You are on page 1of 8

Journal of Archaeological Science 40 (2013) 2128e2135

Contents lists available at SciVerse ScienceDirect

Journal of Archaeological Science
journal homepage: http://www.elsevier.com/locate/jas

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 Ias¸i, Department of Geology, Archaeoinvest Platform, Bulevardul Carol I 20A, 700505 Ias¸i, 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.
Ó 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 CucutenieArius¸deTripolye cultural complex spread across
350,000 km2, from the south-east of Transylvania (Romania,
CucutenieArius¸d 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 final phase of the Cucuteni culture, the
decoration of the pots becomes more sophisticated. The meander
almost disappears, while the spiraled decorative motifs are oversimplified. Zoomorphic and anthropomorphic representations
become more frequent and the three colors e red, black and

* Corresponding author. Tel./fax: þ40 232201462.
E-mail address: nicolae.buzgar@uaic.ro (N. Buzgar).
0305-4403/$ e see front matter Ó 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 identified 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 (þquartz) 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.

Neither Mn carbonates nor Mn silicates were identified. 2. We consider that the region underwent a sudden subsidence during the Quaternary period and that. Buzgar et al. Materials and methods Raman measurements were performed on 127 shards of the Cucuteni culture from 10 archaeological sites located between the . Thus it concluded that the raw materials used for black pigment were of sedimentary genesis and could not have originated from Iacobeni. using Raman and FT-IR spectrometry. At the time the paper was published. 1. Further investigations are necessary in order to clarify both the genesis of these corpuscles and the extent of that horizon. situated in the Neamt¸ county (north eastern part of Romania). regardless of their petrographic nature (Fig. this metasomatism of Quaternary clasts manifested itself. The second hypothesis was put forth in Buzgar et al. the only known larger sedimentary Mn accumulation was that of Nikopol (Ukraine) and as such it was considered a possible source for raw material. It pointed out that the black pigment consists of Mn  Fe oxihydroxides and quartz. Plot on the geological map (Neamt¸ county e NE of Romania) of the manganiferous corpuscles observation points (modified after Murgeanu and Miraut¸a . The aim of this study is to characterize the Cucuteni black pigment and raw material. resulting in manganiferous corpuscles (Fig. red horizon (in the web version)). XRD and mineralogical studies on the spherical or oblate black corpuscles discovered in a Cucuteni pot at Fetes¸ti e La Schit (Suceava county). 5). 2129 Further field investigations led to the discovery of a horizon of Mn  Fe corpuscles in the Quaternary clastic accumulations of that region (Fig. The metasomatism of Quaternary clastic accumulations has different intensities. with Mn  Fe oxyhydroxides. atomic absorption spectrometry and X-ray diffractometry. i. Taking into account the above. from the top of the Mn level (Fig. 4). These corpuscles were formed through metasomatism. 3. a case of desert varnish. we believe that clasts with Fe oxyhydroxide crusts. The duration of simultaneous processes in turn conditioned the horizon thickness of Mn  Fe oxyhydroxides.e. / Journal of Archaeological Science 40 (2013) 2128e2135 Fig. at times with a semi-metallic gloss and black-blue iridescent aspect. as well as to evaluate its possible economic importance. Manganiferous corpuscles collected from the Calu riverbed (right tributary of the Bistrit¸a river). and went on simultaneously with the subsequent uprising. on the clastewater interface.N. 1) were initially discovered in the riverbed of a right side tributary of the Bistrit¸a river (Fig. in the resulting aquatic environment. is ruled out. This paper indicates for the first time the presence of accumulations of manganiferous corpuscles in Quaternary detrital deposits. 2. at the bottom of the basin. depending on the Mn/Fe ratio and petrographic nature of premetasomatic clasts. 3). The confinement 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 final phase of subsidence. As a working hypothesis. These manganiferous corpuscles (Fig. were the source of the red pigment. 1968). This process affected all premetasomatic clasts in the horizon. Fig. deposition of a thin layer with Mn  Fe oxyhydroxides on a lithic substrate. 2). from forming a crust up to a total substitution of minerals of premetasomatic clasts. The color of manganiferous corpuscles varies from dark brown to black. (2010b) and based on the Raman.

