Journal of Archaeological Science 40 (2013) 914e925

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Journal of Archaeological Science

journal homepage: http://www.elsevier.com/locate/jas

Physical study of the Cucuteni pottery technology

Florica Matau a, b, Valentin Nica a, Petronel Postolache a, Irina Ursachi a, Vasile Cotiuga b, c,
Alexandru Stancu a, *
a

Faculty of Physics, Alexandru Ioan Cuza University of Iasi, Boulevard Carol I, 11, 700506 Iasi, Romania
Department of Sciences, ARHEOINVEST Platform of Interdisciplinary Research in Archaeology, Alexandru Ioan Cuza University of Iasi, Lascar Catargi St., 54, 700107 Iasi, Romania
c
Faculty of History, Alexandru Ioan Cuza University of Iasi, Boulevard Carol I, 11, 700506 Iasi, Romania
b

a r t i c l e i n f o

a b s t r a c t

Article history:
Received 20 December 2011
Received in revised form
1 August 2012
Accepted 22 August 2012

Most of our knowledge concerning the Cucuteni pottery is based on traditional archaeological methods
(typology, style and context analysis) and only a few interdisciplinary studies have been published. As
there is a strong interest in revealing the basic pottery technology used by the Cucuteni communities we
have investigated a signicant number of pottery samples from 22 archaeological sites located in Eastern
Romania by several physical analysis techniques: X-ray diffraction (XRD) and by magnetic measurements, including a rst-order reversal curve (FORC) diagram study on the samples showing a hysteretic
behavior. The main results presented in this study are discussed and compared with actual knowledge on
the ancient Cucuteni pottery.
2012 Elsevier Ltd. All rights reserved.

Keywords:
Cucuteni culture
Pottery technology
Magnetic measurements
FORC diagram
Rietveld analysis

1. Introduction
Archaeological research based on the examination of ware
shape, color, decoration and overall fabric provides a wealth of
information concerning typological, stylistic and functional issues.
To complement such taxonomy schemes, archaeologists often
resort to an interdisciplinary approach involving physical sciences.
The physical properties of the potteries like color, texture and
size of the clay particles composing them can be used in order to
determine the technology of manufacture and method of ring
adopted by the Cucuteni communities. The estimation of the ring
temperatures throws light on the pyro-technological abilities of the
Cucuteni artisans and on the pottery production scale during the
Chalcolithic period in South-Eastern Europe. In the pottery
production process the heating rate and length of exposure time to
heat (the soaking time) appear to be the most suitable parameters
for understanding the ring technology. For this reason the estimate ring temperature on potshards is evaluated as equivalent
ring temperature which may not be the same with the ring
temperature set initially (Gosselain, 1992; Livingstone Smith,
2001). From the knowledge of the equivalent ring temperature

* Corresponding author. Fax: 40 232 201205.

E-mail address: alstancu@uaic.ro (A. Stancu).
0305-4403/$ e see front matter 2012 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.jas.2012.08.021

one may be able to conclude how the ring process evolved and
how the raw clay was tempered and used to model the vessels.
We are targeting the Cucuteni culture area which was not yet
systematically studied with modern physical characterization tools.
This objective is obviously very ambitious and requires time and
resources and cannot be accomplished in one step or study.
Accordingly, this papers aim is to start this project by analyzing
a signicant sample of Cucuteni culture pottery (50 potshards)
from a wide geographical area within Romania. X-ray diffraction
(XRD) and magnetic measurements, including a rst-order reversal
curve (FORC) study are the main physical techniques presented in
this paper to estimate the ring temperature.
Examples of studies covering similar topics using different
research techniques can be found in the literature (Maniatis and
Tite, 1981; Maggetti et al., 2011; Tudisca et al., 2011). Previous
research has included mostly measurements of the susceptibility
and intensity of natural magnetization of archaeological samples,
saturation isothermal remanence and also anhysteretic remanent
magnetization (ARM) intensities (McDougall et al., 1983). Most of
these studies have applied rock magnetic characterization to
obsidian samples from Eastern Mediterranean region (McDougall
et al., 1983), Argentinian and Chilean Patagonia (Vasquez et al.,
2001), and central Mexico (Urrutia-Fucugauchi, 1999). Mooney
et al. (2003) employed magnetic susceptibility and isothermal
remanence measurements to provenance studies of archaeological
ochre quarries from Australia. In order to identify clay sources and

F. Matau et al. / Journal of Archaeological Science 40 (2013) 914e925

distinguish different stages of Venezuelan pottery craftsmanship

a two-fold magneto/dielectric technique was used (ConstanzoAlvarez et al., 2006; Rada et al., 2008; Rada Torres et al., 2011).
Unfortunately, not too many papers on the archaeometric study of
the Cucuteni pottery from this area can be found in the literature.
We mention that for over a century the Cucuteni ceramics
analysis has been based on typology and the macroscopic recognition of special fabric texture, and it should be stressed that this
classical approach is still relevant (Schmidt, 1932; Monah, 1997;
Lazarovici, 2010). Recently a physicalechemical approach has been
advanced with considerable success but only for the investigation
of the pigments. Constantinescu et al. (2007) used two analytical
methods, X-ray Fluorescence (XRF) and Synchrotron Radiation Xray Diffraction (SR-XRD) in order to investigate the mineralogical
composition of pigments which decorate most of the Cucuteni
ceramics. Also, the Raman spectroscopy was considered to be
a valuable technique for determining the provenance of the
pigments used to decorate the Cucuteni pottery (Buzgar et al.,
2010).
All these physico-chemical methods must be looked upon as
important supplements to the classical typological approach for the
study of pottery technology.
In the next section the general context of the problem is introduced. Then the samples used in this study are described and after
that, in the following sections the X-ray diffraction and magnetic
studies are presented. The results are discussed and the main
conclusions are presented.
2. The archaeological context
The CucutenieTrypillia civilization evolved during the VeIVth
millennia BC and was spread over a vast territory, with a total
area of more than 350,000 km2 in Romania, Ukraine and the
Republic of Moldova (Monah, 1997; Ursulescu, 2008; Lazarovici,
2010) (see Fig. 1). It is perhaps one of the most attractive subjects
when analyzing South-Eastern European prehistory. Its importance
is not limited to spectacular excavated artifacts that include

