic accumulations of that
region (Fig. 3). These corpuscles were formed through metasomatism. This process affected all premetasomatic clasts in the horizon,
regardless of their petrographic nature (Fig. 4). The color of manganiferous corpuscles varies from dark brown to black, at times with
a semi-metallic gloss and black-blue iridescent aspect, depending on
the Mn/Fe ratio and petrographic nature of premetasomatic clasts.
The metasomatism of Quaternary clastic accumulations has different intensities, from forming a crust up to a total substitution of
minerals of premetasomatic clasts, with Mn  Fe oxyhydroxides,
resulting in manganiferous corpuscles (Fig. 5).
Taking into account the above, a case of desert varnish, i.e.
deposition of a thin layer with Mn  Fe oxyhydroxides on a lithic
substrate, is ruled out. We consider that the region underwent
a sudden subsidence during the Quaternary period and that, in the
resulting aquatic environment, this metasomatism of Quaternary
clasts manifested itself.
The connement of Mn  Fe corpuscles to a single horizon of the
Quaternary stack can be explained by the following sequence of
events: this Mn  Fe metasomatism was initiated in the nal phase
of subsidence, at the bottom of the basin, on the clastewater interface, and went on simultaneously with the subsequent uprising. The
duration of simultaneous processes in turn conditioned the horizon
thickness of Mn  Fe oxyhydroxides. Further investigations are
necessary in order to clarify both the genesis of these corpuscles and
the extent of that horizon, as well as to evaluate its possible economic importance. As a working hypothesis, we believe that clasts
with Fe oxyhydroxide crusts, from the top of the Mn level (Fig. 3, red
horizon (in the web version)), were the source of the red pigment.
The aim of this study is to characterize the Cucuteni black pigment and raw material, using Raman and FT-IR spectrometry,
atomic absorption spectrometry and X-ray diffractometry.
2. Materials and methods
Raman measurements were performed on 127 shards of the
Cucuteni culture from 10 archaeological sites located between the

, 1968).
Fig. 2. Plot on the geological map (Neamt county e NE of Romania) of the manganiferous corpuscles observation points (modied after Murgeanu and Mirauta

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N. Buzgar et al. / Journal of Archaeological Science 40 (2013) 2128e2135

Fig. 3. Mg  Fe horizon in Quaternary clastic accumulations.

Eastern Carpathians and the Prut river (Fig. 6). To determine the
composition of the black pigment, we have only used Raman
spectrometry for two reasons. First, Raman analysis was sufciently
relevant and second, we avoided damaging the artifacts studied.
Manganiferous corpuscles were collected from the Calu riverbed
(right tributary of the Bistrita river). They were analyzed through
Raman spectrometry, and then ground to 2e3 mm and analyzed by
XRD, FT-IR, Raman and AAS.
Raman spectra were acquired using a Horiba Jobin-Yvon RPA-HE
532 Raman Spectrometer with a multichannel air cooled (70
C)
CCD detector, using a frequency doubled NdYag laser at 532 nm and
a nominal power of 100 mW. The spectral resolution was 3 cm1
and the spectral range between 200 and 3400 cm1. The Raman
system includes a Superhead ber optic Raman probe for