Sulfur and cyclohexane bands were used for the calibration of the frequencies of the Raman spectra. Raw material Fig. diluted to volume (500 ml) and analyzed. Raman spectra were acquired using a Horiba Jobin-Yvon RPA-HE 532 Raman Spectrometer with a multichannel air cooled (70  C) CCD detector. analyzed by Raman and FT-IR spectrometry. The spectral resolution was 3 cm1 and the spectral range between 200 and 3400 cm1. 3. 3. First.02 . Also. The calibration was performed using CertiPUR (Merck) standard solutions for the following elements: Al. Buzgar et al. Fe. Several corpuscles of Mn collected from the Calu affluent (right tributary of the Bistrita river. Mg  Fe horizon in Quaternary clastic accumulations. absorption spectra were plotted. 2. Raman and AAS. Different petrographical nature of premetasomatic clasts (1 e limestone. 3 e sandstone). The Raman system includes a “Superhead” fiber optic Raman probe for non-contact measurements. 30 mA.2130 N. using a KBr pellet technique. cooled. The homogenized samplereagents mixture was heated for 4 h at 100  C.1. 6). After Raman analysis. Eastern Carpathians and the Prut river (Fig.0 /min. The infrared spectra were processed using the OPUS 6. Results and discussions 3. Mn. The measurements were taken at room temperature. preset time 2.00 s. To determine the composition of the black pigment. 2 e bituminous brown marls. Ca. FT-IR. corpuscles were ground to at 2e3 mm and the resulting powder sample was analyzed through several additional methods. scan speed 2. Na and K. WD ¼ 10.30 mm. we have only used Raman spectrometry for two reasons. SiO2 was analyzed by a gravimetric method. 4. scatter slit 1.00 . Fig.5 software and for resulting spectra. Raman spectra were processed in the LabSpec 5. NA ¼ 0. Powder X-ray diffraction analysis was performed on a Shimadzu X-ray diffractometer LabX XRD-6000. receiving slit 0. scan range (2q) 5e80. with a 50X LWD Olympus visible objective. and then ground to 2e3 mm and analyzed by XRD. Mg. values of peaks). divergence slit 1. Manganiferous corpuscles were collected from the Calu riverbed (right tributary of the Bistrit¸a river).0. Chemical analysis was performed using an Analytik Jena vario F6 atomic absorption spectrometer (AAS). Measurement conditions were: Cu anode. we avoided damaging the artifacts studied. sampling pitch 0. For the partial dissolution technique we used a mixture of nitric and hydrochloric acid (1:3) without addition of any water. .50.6 mm. the powder was heated to 750  C under atmospheric conditions for 6 h and after cooling.00 . Raman analysis was sufficiently relevant and second. using a frequency doubled NdYag laser at 532 nm and a nominal power of 100 mW. point no.25 software (removing background noise. They were analyzed through Raman spectrometry. 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. smoothing. 1 and 2) were analyzed by Raman spectrometry. / Journal of Archaeological Science 40 (2013) 2128e2135 Fig. The data were acquired through 20e50 acquisitions at a laser magnification of 70e100% and 2e10 s exposure in order to improve the signal-to-noise ratio. 40 kV.