915

remains of multi-stage wattle-and-daub constructions, a wide

variety of tools, diverse anthropomorphic and zoomorphic gures,
and sophisticated polychrome pottery that have signicantly
enriched our knowledge of daily life and artistic handicraft of Old
European civilizations. On the contrary, the CucutenieTrypillia
civilization offer very useful data on a transformation in human
social evolution and the role technological development assumes in
bringing forth an early form of ranked social organization (Ellis,
1984).
More than a century elapsed since the discovery of the
CucutenieTrypillia eponymous sites. The Cucuteni culture is named
after an archaeological site in North-Eastern Romania, rst
explored by enthusiastic dilettante archaeologists from 1885 to
1890 (Diamandy, 1889; Butzureano, 1891). The Transylvanian
variant is named after a site excavated there prior to World War I,
Ariusd (in Hungarian Ersd) (Lszl, 1927), and the variants in
Ukraine are named Trypillia (in Russian Tripolye) after a site excavated near the Dnieper River in 1896e1897 (Chvojko, 1901). Efforts
of several generations of researchers made it possible to dene the
CucutenieTrypillia area and to build a chronological framework for
its evolution (Schmidt, 1932; Passek, 1935; Mantu, 1998).
Russian and Ukrainian archaeologists describe Trypillia as one
culture with several phases. In contrast, Romanian archaeologists
describe Pre-Cucuteni, Cucuteni and Horodistea-Erbiceni as three
different civilizations that correspond to the Trypillia phases: PreCucuteni is equivalent to Trypillia A, Cucuteni (A, AeB and B) to
Trypillia BIeCI and Horodistea-Erbiceni to Trypillia CII (Lazarovici,
2010).
During the long evolution of this civilization, the ceramic
production technology was undergoing major transformations. The
painted ware of the CucutenieTrypillia civilization indicates technological advancement and high creativity similar to any other preBronze Age society in the Old World. The technological skill can be
tracked in every step of the manufacturing process: the high degree
of clay renement, the manipulation of clay without the assistance
of temper, the development of the potters wheel, the choice of raw
materials for specic colors under carefully controlled atmospheric

Fig. 1. The location of the CucutenieTrypillia civilization in Romania, Ukraine and the Republic of Moldova.

916

F. Matau et al. / Journal of Archaeological Science 40 (2013) 914e925

conditions, as well as the use of high ring temperature and the

construction of elaborate up-draught kilns (Ellis, 1984).
This study focuses on the Cucuteni pottery in Romania, but it
should be remembered that closely related prehistoric communities lived in Ukraine, and the designation CucutenieTrypillia often
is used to refer to the entire cultural tradition.
3. Sampling and analytical methods

experimental diffraction patterns (Rwp) and an estimation of the

best possible Rwp prole based on the statistical noise of the
measured diffraction pattern (Rexp). The quality of the t is determined from the expected and weighted prole R-factors:
GOF (Rwp/Rexp)2 that for the best tting should be equal to 1
(Young, 1993). The relative mineralogical phase compositions
expressed as weight percent (wt%) of crystalline phases with corresponding standard deviation and the GOF obtained from the
Rietveld renement are listed in Table 2.

3.1. Sample selection

3.3. Magnetic measurements
The data set for this investigation contains 50 pottery fragments
sampled to represent the stylistic and technological diversity of the
Cucuteni cultures potshards (see Fig. 2 and Table 1). These potshards were selected from twenty-two archaeological sites (see
Fig. 3). Samples were taken from the body of the pottery fragments,
avoiding 1 mm surface layer.
3.2. XRD analysis
All the solid samples were ground in an agate mortar and gently
side-pressed into a top-loaded holder in order to minimize preferred
orientation. XRD patterns were recorded using Shimadzu LabX XRD6000 powder diffractometer with a diffracted beam graphite
A). The specimens
monochromator of CuKa radiation (l 1.5406 
mounted in reection mode were analyzed in ambient atmosphere
over the range 2q 2e100 with scanning angle rate of 0.03 and
a 2 s/step count time. Qualitative analysis was automatically
performed (Shimadzu LabX software) by comparison with the
reference powder patterns included in ICDD Powder Diffraction
File (PDF2-2004). Mineral phase quantication was made by the
Rietveld method.
The software Diffracplus TOPAS Version 2.1 (Bruker AXS GmbH,
Germany, 2003) which implements fundamental parameters
approach (FPA) (Cheary and Coelho, 1992) was used for quantitative
phase analysis by Rietveld renement. The FPA uses a convolutionbased prole tting calculated from the emission prole, instrumental and sample contributions without a reference sample. The
global factors included the scale factor, 2q zero error correction,
Lorentz polarization factor, Chebyshev polynomials of background
tting and crystal linear absorption coefcient were rened for all
the patterns. Positions, occupancy factors and overall isotropic
displacement parameters of individual atoms for all phases, except
for general atomic positions of quartz, were xed during phase
analysis. The effect of preferred orientation for some crystalline
phase (e.g. mica) was taken into account using the MarcheDollase
function (Dollase, 1986). Lattice parameters and mean crystallite
size of the mineral phases were also optimized in order to provide
the best pattern tting (Young, 1993). The starting values for atomic
parameters were extracted from the Inorganic Crystal Structure
Database (ICSD) (ICSD, 2011).
The Rietveld renement method uses a non-linear least squares
approach to simulate the measured pattern prole (Rietveld, 1969).
The quality of the tting procedure is indicated by a weighted
sum of squares of deviations between the calculated and the