non-contact measurements, with a 50X LWD Olympus visible

objective, NA 0.50, WD 10.6 mm. Sulfur and cyclohexane bands
were used for the calibration of the frequencies of the Raman
spectra. The data were acquired through 20e50 acquisitions at
a laser magnication of 70e100% and 2e10 s exposure in order to
improve the signal-to-noise ratio. Raman spectra were processed in
the LabSpec 5.25 software (removing background noise, smoothing, values of peaks).
Powder X-ray diffraction analysis was performed on a Shimadzu
X-ray diffractometer LabX XRD-6000. Measurement conditions
were: Cu anode, 40 kV, 30 mA, divergence slit 1.00
, scatter slit
1.00
, receiving slit 0.30 mm, scan range (2q) 5e80.0, scan speed
2.0
/min, sampling pitch 0.02
, preset time 2.00 s.
FT-IR spectra were collected with a Bruker Vertex 70 FTIR
spectrometer with a spectral resolution of 3 cm1 and the spectral
range of 370e7000 cm1. The measurements were taken at room
temperature, using a KBr pellet technique. The infrared spectra
were processed using the OPUS 6.5 software and for resulting
spectra, absorption spectra were plotted.
Chemical analysis was performed using an Analytik Jena vario
F6 atomic absorption spectrometer (AAS). The calibration was
performed using CertiPUR (Merck) standard solutions for the
following elements: Al, Fe, Mn, Mg, Ca, Na and K. For the partial
dissolution technique we used a mixture of nitric and hydrochloric
acid (1:3) without addition of any water. The homogenized samplereagents mixture was heated for 4 h at 100
C, cooled, diluted to
volume (500 ml) and analyzed. SiO2 was analyzed by a gravimetric
method.
3. Results and discussions
3.1. Raw material

Fig. 4. Different petrographical nature of premetasomatic clasts (1 e limestone;

2 e bituminous brown marls; 3 e sandstone).

Several corpuscles of Mn collected from the Calu afuent (right

tributary of the Bistrita river, Fig. 2, point no. 1 and 2) were analyzed
by Raman spectrometry. After Raman analysis, corpuscles were
ground to at 2e3 mm and the resulting powder sample was analyzed through several additional methods. Also, the powder was
heated to 750
C under atmospheric conditions for 6 h and after
cooling, analyzed by Raman and FT-IR spectrometry.

N. Buzgar et al. / Journal of Archaeological Science 40 (2013) 2128e2135

2131

Fig. 5. Different phases of metasomatism (1 e crust; 2 e clast is almost substituted by Mn minerals; 3 e clast is completely substituted by Mn minerals).

There are two different Raman spectra recorded from Mn corpuscles, as shown in Fig. 8(A). The main component is birnessite,
with characteristic Raman lines at 485, 506, 555, 575, 646e641 and
696 cm1, in good agreement with Julien et al. (2003). The second
mineral present in the raw material is goethite, with the main
Raman band at 566 cm1. The Raman line which occurs at 646 cm1
in sample 2, is an overlap of Raman lines for birnessite and goethite.
Quartz was identied in one of the analyzed points of sample 2,
which indicates that the premetasomatic clast was a sandstone
clast. Quartz is a very stable mineral under hypergene conditions,
preserving itself in Mn corpuscles more than other minerals (e.g.
feldspar, mica, calcite, clay minerals) from premetasomatic clasts.
The K, Na and Ca cations from these minerals were either leached or
caught in the lattice of birnessite. In our samples, the main Raman
line of birnessite appears shifted between 641 and 646 cm1, which
indicates the presence of large cations in its structure, such as Na
and K, in agreement with Julien et al. (2003). These cations are
primarily derived from feldspar, a common mineral component of
sandstone clasts.
Chemical analysis of sample performed by AAS, showed that the
raw material consists mainly of Mn and Fe oxyhydroxides (Table 1)
and the Mn/Fe ratio is 7.31. This value is much higher than the value
for Mn ore from Iacobeni (which is less than 1) or from Nikopol
(approximately 1), both of which were outlined by Constantinescu

et al. (2007). Likewise, the high content of SiO2 and low content of
Al2O3 indicate the presence of quartz in the sample.
XRD study on the same powder revealed the presence of birnessite, goethite and quartz (Fig. 7). The interlayer distances di were
attributed to the aforementioned minerals in agreement with
Julien et al. (2003), Gualtieri and Venturelli (1999), Levien et al.
(1980), Lopano et al. (2009) and JCPDS standards.
Raman analysis of the sample after heating to 750
C reveals the
presence of anhydrous minerals, as expected. Pyrolusite and
hematite occur instead of birnessite and goethite (Fig. 8, B). The
presence of pyrolusite is marked by the Raman lines at 288, 358sh,
478, 527, 644vs and 869sh cm1 (sh e shoulder; vs e very strong),
in good agreement with Buzgar et al. (2009).
According to several authors (e.g. Downs, 2006; Buzgar et al.,
2009), hematite shows Raman lines around 222, 242, 292vs, 408,
499, 611, 658, 814 and 1063 cm1. Other than the 408 cm1 Raman
line, all the other Raman lines assigned to hematite are overlapped
with Raman lines of pyrolusite. The same situation occurs in the
case of quartz.
The IR spectra of raw material before and after heating to 750
C
are shown in Fig. 9 in the spectral region 370e2000 cm1. Analogous to the Raman discussion, the heat treatment of raw material
leads to a transformation of Mn and Fe minerals. The infrared
analysis corroborates with ndings of XRD and Raman analysis and