646e641 and 696 cm1.g. Downs. showed that the raw material consists mainly of Mn and Fe oxyhydroxides (Table 1) and the Mn/Fe ratio is 7.. 506.31.g. is an overlap of Raman lines for birnessite and goethite. 2006. in agreement with Julien et al. the heat treatment of raw material leads to a transformation of Mn and Fe minerals. mica. 6. Lopano et al. (1980). the black square is the area were the manganiferous corpuscles are found. 814 and 1063 cm1. 8. (2003). 478. as shown in Fig. The presence of pyrolusite is marked by the Raman lines at 288. Pyrolusite and hematite occur instead of birnessite and goethite (Fig. 242. B). In our samples. both of which were outlined by Constantinescu et al. These cations are primarily derived from feldspar. Likewise. with the main Raman band at 566 cm1. Other than the 408 cm1 Raman line. calcite. 7). (2003). 527. Gualtieri and Venturelli (1999). There are two different Raman spectra recorded from Mn corpuscles. 658. Different phases of metasomatism (1 e crust. clay minerals) from premetasomatic clasts. as expected. The archaeological site map. feldspar. 3 e clast is completely substituted by Mn minerals). . Na and Ca cations from these minerals were either leached or caught in the lattice of birnessite. vs e very strong). The same situation occurs in the case of quartz. 9 in the spectral region 370e2000 cm1. all the other Raman lines assigned to hematite are overlapped with Raman lines of pyrolusite. with characteristic Raman lines at 485. 611. goethite and quartz (Fig. The second mineral present in the raw material is goethite. Buzgar et al. The K. This value is much higher than the value for Mn ore from Iacobeni (which is less than 1) or from Nikopol (approximately 1). 575. 555. Levien et al. (2009). which indicates that the premetasomatic clast was a sandstone clast. (2007). 2009). 644vs and 869sh cm1 (sh e shoulder. Raman analysis of the sample after heating to 750  C reveals the presence of anhydrous minerals. a common mineral component of sandstone clasts. The infrared analysis corroborates with findings of XRD and Raman analysis and Fig. The interlayer distances di were attributed to the aforementioned minerals in agreement with Julien et al. Quartz is a very stable mineral under hypergene conditions. 408. The main component is birnessite. Buzgar et al. preserving itself in Mn corpuscles more than other minerals (e. Chemical analysis of sample performed by AAS. 358sh. the main Raman line of birnessite appears shifted between 641 and 646 cm1. / Journal of Archaeological Science 40 (2013) 2128e2135 2131 Fig.N. The Raman line which occurs at 646 cm1 in sample 2. (2003). hematite shows Raman lines around 222. 8(A). Analogous to the Raman discussion. The IR spectra of raw material before and after heating to 750  C are shown in Fig. the high content of SiO2 and low content of Al2O3 indicate the presence of quartz in the sample. such as Na and K. in good agreement with Buzgar et al. which indicates the presence of large cations in its structure. (2009) and JCPDS standards. 499. XRD study on the same powder revealed the presence of birnessite. 5. in good agreement with Julien et al. 2 e clast is almost substituted by Mn minerals. Quartz was identified in one of the analyzed points of sample 2. According to several authors (e. 292vs.

1083 and 1165 cm1. which are in good agreement with data from literature (Downs. Py and Hem are standards for quartz. but the latter band is an overlap of quartz. In the case of the heated sample. 7. In addition to the quartz absorption bands. 2006. gives further information about the transformations which occur when the pottery is heated to 750  C. the absorption lines of quartz are found to be overlapped with those of birnessite and goethite at 465. Krishnamurti and Huang. in agreement with Downs (2006). 648 cm1 and the overlapped lines at 465 and 798 cm1. 609 and 1083 cm1. 1973). In the infrared spectrum of the unheated sample.. Buciuman et al. In addition. 581. The presence of quartz is also confirmed by the doublet 779 cm1 and 798 cm1. to 750  C. A e manganiferous corpuscles. The absorption peak at 396 cm1 can be assigned to n(FeeO) and the 465 cm1 peak to the same FeeO vibration. heating to higher temperatures than 750  C Fig. 515 and 729sh cm1. As expected. two overlapped peaks of hematite at 522 and 438sh cm1 appear. B e powder sample. .. because KBr is hygroscopic (Potter and Rossman. due to the aluminum incorporated in the goethite structure (Mendelovici et al. 8. / Journal of Archaeological Science 40 (2013) 2128e2135 Fig. the presence of amorphous oxide of Mn is highlighted by two absorption lines which arise at 1400 and 695 cm1. 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. A comparison of both infrared spectra (unheated and heated samples) in the spectral region 450e650 cm1 shows a wavenumber shifting to higher values. which are in good agreement with literature data (Kang et al. after heating in atmospheric conditions for 6 h. 1999. The presence of quartz is indicated in the spectral region 900e 1200 cm1 by three absorption lines at 1040. The infrared spectrum of the unheated sample shows the common characteristics of birnessite with the absorption peaks at 465. 1987). Elderfield and Glasby. Q e quartz. 1987). after Buzgar et al. Q. 1979).2132 N. The infrared spectrum of the heated sample clearly reveals the presence of pyrolusite with absorption peaks at 465sh. Gth e goethite. (2009). 2007. 515 and 798 cm1. Bir e birnessite. due to the transformation of birnessite into pyrolusite. Although the spectrum of the heated sample shows a very weak peak around 1620 cm1. the presence of goethite is clearly shown by absorption lines at 396. The disappearance of water molecules from the heated sample causes the disappearance of 1623 cm1 absorption peak. 522. Also. X-ray powder diffraction diagram of raw material. as Renuka and Ramamurthy (2000) also found. pyrolusite and hematite. Buzgar et al. Raman spectra of raw material. 1979).. this is due to the water absorbed in the pellet sample.