Magnetization curves of the powdered pottery fragments were

made with a vibrating sample magnetometer (Princeton Measurements Co. MicroMag VSM&AGM 2900-3900). The maximum eld
applied was 1.2 T. Measurements were carried out at room
temperatures with less than 1 s averaging time per point. This
measurement system is very good especially when a large number
of data are required, like in the FORC technique that contains typically about 10,000 experimental points for one diagram.
4. Results and discussion
4.1. XRD measurements
Technological issues are revealed by mineralogical studies
aiming to determine the type of raw clays and tempering materials
used, as well as the ring temperature and atmosphere to which
they have been submitted. For the reconstruction of the Cucuteni
pottery technology what becomes important is not the hightemperature thermal behavior of individual clay minerals, but the
transformations at high temperatures of the various phases. These
phases can be the result of the decomposition of the clay minerals
themselves, and also of any non-plastic inclusions which might be
present, such as carbonates or even organic material (Pollard and
Heron, 2008).
The XRD results showed different mineralogical and phase
contents for all the selected Cucuteni shards. Quartz [SiO2], clay
minerals: illite/muscovite [(K, H3O)Al2Si3AlO10(OH)2]/[KAl2Si3AlO10(OH)2] and kaolinite [Al2Si2O5(OH)4], feldspars (K-feldspar
(KAlSi3O8), and plagioclase albite [NaAlSi3O8] and anorthite
[Ca(Al2Si2O8)]), carbonated minerals: calcite [CaCO3], pyroxenes:
diopside [CaMg(Si2O6)] and augite [(Ca, Na) (Mg, Fe, Al, Ti) (Si,
Al)2O6], clinochlore [Al2Mg5Si3O10(OH)8] and iron minerals;
hematite [a-Fe2O3] and magnetite [Fe3O4] were identied (Table 3).
The study of the present mineralogical contents of the Cucuteni
pottery samples enables to estimate the equivalent ring temperature. We noted that the process of ring does not necessarily
achieve a mineral assemblage which is at thermodynamic equilibrium, and this must be remembered in any attempt to predict the
ring properties (Rathossi et al., 2004). The melting point of various
phases becomes critical in high temperature reactions, since
impurities in the clay usually mean that sufcient uxes are present
to melt (or sinter) at least some of the phases (Pollard and Heron,
2008).

Fig. 2. Representative samples of the Cucuteni painted pottery.

F. Matau et al. / Journal of Archaeological Science 40 (2013) 914e925

917

Table 1
Archaeological analysis of the Cucuteni pottery samples.
Sample Site
Paste
Kneading
Coarse size
Firing atmosphere
acronym
Fine Medium Poor Fine Poor Small Different sizes Oxidizing

Style
Reducing Cucuteni A Cucuteni AeB Cucuteni B Cucuteni C

Complete Incomplete
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50

A
A
B
B
C
C
D
D
D
D
E
E
E
F
F
F
G
G
G
H
H
I
I
B
B
J
J
J
K
K
K
K
L
M
M
N
O
O
P
P
Q
R
R
S
S
S
T
U
U
V

*
*

*
*
*
*

*
*

*
*

*
*

*
*
*

*
*
*
*

*
*
*
*

*
*
*

*
*
*
*

*
*
*
*
*
*
*
*
*
*
*
*

*
*
*
*
*

*
*

*
*
*
*

*
*

*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*

*
*
*
*
*
*
*
*
*
*
*

*
*
*
*
*
*
*
*
*
*
*
*

*
*

*
*
*

*
*
*
*

*
*
*

*
*
*
*

*
*

*
*

*
*
*
*
*

*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*

*
*

*
*
*
*
*

*
*
*
*
*
*
*
*
*
*
*

*
*

*
*

*
*
*
*

*
*
*

*
*
*

*
*
*
*
*
*
*
*
*

*
*

*
*
*

*
*

*
*

*
*

*
*

*
*

*
*
*
*

*
*

*
*

*
*

*
*

*
*

*
*

*
*

The mineralogical composition of most of the selected pottery

samples determined within the XRD analysis, due to the high
temperatures they have been red, do not provide signicant
information on the mineralogical composition of the clay that has
been used for their production. The destruction of the pre-existing
matrix structure does not occur instantaneous (Jordn et al., 1999).
The now-existing pottery matrix was obtained through the ring
process in which these crystalline phases, once they exceed their
stability limits, partially decompose and simultaneously others are
being formed (Jordan et al., 2008).
The ceramic materials from the studied pottery samples can be
dened as illitic clays with high sand content, except samples 9D and
12E in which kaolinite is present together with illite/muscovite. The
results from the XRD analysis of the mineralogical transformations
show the persistence of illite/muscovite up to at least 900  C
(Rathossi et al., 2004; Jordan et al., 2008; ssi et al., 2011) in samples.

*
*
*
*

These correspond with the phyllosilicates evolution upon ring

which starts with the dehydroxylation of the illite/muscovite phase
at 700  C, till it disappears at 900  C (Cultrone et al., 2001). According
to Papachristodoulou et al. (2006), the complete destruction of illite/
muscovite ranges between 950  C and 1000  C and, depending on
the composition of the ceramic body, ensures the development of
diopside and also gives increment to iron oxides, such as hematite. If
the ring temperature does not exceed this range, these minerals
still continue to exist as can be observed in 42 potshards.
Quartz remains the main abundant phase at any ring
temperature, except in samples 7D, 17G, 20H, 26J, 27J, 28J, 34M,
39P and 40P in which K-feldspar is the dominant phase. New
phases develop in the pottery samples upon ring: diopside and
augite appear at 800e900  C and show a signicant increase in
quantity and in the main diffraction peak at higher temperatures
(ssi et al., 2011).

918

F. Matau et al. / Journal of Archaeological Science 40 (2013) 914e925

Fig. 3. Distribution map of the Cucuteni sites from where the pottery samples were selected for analysis. Legend: A: Ghelaiesti, Neamt county, B: Lunca, Neamt county, C: Tolici,
Neamt county, D: Trusesti, Botosani county, E: Izvoare, Neamt county, F: Solca, Suceava county, G: Valeni, Neamt county, H: Bodesti, Neamt county, I: Raucesti, Neamt county, J:
Tg. Ocna, Bacau county, K: Poduri, Bacau county, L: Dumestii Noi, Vaslui county, M: Rafaila, Vaslui county, N: Bacesti, Vaslui county, O: Malusteni, Vaslui county, P: Vorniceni,
Botosani county, Q: Scanteia, Iasi county, R: Fetesti, Suceava county, S: Cucuteni, Iasi county, T: Sangeorgiu de Mures, Mures county, U: Ariusd, Covasna county, V: Malnas, Covasna
county.