Fig. 6. The archaeological site map; the black square is the area were the manganiferous corpuscles are found.

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N. Buzgar et al. / Journal of Archaeological Science 40 (2013) 2128e2135

Fig. 7. X-ray powder diffraction diagram of raw material; Bir e birnessite, Gth e goethite, Q e quartz.

gives further information about the transformations which occur

when the pottery is heated to 750
C.
The infrared spectrum of the unheated sample shows the
common characteristics of birnessite with the absorption peaks at
465, 515 and 729sh cm1, which are in good agreement with literature data (Kang et al., 2007; Krishnamurti and Huang, 1987).
The presence of quartz is indicated in the spectral region 900e
1200 cm1 by three absorption lines at 1040, 1083 and 1165 cm1,
in agreement with Downs (2006). The presence of quartz is also
conrmed by the doublet 779 cm1 and 798 cm1.
As expected, the presence of goethite is clearly shown by absorption lines at 396, 581, 648 cm1 and the overlapped lines at 465
and 798 cm1. The absorption peak at 396 cm1 can be assigned to
n(FeeO) and the 465 cm1 peak to the same FeeO vibration, due to
the aluminum incorporated in the goethite structure (Mendelovici
et al., 1979). Also, the absorption lines of quartz are found to be
overlapped with those of birnessite and goethite at 465, 515 and
798 cm1.
In the infrared spectrum of the unheated sample, the presence
of amorphous oxide of Mn is highlighted by two absorption lines
which arise at 1400 and 695 cm1, but the latter band is an overlap

of quartz. In the case of the heated sample, the IR spectrum only

shows the 695sh cm1 band overlapped with that of quartz and
the 1400 cm1 absorption band is absent because the amorphous
state disappears when heating to 750
C (Krishnamurti and
Huang, 1987).
The infrared spectrum of the heated sample clearly reveals the
presence of pyrolusite with absorption peaks at 465sh, 522, 609
and 1083 cm1, which are in good agreement with data from literature (Downs, 2006; Buciuman et al., 1999; Eldereld and Glasby,
1973). In addition to the quartz absorption bands, two overlapped
peaks of hematite at 522 and 438sh cm1 appear.
The disappearance of water molecules from the heated sample
causes the disappearance of 1623 cm1 absorption peak. Although
the spectrum of the heated sample shows a very weak peak around
1620 cm1, this is due to the water absorbed in the pellet sample,
because KBr is hygroscopic (Potter and Rossman, 1979).
A comparison of both infrared spectra (unheated and heated
samples) in the spectral region 450e650 cm1 shows a wavenumber shifting to higher values, due to the transformation of
birnessite into pyrolusite, as Renuka and Ramamurthy (2000) also
found. In addition, heating to higher temperatures than 750
C

Fig. 8. Raman spectra of raw material; A e manganiferous corpuscles; B e powder sample, after heating in atmospheric conditions for 6 h, to 750
C; Q, Py and Hem are standards
for quartz, pyrolusite and hematite, after Buzgar et al. (2009).