1999). 127 samples of Cucuteni shards were studied through Raman spectrometry. 2007. M3þ ¼ Mn... a well-defined Raman peak is exhibited at 457 cm1. The presence of hematite in the black pigment is conditioned by the Mn/Fe ratio and mineralogical composition of the used raw materials.Mn3+)2O4 620 Fig. 1971) and the appearance of hausmannite molecules (3Mn4þMn4þO2 / 2Mn2þMn3þ2 O3). Hematite is stable in all ranges of firing temperatures. 359. Fig. and Mn3þ can be substituted by Fe3þ...Mn)2O4). magnetite) and quartz.Mg.32 0. the main Raman band is shifted to lower wavenumbers (626 cm1). respectively 626e645 cm1) are shifted to right or to the left depending on the chemical composition of raw material. the Raman bands are overlapped by the Raman bands of . 10). In this case.N. The presence of pyrolusite is marked by the Raman lines at 288. taking into account that firing temperatures of pottery were between 700 and 800  C and rarely higher. which is assigned to quartz.48 54. pyrolusite may contain Fe3þ. Mihoveni. magnetite Fe2+Fe3+2O4 626 ~670 cm-1 (Buzgar et al. The presence of Mg-jacobsite is conditioned by a raw material richer in Mg. jacobsite. Sample SiO2 Al2O3 Fe2O3a MnO MgO CaO Na2O K2O 1 22.uaic. 9. The Raman lines 288 (overlapped) and 457 cm1 are assigned to jacobsite. For this reason. most of Mn3þ is reduced to Mn2þ.Fe) (Fe. forming Mg-jacobsite ((Mn. respectively magnetite. Mg. causes pyrolusite to turn into hausmannite (Buciuman et al. FT-IR spectra of raw material.2. which determines transformation of pyrolusite and jacobsite into hausmannite. the main components identified by XRD.Fe2+)(Fe3+. Black pigment Cation-exchange reactions may occur in the reticular structure of minerals during the heating of the black pigment. 2009) At firing temperatures around 900  C.. All of above mentioned transformations are conditioned by the Mn/Fe/Mg ratio of raw materials and the firing temperatures of pottery.Mg2+. 1982. the values increase to 626 cm1.jacobsite jacobsite 600 Fe – jacobsite → (Mn2+. the main Raman line of this mineral shifts to that of magnetite. Haussmanite and magnetite can be found occasionally. and thus the main Raman band is shifted to 600 cm1.Mn)2O4 jacobsite (5) 3. The most intense Raman lines of pyrolusite and jacobsite (601e626 cm1. / Journal of Archaeological Science 40 (2013) 2128e2135 Fe3þ2O3 hematite Table 1 Chemical composition (AAS) of raw material (wt%). 1981. Because Mn4þ is reduced to Mn3þ at temperatures of about 550e600  C (Tinsley and Sharp. Buzgar et al. hematite and quartz (Fig. 2007). This transformation is explained in the next section. at 25  C and after heating in atmospheric conditions for 6 h at 750  C. M3þ ¼ Fe / FeFe2O4 magnetite (4) M2þ ¼ Mn. The following five minerals can occur in the composition of the Cucuteni black pigment: beMn4þO2 pyrolusite (1) Mg . Raman spectra of these samples are found on the website project http://rdrs. Niculescu et al. 10A).17 0.87 a 2133 (2) M2þM3þ2O4: Fe2O3 as Fe total. In some Cucuteni shard spectra (e. Therefore. The presence of jacobsite requires firing temperatures above 600  C and also the presence of organic matter in raw material (necessary to reduce Fe3þ from goethite to Fe2þ in jacobsite).Fe. haussmanite. A higher firing temperature of pottery can determine the transformation Mn3þ / Mn2þ (Tinsley and Sharp. In the case of hematite. The main minerals identified are pyrolusite..Mg) (Fe. M2þ ¼ Mn. jacobsite.67 0. 10A). pyrolusite and jacobsite are the most common. as follows: As shown by several authors (Stos-Gale and Rook. as these two minerals are isostructural. SR-XRD and Raman spectrometry in the Cucuteni black pigment are MneFe oxides (pyrolusite.ro. 479 and 581 cm1 (Fig.36 1. 1971). the combustion temperature of the pottery and the laser power at which the sample was analyzed. Constantinescu et al. Buzgar et al.83 1. Fe.g. we present some crystallochemical data of Mn and Fe oxides. The other polymorphic members of MnO2 have not been taken into account because they convert to pyrolusite at about 510  C. To understand this shift. Fe / (Mn. In this case the main Raman band of pyrolusite is shifted to the highest wavenumbers (for hausmannite. The same phenomenon can be induced by the high laser power (Goodall et al. about 665 cm1). Part of Fe2þ from jacobsite can be substituted by Mg.95 7. If the Fe2þ content of jacobsite increase. the different data presented by different authors regarding the main minerals of the Cucuteni black pigment are not in contradiction but complement one another. 2010b). M3þ ¼ Mn / MnMn2O4 hausmannite (3) M2þ ¼ Fe. 2010a.