Calcite decomposition into CaO and CO2 begins at a temperature of 650  C and this phase disappears at 900  C, giving rise to
new high temperature calco-silicates and alumino-calco-silicates
such as the members of the pyroxene group (diopside) and some
of the plagioclase feldspars (anorthite) (Riccardi et al., 1999;
Cultrone et al., 2001; Papachristodoulou et al., 2006; ssi et al.,
2011). Calcite is present in samples 8D, 14F, and 25B in various
amount ranging from 16.9% in sample 8D, to 25.1% in sample 14F
and 47.3% in sample 25B as it was determined by the Rietveld
quantitative analysis. The absence of diopside in sample 8D
indicates that calcite is of primary origin and not a result of postburial deposition processes, allowing to consider that the shard
was submitted to a low ring temperature below 800  C
(Papachristodoulou et al., 2006). The high amount of calcite in
samples 14F and 25B could be explained by the crushed shells
used as temper in the Cucuteni C pottery type (Dodd-Opritescu,
1982). The presence of diopside (1%) in sample 25B indicates
that the ring temperature was of at least 850  C (Maggetti et al.,
2011; Papachristodoulou et al., 2006).
Iron minerals found in the samples may also help assessing the
ring temperature and atmosphere (ssi et al., 2011). Hematite is
present in different quantities ranging from 0.5% (sample 49U) up
to 3.9% (sample 26J) in 45 of the selected samples. Besides hematite, 11 pottery samples (5C, 13E, 16F, 19G, 24B, 28B, 32K, 33L, 36N,
40P and 50V) contain different amounts of magnetite (from 1.9% in
sample 24B up to 7.9% in sample 50V). Samples 35M (2%) and 48U
(7.9%) have only magnetite as iron minerals. For the shards containing only hematite we estimate that the ring cycle was ended in
oxidative atmosphere (Papachristodoulou et al., 2006; ssi et al.,
2011). The association of hematite with magnetite is due to the
incomplete reduction phase of Fe3 compounds during the
reducing phase of ring (Mangone et al., 2008).

The neo-mineral formation temperatures may be affected by

ring type such as pit or kiln ring. Calcite decomposition ends
around 825  C in kiln ring but tends to 875  C in pit ring
conditions (Maritan et al., 2006). These mineralogical transformations are related to peak ring temperature, soaking time,
abundance and type of mineral/phases present, ring atmosphere,
pressure and the specic area of components (ssi et al., 2011). Also,
these are inuenced by the surface area from where the sample was
selected (Maggetti et al., 2011).
4.2. Magnetic measurements
The use of magnetic measurements on potshards was suggested
many years ago (Coey et al., 1979) and its importance was especially
due to the variety of the magnetic properties shown by samples of
pottery (Schmidt, 2007). Magnetic measurements were used in
investigation of the source materials (Evans, 1979; McDougall et al.,
1983; Urrutia-Fucugauchi, 1999; Rasmussen, 2001; Vasquez et al.,
2001; Mooney et al., 2003; Linford, 2005), manufacture techniques used (Coey et al., 1979; van Klinken, 2001; ConstanzoAlvarez et al., 2006; Beatrice et al., 2008; Rada et al., 2008; Rada
Torres et al., 2011), or in archaeomagnetic dating of archaeological sites (Kovacheva et al., 2001; Zananiri et al., 2007; Suteu et al.,
2008; Spassov et al., 2008; Catanzariti et al., 2008; de Marco et al.,
2008; Herries et al., 2008).
Essentially, these methods are built on the idea that the
magnetic properties of pottery samples can be correlated not only
with the composition of the clay but also with the thermal process
used during the production. The magnetic characterization techniques specic to these studies are originated in the paleomagnetic
studies targeted on the magnetic carriers of remanent magnetization and on the various magnetization processes responsible for the

Table 2
The quantitative mineralogical phase compositions. The Rietveld analysis.
Quartz

K-Feldspar

Muscovite

Albite

Diopside

Augite

Anorthite

Hematite

Magnetite

Calcite

Kaolinite

Clinochlore

Rexp

Rwp

GOF

DW

39.7 (7)
37.7 (2)
52.8 (7)
43.8 (2)
50.8 (7)
56.5 (6)
28.6 (2)
31.1 (1)
26.8 (9)
29.8 (1)
44.9 (9)
27.0 (5)
38.8 (2)
30.5 (5)
33.2 (6)
43.6 (9)
32.4 (4)
39.1 (3)
47.3 (6)
26.4 (3)
33.4 (7)
37.1 (3)
29.1 (6)
36.2 (1)
13.9 (1)
18.8 (1)
27.0 (6)
29.1 (3)
51.1 (5)
31.4 (7)
36.9 (2)
44.2 (9)
48.8 (4)
30.9 (9)
38.4 (8)
34.5 (6)
49.2 (7)
43.2 (1)
16.2 (1)
9.7 (4)
44.1 (5)
43.1 (7)
55.0 (1)
38.6 (7)
44.6 (5)
41.4 (4)
43.6 (4)
48.9 (7)
36.8 (5)
41.8 (1)

31.9 (8)
32.9 (2)
12.9 (8)
13.9 (9)
22.3 (5)
14.4 (5)
29.3 (2)
13.1 (2)
22.0 (8)
20.3 (7)
12.0 (1)
23.1 (2)
38.0 (1)
2.7 (3)
29.4 (1)
33.8 (3)
34.3 (8)
21.1 (1)
38.8 (1)
41.6 (1)
22.3 (4)
10.4 (1)
10.5 (1)
17.7 (1)
7.5 (5)
36.8 (8)
36.7 (5)
37.2 (8)
9.8 (5)
9.4 (7)
30.0 (5)
23.5 (1)
16.1 (5)
32.6 (1)
26.4 (9)
22.1 (1)
15.2 (3)
5.8 (2)
54.5 (8)
57.3 (8)
17.4 (4)
17.2 (4)
18.4 (1)
24.2 (6)
12.1 (6)
19.8 (8)
3.8 (8)
3.7 (9)
36.2 (1)
34.2 (1)

n.d.
10.5 (1)
11.2 (2)
15.7 (2)
7.7 (1)
15.6 (9)
21.1 (1)
21.5 (2)
22.3 (5)
12.9 (4)
18.6 (5)
8.1 (7)
n.d.
18.4 (4)
23.5 (8)
10.9 (5)
6.1 (2)
25.9 (2)
n.d.
15.5 (3)
10.2 (3)
24.5 (9)
38.5 (9)
31.6 (1)
17.7 (2)
n.d.
n.d.
3.5 (1)
11.3 (5)
13.0 (1)
4.6 (7)
7.7 (8)
3.5 (4)
1.7 (8)
7.8 (7)
12.1 (1)
10.6 (2)
15.9 (7)
n.d.
n.d.
10.6 (9)
15.8 (7)
3.5 (8)
7.4 (4)
11.0 (2)
10.5 (4)
39.2 (6)
36.1 (5)
11.7 (7)
n.d.