N. Buzgar et al. / Journal of Archaeological Science 40 (2013) 2128e2135

Fe32O3 hematite

Table 1
Chemical composition (AAS) of raw material (wt%).
Sample

SiO2

Al2O3

Fe2O3a

MnO

MgO

CaO

Na2O

K2O

22.36

1.95

7.48

54.67

0.32

0.83

1.17

0.87

2133

(2)

M2M32O4:

Fe2O3 as Fe total.

causes pyrolusite to turn into hausmannite (Buciuman et al., 1999).

This transformation is explained in the next section.

M2 Mn, M3 Mn / MnMn2O4 hausmannite

(3)

M2 Fe, M3 Fe / FeFe2O4 magnetite

(4)

M2 Mn, Fe, Mg, M3 Mn, Fe / (Mn,Fe,Mg) (Fe,Mn)2O4

jacobsite

(5)

3.2. Black pigment

Cation-exchange reactions may occur in the reticular structure
of minerals during the heating of the black pigment. Because Mn4
is reduced to Mn3 at temperatures of about 550e600
C (Tinsley
and Sharp, 1971), and Mn3 can be substituted by Fe3, pyrolusite
may contain Fe3. In this case, the main Raman band is shifted to
lower wavenumbers (626 cm1). A higher ring temperature of
pottery can determine the transformation Mn3 / Mn2 (Tinsley
and Sharp, 1971) and the appearance of hausmannite molecules
(3Mn4Mn4O2 / 2Mn2Mn32 O3). In this case the main Raman
band of pyrolusite is shifted to the highest wavenumbers (for
hausmannite, about 665 cm1). The same phenomenon can be
induced by the high laser power (Goodall et al., 2007).
The presence of jacobsite requires ring temperatures above
600
C and also the presence of organic matter in raw material
(necessary to reduce Fe3 from goethite to Fe2 in jacobsite). Part of
Fe2 from jacobsite can be substituted by Mg, forming Mg-jacobsite
((Mn,Mg,Fe) (Fe,Mn)2O4), and thus the main Raman band is shifted
to 600 cm1.
If the Fe2 content of jacobsite increase, the main Raman line of
this mineral shifts to that of magnetite, as these two minerals are
isostructural; the values increase to 626 cm1, as follows:

As shown by several authors (Stos-Gale and Rook, 1981;

Niculescu et al., 1982; Constantinescu et al., 2007; Buzgar et al.,
2010a, 2010b), the main components identied by XRD, SR-XRD
and Raman spectrometry in the Cucuteni black pigment are
MneFe oxides (pyrolusite, haussmanite, jacobsite, magnetite) and
quartz.
127 samples of Cucuteni shards were studied through Raman
spectrometry. Raman spectra of these samples are found on the
website project http://rdrs.uaic.ro. The main minerals identied are
pyrolusite, jacobsite, hematite and quartz (Fig. 10A). The most
intense Raman lines of pyrolusite and jacobsite (601e626 cm1,
respectively 626e645 cm1) are shifted to right or to the left
depending on the chemical composition of raw material, the
combustion temperature of the pottery and the laser power at
which the sample was analyzed. To understand this shift, we present some crystallochemical data of Mn and Fe oxides. The following ve minerals can occur in the composition of the Cucuteni
black pigment:

beMn4O2 pyrolusite

(1)

Mg - jacobsite

jacobsite

600

Fe jacobsite

(Mn2+,Mg2+,Fe2+)(Fe3+,Mn3+)2O4
620

Fig. 9. FT-IR spectra of raw material, at 25
C and after heating in atmospheric conditions for 6 h at 750
C.

magnetite
Fe2+Fe3+2O4

626

~670 cm-1 (Buzgar et al., 2009)