. Zahn... higher firing temperatures of pottery. Rutile and anatase were occasionally found in Cucuteni black pigment. N. At lower firing temperatures. Popescu.T. At higher temperatures. 2003. Popovici. Depending on the petrographic nature of premetasomatic clasts. G.I.. with exception of 243 and 412 cm1. Bodi. The origin of carbon is most probably related to the lithologic nature of clasts (e. V. Eastern and Central European Studies Series. 2006. At a higher firing temperature of pottery (about 900  C). N.. 10B). Samples’ names represent the name of places where archeological sites are situated (see Fig. Ti oxides may occur occasionally. 10A).I.. pyrolusite and jacobsite appear together. but each has a clearly distinguishable Raman line (e.1016/j. Cuza” Din Iasi e Geologie 56. in press. I.g. I. 2010b.I. pyrolusite and/or jacobsite. A. 251e258. Vlaicu.. M. A. N. Supplementary data related to this article can be found at http:// dx. the latter of which is a relict mineral of the raw material.T.. bitumen turns into carbon. As¸tefanei. Buzatu. A. below circa 750  C. with marls as premetasomatic clasts). 281e288. raw material containing bitumen is less wide spread. The Raman Study of the White Pigment Used in Cucuteni Pottery. A. Quartz is preserved as a relict mineral. Buzgar. Clay minerals can also be present as relict minerals (e. Vibrational spectroscopy of bulk and supported manganese oxides. Buzgar. pyrolusite and jacobsite turns into hausmannite... The RRUFF Project: an Integrated Study of the Chemistry. code 2119/2009. It is often associated with hematite and quartz. A. Romania..org/10. carbon burns and turns into CO2. 10B). Analele Stiintifice Ale Universitatii “Al.. Apopei.doi. The main components of manganiferous corpuscles are birnessite and goethite.. 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. Peter Lang Publishing Group.. the raw material also contains relict minerals. The Raman lines at 626. in excess of circa 750  C. respectively Mg in the raw material. Documenta Prehistorica 34. http://rdrs. 4. R. project number PNII e IDEI. Buzgar.I. As¸tefanei. Downs.. Raman and XRD studies of black pigment from Cucuteni ceramics. Buzatu. Program and By firing. Appendix A. Firstly. 10. A. Depending on the chemistry and mineralogical composition of raw material.jas. with stronger intensities close to the positions of the CeC sp3 and sp2 type vibrations around 1375 cm1 and 1595 cm1 (Fig.12. Physical Chemistry Chemical Physics 1. The authors would like to thank the anonymous reviewer for valuable comments and suggestions to improve the quality of the paper. / Journal of Archaeological Science 40 (2013) 2128e2135 Fig. Analele Stiintifice Ale Universitatii “Al. Apopei.uaic. The Raman study of white.. The raw material is represented by manganiferous corpuscles from the Neamt¸ county. D. 427 and 273 cm1 have been assigned to anatase (Fig. Acknowledgments The present work was supported by CNCSIS eUEFISCSU.g. Bodi. G.M. Burghelea..I. birnessite turns into pyrolusite and goethite into hematite.. Raman and Infrared Spectroscopy of Minerals. Typical Raman spectra of the Cucuteni black pigment. 5e14. Dumitras¸cu. 6)..R. D. B. Buzgar et al. Apopei.. Phase and chemical composition analysis of pigments used in Cucuteni Neolithic painted ceramics. Buzgar. Cuza” Din Iasi e Geologie 56. Constantinescu.ro. A. N.2012.  Chromatic characterisation of Cucuteni ceramics e Scânteia A2. The most common is quartz from sandstone clasts. red and black pigments used in Cucuteni neolithic painted ceramics. 2009. Melinescu. Carbon appears in some spectra of the Cucuteni shards as an extremely wide “massive” of Raman diffusion between circa 1200 cm1 and 1600 cm1. They were formed by metasomatism of clasts from Quaternary detrital deposits.. were used... R. bituminous brown marls) affected by metasomatism. Craciun. Mihoveni..034. I. Patcas.. D. Conclusions References The main component of the black pigment from Cucuteni ceramics is pyrolusite.g.. Buciuman. especially in the dark brown pigment. Supplementary data . G. Fig. The fact that carbon was rarely identified in the Cucuteni black pigment is due to two reasons. E. Revista Româna de Materiale 33. Romanian Database of Raman Spectra. A. G. F. Bugoi. 1999. Buzatu. IV. D. Crystallography. the pigment can contain jacobsite or Mg-jacobsite.. 2010a. respectively magnetite. NE part of Romania. R. Buzatu. Secondly. Bodi. F.I. 2007.I..2134 N. Pantos.. In many spectra. 519 and 392 cm1 have been attributed to rutile and the Raman bands at 607. 185e190. vol.