5.9 (8)
3.5 (8)
7.2 (4)
8.4 (7)
3.3 (5)
4.6 (3)
6.4 (1)
9.5 (6)
5.4 (7)
9.6 (8)
12.1 (6)
5.0 (3)
2.6 (3)
3.2 (5)
5.0 (2)
0.9 (9)
4.0 (8)
5.9 (6)
3.3 (2)
2.9 (3)
7.3 (2)
15.3 (1)
14.9 (8)
4.8 (2)
7.0 (4)
8.6 (6)
5.6 (2)
5.5 (4)
9.9 (1)
10.9 (8)
10.0 (1)
7.0 (4)
7.0 (4)
4.6 (1)
1.4 (3)
4.7 (6)
7.4 (2)
12.8 (3)
3.3 (3)
4.9 (3)
7.4 (2)
3.2 (9)
0.6 (4)
4.7 (5)
10.8 (8)
8.5 (6)
7.0 (9)
8.2 (8)
2.1 (9)
3.3 (3)

9.4 (3)
4.7 (1)
1.5 (9)
4.0 (4)
1.6 (5)
1.8 (3)
3.4 (2)
n.d.
4.1 (7)
10.8 (2)
2.4 (1)
12.0 (2)
1.0 (3)
n.d.
3.1 (9)
1.0 (7)
4.5 (1)
2.1 (4)
1.0 (3)
2.5 (1)
7.8 (7)
2.7 (3)
1.2 (9)
0.8 (9)
1.0 (8)
16.8 (4)
5.2 (1)
8.1 (2)
1.1 (5)
6.9 (1)
2.8 (1)
2.1 (8)
4.9 (4)
6.5 (9)
1.8 (2)
2.2 (4)
1.2 (6)
8.3 (7)
1.4 (9)
1.6 (6)
4.8 (5)
5.1 (3)
2.6 (4)
4.8 (3)
9.4 (3)
7.1 (3)
1.6 (7)
0.6 (7)
2.6 (2)
3.9 (5)

6.1 (6)
5.4 (1)
9.3 (3)
5.6 (4)
3.4 (7)
0.6 (6)
5.7 (2)
1.4 (4)
3.5 (2)
6.1 (5)
5.7 (3)
13.4 (1)
10.3 (7)
4.4 (8)
1.1 (2)
1.3 (5)
10.4 (5)
1.3 (5)
0.8 (6)
7.4 (9)
13.0 (1)
5.1 (7)
1.8 (5)
0.7 (5)
1.8 (5)
12.2 (8)
13.1 (2)
7.7 (9)
6.6 (6)
23.1 (1)
7.1 (4)
9.5 (5)
7.2 (1)
2.8 (4)
11.7 (9)
11.9 (2)
8.7 (3)
9.4 (7)
14.6 (1)
15.2 (5)
7.6 (9)
4.6 (5)
8.1 (1)
9.9 (1)
5.5 (9)
7.7 (2)
1.1 (4)
n.d.
1.0 (3)
2.0 (5)

5.1 (1)
3.3 (4)
2.7 (9)
7.0 (1)
5.2 (1)
4.9 (4)
2.4 (4)
3.0 (8)
12.1 (2)
8.3 (1)
2.4 (6)
3.0 (5)
3.4 (6)
15.4 (3)
2.6 (4)
7.0 (5)
2.8 (4)
0.8 (2)
1.7 (5)
2.1 (2)
4.0 (1)
2.9 (7)
2.0 (1)
3.1 (4)
3.5 (5)
2.5 (6)
10.4 (7)
4.7 (3)
8.3 (5)
3.8 (1)
6.2 (4)
1.1 (4)
8.24)
8.6 (4)
10.1 (2)
6.5 (3)
5.9 (1)
1.7 (3)
7.7 (3)
5.6 (9)
3.9 (6)
9.5 (4)
2.1 (8)
7.3 (1)
3.7 (1)
2.3 (2)
1.9 (3)
2.1 (4)
4.9 (4)
4.7 (4)

1.6 (7)
1.8 (1)
2.0 (2)
1.3 (5)
1.9 (6)
1.2 (8)
2.9 (6)
n.d.
1.5 (6)
1.9 (3)
1.6 (7)
0.90 (1)
2.1 (3)
n.d.
1.9 (1)
1.1 (1)
1.3 (7)
3.5 (4)
3.0 (2)
1.3 (5)
1.7 (1)
1.7 (2)
1.7 (8)
3.0 (1)
n.d.
3.9 (7)
1.7 (8)
1.7 (5)
1.6 (8)
1.2 (5)
2.1 (6)
2.2 (8)
1.8 (6)
1.9 (2)
n.d.
2.4 (5)
1.5 (6)
2.6 (9)
2.1 (3)
1.1 (6)
3.7 (9)
1.1 (1)
1.5 (1)
1.1 (7)
2.5 (7)
2.4 (2)
1.3 (9)
n.d.
0.5 (8)
1.9 (8)

n.d.
n.d.
n.d.
n.d.
3.4 (4)
n.d.
n.d.
n.d.
n.d.
n.d.
n.d.
n.d.
3.5 (9)
n.d.
n.d.
3.8 (1)
n.d.
n.d.
3.9 (7)
n.d.
n.d.
n.d.
n.d.
1.9 (3)
n.d.
n.d.
n.d.
2.1 (6)
n.d.
n.d.
n.d.
2.2 (7)
2.2 (1)
n.d.
2.0 (1)
3.3 (1)
n.d.
n.d.
n.d.
4.2 (1)
n.d.
n.d.
7.9 (7)
1.6 (4)
n.d.
n.d.
n.d.
3.8 (5)
n.d.
7.9 (3)

n.d.
n.d.
n.d.
n.d.
n.d.
n.d.
n.d.
16.9 (7)
n.d.
n.d.
n.d.
n.d.
n.d.
25.1 (2)
n.d.
n.d.
n.d.
n.d.
n.d.
n.d.
n.d.
n.d.
n.d.
n.d.
47.3 (2)
n.d.
n.d.
n.d.
n.d.
n.d.
n.d.
n.d.
n.d.
n.d.
n.d.
n.d.
n.d.
n.d.
n.d.
n.d.
n.d.
n.d.
n.d.
n.d.
n.d.
n.d.
n.d.
n.d.
n.d.
n.d.