At ring temperatures around 900
C, most of Mn3 is reduced

to Mn2, which determines transformation of pyrolusite and
jacobsite into hausmannite, respectively magnetite. All of above
mentioned transformations are conditioned by the Mn/Fe/Mg ratio
of raw materials and the ring temperatures of pottery. For this
reason, the different data presented by different authors regarding
the main minerals of the Cucuteni black pigment are not in contradiction but complement one another.
Therefore, taking into account that ring temperatures of pottery were between 700 and 800
C and rarely higher, pyrolusite and
jacobsite are the most common. Haussmanite and magnetite can be
found occasionally.
The presence of Mg-jacobsite is conditioned by a raw material
richer in Mg. Hematite is stable in all ranges of ring temperatures.
The presence of hematite in the black pigment is conditioned by the
Mn/Fe ratio and mineralogical composition of the used raw materials. The other polymorphic members of MnO2 have not been
taken into account because they convert to pyrolusite at about
510
C.
The presence of pyrolusite is marked by the Raman lines at 288,
359, 479 and 581 cm1 (Fig. 10A). The Raman lines 288 (overlapped) and 457 cm1 are assigned to jacobsite. In some Cucuteni
shard spectra (e.g. Mihoveni, Fig. 10), a well-dened Raman peak is
exhibited at 457 cm1, which is assigned to quartz. In the case of
hematite, the Raman bands are overlapped by the Raman bands of

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N. Buzgar et al. / Journal of Archaeological Science 40 (2013) 2128e2135

Fig. 10. Typical Raman spectra of the Cucuteni black pigment. Samples names represent the name of places where archeological sites are situated (see Fig. 6).

pyrolusite and/or jacobsite, with exception of 243 and 412 cm1. In

many spectra, pyrolusite and jacobsite appear together, but each
has a clearly distinguishable Raman line (e.g. Mihoveni, Fig. 10A).
Carbon appears in some spectra of the Cucuteni shards as an
extremely wide massive of Raman diffusion between circa
1200 cm1 and 1600 cm1, with stronger intensities close to the
positions of the CeC sp3 and sp2 type vibrations around 1375 cm1
and 1595 cm1 (Fig. 10B). The origin of carbon is most probably
related to the lithologic nature of clasts (e.g. bituminous brown
marls) affected by metasomatism. At lower ring temperatures,
below circa 750
C, bitumen turns into carbon. At higher temperatures, carbon burns and turns into CO2. The fact that carbon was
rarely identied in the Cucuteni black pigment is due to two reasons. Firstly, raw material containing bitumen is less wide spread.
Secondly, higher ring temperatures of pottery, in excess of circa
750
C, were used.
Rutile and anatase were occasionally found in Cucuteni black
pigment. The Raman lines at 626, 519 and 392 cm1 have been
attributed to rutile and the Raman bands at 607, 427 and 273 cm1
have been assigned to anatase (Fig. 10B).

Supplementary data related to this article can be found at http://

dx.doi.org/10.1016/j.jas.2012.12.034.

4. Conclusions

References

The main component of the black pigment from Cucuteni

ceramics is pyrolusite. It is often associated with hematite and
quartz, the latter of which is a relict mineral of the raw material.
Depending on the chemistry and mineralogical composition of raw
material, the pigment can contain jacobsite or Mg-jacobsite, especially in the dark brown pigment. At a higher ring temperature of
pottery (about 900
C), pyrolusite and jacobsite turns into hausmannite, respectively magnetite. Ti oxides may occur occasionally.
The raw material is represented by manganiferous corpuscles
from the Neamt county, NE part of Romania. They were formed by
metasomatism of clasts from Quaternary detrital deposits. The
main components of manganiferous corpuscles are birnessite and
goethite. Depending on the petrographic nature of premetasomatic
clasts, the raw material also contains relict minerals. The most
common is quartz from sandstone clasts. Clay minerals can also
be present as relict minerals (e.g. with marls as premetasomatic
clasts).

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By ring, birnessite turns into pyrolusite and goethite into

hematite. Quartz is preserved as a relict mineral. The formation of
jacobsite and Mg-jacobsite depends on the presence of organic
matter (the source of which could be bituminous brown marls) in
raw material and on a high content of Fe, respectively Mg in the raw
material.
Acknowledgments
The present work was supported by CNCSIS eUEFISCSU,
Romania, project number PNII e IDEI, code 2119/2009.
The authors would like to thank the anonymous reviewer for
valuable comments and suggestions to improve the quality of
the paper.
Appendix A. Supplementary data

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