A. Structure and elastic properties of quartz at pressure. 864e869. 2000. M.. L. and structural relationships by infrared spectroscopy. 666e673. The catalytic role of birnessite in the transformation of iron... G..M. In situ study of the goethiteehematite phase transformation by real time synchrotron powder diffraction. 895e904.M.. D. R. G. Lopano. Ukraine. 155e161.R. Occasional Paper 19. 117e122.P. J. Analysis of pigments used for decorations of Neolithic pottery from Bilcze Zlote. 2009.. Massot. G. Fredericks.. Geological Map. S. Spectrochimica Acta A 67.000 Scale... ut¸a . R. P. Popovici.. Liu. Levien. Infrared spectra of manganese nodules and ferromanganese sediments. Tinsley.. Krishnamurti. 1980. 43e48. R. S. Stos-Gale. 144e152. Pereira-Ramos. C.. Huang. Scientific Studies in Ancient Ceramics. C. Romania. G. Studia Antiqua et Archaeologica.. 34. Geological Institute Bucharest. Ias¸i (Romania) 7.M. Zhang. In: Hughes. Chemical Geology 11. Goodall. M. H. Bach.. R.. 920e930. D. 1973.. hydration. IR spectra of manganese oxides with either layered or tunnel structures.. A. 1968.. Gualtieri. Murgeanu. R. 345e356. C. Z... Solid State Ionics 159. Thermal analysis of manganese dioxide in controlled atmospheres..N. R.. The tetravalent manganese oxides: identification. M.-M. 368e372. Japan.. Journal of Power Sources 87. S. Clay and Clay Minerals 27. R.J. Glasby. Buzgar et al.R. Weidner. Ramamurthy. S.G. J. C. Aluminum-bearing goethite in Venezuelan Laterites. (Ed.. Viel. Sharer. H. Niculescu. An investigation on layered birnessite type manganese oxides for battery applications. 2007.. E.E. pp. J.. Rook. CucutenieTripolye cultural complex: relations and synchronisms with other contemporaneous cultures from the Black Sea area.. Coltos. P. . J.. 205e206. American Mineralogist 94. Yariv. Post..J. K.). 2007.. Canadian Journal of Soil Science 67. 2000. Analysis of pigments used for decorations of Cucuteni pottery.P. 1199e1218. 1:200.. Julien.. Elderfield..F. Villalba.. P. 2003. Potter. 816e826.M. R. Venturelli. 1982. Mira Piatra-Neamt¸ Sheet. British Museum. Raman spectra of birnessite manganese dioxides. 2135 Mantu. Raman microprobe analysis of stucco samples from the buildings of Maya Classic Copan. 1999. L. Journal of Archaeological Science. Rossman.H.P. American Mineralogist 64. D. 1987. P... 1981.. Journal of Thermal Analysis 3. Sharp. 533e543. Baddour-Hadjean.. C.H.. Cercet ari de Restaurare s¸i Conservare 2. G. 1979.J..L. American Mineralogist 65. E. Prewitt.T. Z. Kang.M. Heaney. 267. / Journal of Archaeological Science 40 (2013) 2128e2135 Abstracts of the 19th General Meeting of the International Mineralogical Association in Kobe. 1971.J. Ooi. 1979. Edwards. Renuka.. Mendelovici. Cs-exchange in birnessite: reaction mechanisms inferred from time-resolved X-ray diffraction and transmission electron microscopy..M. American Mineralogist 84.. Hall..S.. D. Franger. S.