n.d.
n.d.
n.d.
n.d.
n.d.
n.d.
n.d.
n.d.
1.9 (2)
n.d.
n.d.
7.3 (7)
n.d.
n.d.
n.d.
n.d.
n.d.
n.d.
n.d.
n.d.
n.d.
n.d.
n.d.
n.d.
n.d.
n.d.
n.d.
n.d.
n.d.
n.d.
n.d.
n.d.
n.d.
n.d.
n.d.
n.d.
n.d.
n.d.
n.d.
n.d.
n.d.
n.d.
n.d.
n.d.
n.d.
n.d.
n.d.
n.d.
n.d.
n.d.

n.d.
n.d.
n.d.
n.d.
n.d.
n.d.
n.d.
3.2 (5)
n.d.
n.d.
n.d.
n.d.
n.d.
n.d.
n.d.
n.d.
n.d.
n.d.
n.d.
n.d.
n.d.
n.d.
n.d.
n.d.
n.d.
n.d.
n.d.
n.d.
n.d.
n.d.
n.d.
n.d.
n.d.
n.d.
n.d.
n.d.
n.d.
n.d.
n.d.
n.d.
n.d.
n.d.
n.d.
n.d.
n.d.
n.d.
n.d.
n.d.
n.d.
n.d.

7.44
6.40
7.24
7.07
7.36
7.11
6.35
6.84
7.50
7.46
7.19
7.38
7.38
7.28
6.12
7.04
7.35
7.12
7.24
7.34
7.44
7.19
7.15
7.35
7.56
6.46
6.43
6.48
7.28
7.52
6.36
7.39
6.24
6.54
6.41
6.17
6.31
6.29
7.59
7.71
6.32
6.06
7.27
6.34
6.20
7.41
6.70
5.91
7.15
7.27

11.97
11.83
11.42
13.46
11.06
11.16
8.88
12.40
10.38
13.72
9.18
12.17
11.03
11.21
9.55
9.44
10.38
11.05
12.17
10.20
9.85
9.63
9.93
11.20
12.32
11.72
10.17
9.21
10.76
11.05
10.58
10.43
9.01
9.87
9.88
10.12
10.59
9.18
11.24
11.32
11.91
10.51
9.77
11.00
10.70
11.14
12.55
10.82
11.61
11.67

1.61
1.85
1.58
1.90
1.50
1.57
1.40
1.81
1.38
1.84
1.28
1.65
1.49
1.54
1.56
1.34
1.41
1.55
1.68
1.39
1.32
1.34
1.39
1.52
1.63
1.82
1.58
1.42
1.48
1.47
1.66
1.41
1.45
1.51
1.54
1.64
1.68
1.46
1.48
1.47
1.88
1.73
1.35
1.73
1.72
1.50
1.87
1.83
1.62
1.61

0.90
0.72
0.90
0.72
0.92
0.92
1.13
0.70
1.17
0.67
1.34
0.81
1.02
0.98
0.92
1.23
1.06
0.91
0.81
1.08
1.27
1.17
1.11
0.93
0.85
0.66
0.86
1.13
0.98
1.00
0.86
1.13
1.04
0.95
0.94
0.87
0.85
1.07
0.98
0.99
0.62
0.84
1.17
0.84
0.77
1.00
0.68
0.79
0.87
0.91

F. Matau et al. / Journal of Archaeological Science 40 (2013) 914e925

Sample
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50

919

920

F. Matau et al. / Journal of Archaeological Science 40 (2013) 914e925

Table 3
The results of magnetic measurements.
Sample

Units
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50

0.29
0.10
0.22
0.10
0.32
0.11
0.16
0.06
0.09
0.14
0.10
0.10
0.30
0.08
0.13
0.22
0.37
0.03
0.39
0.05
0.09
0.15
0.14
0.04
0.10
0.12
0.24
0.16
0.25
0.10
0.28
0.24
0.12
0.22
0.21
0.23
0.20
0.15
0.22
0.43
0.05
0.14
0.28
0.32
0.20
0.05
0.20
0.12
0.15
0.24

Mass

Saturation

Hc

Ms

emu

Oe

emu/g

0.02
0.02
0.04
0.03
0.02
0.03
0.02
0.06
0.01
0.01
0.02
0.01
0.03
0.03
0.03
0.02
0.02
0.02
0.01
0.01
0.03
0.02
0.04
0.02
0.05
0.03
0.02
0.04
0.01
0.02
0.03
0.03
0.03
0.02
0.03
0.02
0.03
0.02
0.02
0.01
0.04
0.01
0.04
0.02
0.02
0.02
0.02
0.01
0.05
0.02

0.02
0.00
0.02
0.01
0.01
0.01
0.01
0.01
0.00
0.01
0.01
0.00
0.02
0.01
0.01
0.01
0.02
0.00
0.00
0.00
0.01
0.01
0.02
0.00
0.01
0.01
0.01
0.01
0.00
0.00
0.02
0.02
0.01
0.01
0.04
0.01
0.02
0.00
0.00
0.01
0.01
0.01
0.02
0.02
0.01
0.00
0.01
0.00
0.03
0.01

150.41
71.91
102.39
46.00
149.54
51.49
74.25
55.45
44.57
54.90
67.77
58.50
114.57
43.62
65.40
148.90
119.33
36.46
695.19
44.80
55.13
77.52
55.67
30.47
61.80
45.45
75.63
170.44
146.33
56.39
108.39
88.77
84.91
83.60
88.89
98.58
68.91
56.92
268.14
199.61
29.05
66.57
131.84
121.02
110.76
39.97
152.39
88.88
63.79
105.77

0.82
0.21
0.47
0.27
0.67
0.22
0.52
0.10
0.21
0.41
0.25
0.38
0.83
0.24
0.38
0.36
0.89
0.08
0.27
0.18
0.21
0.39
0.51
0.11
0.27
0.26
0.55
0.22
0.35
0.17
0.82
0.64
0.20
0.44
1.35
0.60
0.48
0.30
0.17
1.23
0.16
0.41
0.53
0.90
0.28
0.11
0.36
0.18
0.48
0.48

magnetization of rocks. We mention for example the use of natural

remanent magnetization, the bulk magnetic susceptibility, and the
intensity of isothermal remanent magnetization (McDougall et al.
(1983) for samples from Mediterranean region, Vasquez et al.
(2001) for samples from Argentina and Chilean Patagonia). AF
demagnetization of the saturation isothermal remanent magnetization was reported in Urrutia-Fucugauchi (1999) for samples from
Central Mexico. Rasmussen (2001) added Magnetic Susceptibility
and Luminescence measurements for provenance studies of
pottery at three different sites in Denmark. To distinguish between
different ochre sources from Australia, Mooney et al. (2003) added
the anhysteretic remanent magnetization to the previously used
magnetic parameters (susceptibility and isothermal remanence).
Beatrice et al. (2008) for tile samples from Pompeii and Gravina di
Perugia (Italy) combined magnetic properties with color
measurements. Constanzo-Alvarez et al. (2006) and Rada Torres
et al. (2011) for samples from Venezuelan islands associated
dielectric measurements to magnetic parameters.

Two main difculties in the simpler interpretation of the

magnetic data are always recognized by the researchers working
in paleomagnetism and these problems are mentioned also in the
previously cited articles. One is the size dependence of the
magnetic properties of particles and the other is the strong
inuence of the inter-particle magnetic interaction on any
magnetization process used for the characterization. It is recognized that very small ferromagnetic particles can show a superparamagnetic behavior with no remanence in zero applied eld as
the thermal energy is bigger than the energy barrier between
stable equilibrium states. The bigger particles can have a remanent moment but this remanence depends on the size of the
particles. Small blocked particles have a single-domain behavior
similar to the one described by the well-known StonereWohlfarth
model (Stoner and Wohlfarth, 1948) but as the volume increases
a pseudo single domain state or even a multidomain state can be
observed in the particles. Methods to separate these different
states were studied intensely (Dunlop and zdemir, 1997) but the
results are not always credible. As mentioned for example by
Tauxe (2002) physical interpretation of hysteresis loops is more
complex and simple plots of the ratios alone are virtually meaningless. We also mention that the characterization by single
parameters (like remanence, coercivity, other similar) have the
inherent problem that cant discriminate in a unique form
between different contributions of particles from different
materials with various anisotropies, easy axes orientation,
volumes, shape, etc. The other problem that is avoided carefully
by most of the mentioned studies is the problem of inter-particle
magnetic (mostly magnetostatic) interactions. As the particle
density is not the same in all the samples and consequently the
effect of interactions is unknown in the performed experiments
this adds errors difcult to evaluate in the global magnetic characterization process. As a nal remark on the problems related to
classical magnetic studies we mention the complex behavior of
the reversible component of magnetization in ensembles of
ferromagnetic particles, especially when some of the particles are
superparamagnetic and others, with bigger volumes, are blocked.
The coupling by interactions between the reversible and irreversible (related only to moment switching) make the problem
even more complicated (see for example Bodale et al., 2011). The
reversible component is present in all the susceptibility
measurements and consequently should be accounted correctly in
this type of measurement. Again the correct account of interactions is of paramount importance for the magnetic characterization. The need for new magnetic characterization techniques able
to provide the kind of information not given by the classical
techniques is evident.
About one decade ago, the use of another magnetic characterization technique, namely the rst-order reversal curves (FORC)
diagram method, was proposed by Pike et al. (1999) from the
Department of Geology @ University of Davis, California. In the
mentioned paper and in the subsequent publications (Pike et al.,
1999; Roberts et al., 2000; Pike et al., 2001a, 2001b; Pike, 2003;
Stancu et al., 2003a) it was shown that this technique can offer not
only accurate information concerning the inter-particle interactions in particulate ferromagnetic media but also the distribution of
the particles as a function of the coercive eld. As the potshards are
essentially particulate media a logical consequence would be the
use of this method in archaeomagnetic studies as well.
The FORC technique was in fact described for the rst time by
Mayergoyz (1991) before the publication of the mentioned paper
of Pike et al. (1999). The method was designed to identify the
Preisach distribution (the distribution of coercive and interaction
elds) for systems correctly described by the classical Preisach
model (CPM) (Preisach, 1935). As stated by Mayergoyz (1991) in

F. Matau et al. / Journal of Archaeological Science 40 (2013) 914e925

the representation theorem, the systems should obey to wipingout and congruency properties in order to be described by the
CPM. As a consequence of this theorem one rst has to check
experimentally if the samples show wiping-out and congruency
properties and then to apply an identication technique based on
FORCs measurement. The wiping-out property can be tested by
measuring minor hysteresis loops and observing if these loops are
closing perfectly. Most magnetic samples have this property. The
congruency property is more difcult to be experimentally proven
as it requires to see if the minor loops measured between the
same eld limits (regardless of the way one obtains the initial
point on the minor loop) are congruent (if one translates the loops
along the moment axis the minor loops should be identical). This
property is difcult to be checked extensively as it requires a large
number of measurements. Theoretically, a system obeying
congruency property should have a distribution of interaction
elds not dependent on the magnetic state of the sample, which in
real systems is difcult to imagine. Systematic studies of interaction eld distribution in correlation with the congruency
property were at the origin of modied Preisach models (Della
Torre, 1999).
What is really important in the paper published by Pike and
collaborators (Pike et al., 1999) was the proposal to use the FORC
method as a purely experimental technique which will provide
a distribution, named FORC distribution that will be an approximation of the Preisach distribution and will be characteristic to the
measured sample. In time many laboratories have followed this
idea and gradually a large number of typical diagrams were identied for specic magnetic samples (Stancu et al., 2003a;
Muxworthy et al., 2004; Sagnotti et al., 2005; Wehland et al., 2005;
Carvallo et al., 2006; Smirnov, 2006) and characteristic features
were linked to physical properties of the samples. It has been
shown that some of the typical features observed on experimental
FORC diagrams can be explained within the modied Preisach
models and that the real distributions of interaction and coercive
elds can be calculated from FORC experimental data (Stancu et al.,
2003a; Postolache et al., 2003; Stancu et al., 2006). The FORC
diagram method is now one of the most popular methods to
characterize magnetic hysteresis in various systems: ferromagnetic
(recording materials (Stancu et al., 2000; Muxworthy and Dunlop,
2002; Sagnotti et al., 2005; Smirnov, 2006), natural magnetic
samples e geophysics (Muxworthy, 2001; Wehland et al., 2005;
Roberts et al., 2010), and even in very complex nanomagnetic
structured media (Muxworthy and Williams, 2005; Carvallo et al.,
2006)), non-ferromagnetic (spin-transition materials) (Enachescu
et al., 2005; Tanasa et al., 2005), ferroelectric (Stancu et al.,
2003b) and in other hysteretic systems (Carvallo and Muxworthy,
2006).
The rst-order magnetization curve can be measured starting
in a point from the major hysteresis loop. One can use points on
the descending or ascending branches of the major loop. If one
discusses the FORCs starting from the descending branch of the
major hysteresis loop, the measurement starts after the sample is
positively saturated and then a smaller eld is applied to the
sample (usually applied in the negative direction). This eld is
called reversal eld and is the starting point of one FORC
measurement (see Fig. 4). Instead of continuing the measurement
towards the negative saturation as in the classical measurement of
the descending branch of the major hysteresis loop, starting with
the reversal eld, Hr, the eld is increased gradually until the
positive saturation is obtained again. One FORC is measured
between the reversal eld and the eld sufcient to saturate the
sample in the positive direction again. As the major loop is
considered conventionally as a zero order magnetization curve the
rst-order magnetization curve is the one that has the initial point

921

Fig. 4. First-order reversal curve (FORC) and minor closed loop with one branch from
the FORC and the other a second-order reversal curve (SORC).

on the zero-order curve and for which the eld value changes in
the opposite direction to the measurement on the zero-order
curve. As we have discussed in our example, on the descending
branch of the major loop the eld is decreasing but on the FORC,
starting from Hr the eld is increasing. In a similar manner, if at
a certain moment one interrupts the measurement on the FORC in
a eld Hr1 and instead of increasing the eld one starts decreasing
it we shall obtain a second-order magnetization curve. What is
essential to mention is that the magnetization measured in one
point on the FORC is dependent on two elds (H, Hr) where H is
the actual eld in the experimental point. It can be rather easily
shown that the second order mixed derivative of the moment
measured on the FORC, m
FORC H; Hr , is proportional to the FORC
distribution:

1 v2 m 
FORC H; Hr
2
vHvHr

rFORC H; Hr 

which for the CPM systems is identical with the Preisach distribution, as we have already mentioned.
When applied to experimental data one has to cover the majorhysteresis loop with FORCs (typically 100 experimental curves) and
with a numerical algorithm one evaluates the derivative and
obtains the FORC distribution. As shown in Fig. 5 nally one
represents the contour plot of the FORC distribution in (H, Hr)
coordinates. If one rotates the system with 45 one can represent
the diagram in (Hc, Hs) coordinates (where Hc (H  Hr)/2 is the
coercive eld and Hs (H Hr)/2 Hi is the eld shift that is the
interaction eld Hi with the opposite sign). In the Preisach model
terms the elementary hysteresis (the hysteron) is a rectangular
hysteresis loop and the interactions are shifting the loops along the
eld direction. In this representation one obtains the distribution of
the coercive eld along the abscissa and the distribution of interactions along the ordinate. It is recommended to show one or more
sections along the two coordinates, especially around the
maximum value of the distribution (see Fig. 6).
The magnetic properties of the potshards selected from the
Cucuteni culture may differ greatly as we can observe from Table 3.
In Table 3 it may be seen that Ms is very small (0.10 emu/g) in
samples 8D and 18G, but continues to increase until reaches
1.35 emu/g in sample 35M. The selected pottery samples show,
also, distinctive coercivity values. Hc is 50 Oe for nine pottery
samples, 50e100 Oe for twenty three potshards and 200 Oe for
seventeen ware samples. As an exception, the pottery sample 19G

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F. Matau et al. / Journal of Archaeological Science 40 (2013) 914e925

Fig. 5. Experimental set of FORCs (sample 1A) and the FORC diagram (below) in
Preisach-type (H, Hr) coordinates. The experimental points presented in the inset are
used in the evaluation of the second-order mixed derivative which is proportional to
the FORC distribution.

has a very high coercivity (695 Oe) compared to the rest of the
potshards.
In the case of potshards from Cucuteni, we have measured the
major loops for all the samples and for the some selected samples we
also have measured the FORCs and calculated the FORC distributions.

Fig. 6. Experimental FORC diagram (sample 1A) in rotated coordinates. On the abscissa
is represented the coercive eld of the particles and on the ordinate the interaction
eld (equivalent to a shift of the hysteron along the eld axis).

Fig. 7. Typical magnetic hysteresis loops from Cucuteni pottery samples (samples 2A,
5C, 18G).

In Fig. 8 one shows the most typical plot used in archaeomagnetism

which consist in the representation of the major loop rectangularity,
S (Mr/Ms), where Ms is the saturation and Mr the remanent
magnetic specic moments of the sample, respectively.
This graphic presentation of the data (Fig. 8) shows the possibility of clustering the data in three major group. The potshards
belonging to the rst contain calcite as were determined by the XRD
analysis and has low values for Mr/Ms and Hc. The second group
brings together most of the pottery samples which have different
amounts of hematite, magnetite and diopside in their composition
and shows moderate values for Mr/Ms and Hc. The third group
includes only few samples having hematite and diopside in their
mineralogical structure and high values for Mr/Ms and Hc.
The general aspect of the loops is rather diverse and in
agreement with previous studies performed on archaeological
tiles from Pompei (Beatrice et al., 2008) (see Fig. 7). In our case
one can relate rather well the magnetic measurements with the
other physical analyses presented in this paper. By the measurement of magnetic properties which relate the para- and/or ferromagnetic attributes of the pottery with the ring-induced iron
transformations it is possible to obtain information on the basis of
an almost unique combination of properties related to ring
protocol and mineralogical phase transformations revealed by the
XRD measurements.

F. Matau et al. / Journal of Archaeological Science 40 (2013) 914e925

923

282

Fig. 10. FORC diagram & major hysteresis loop for sample 19G.

Fig. 8. The squareness (S is the ratio between the remanent and the saturation
magnetic moment measured on the major hysteresis loop) versus coercive eld
diagram for the Cucuteni potshards.

The small values of Ms and Hc registered for 27 of the pottery

samples are a characteristic of ceramics rich in Fe3. This is an
indicator of a substantial presence of iron compounds and of
a temperature not higher than 900  C (samples 2A, 3B, 4B, 6C, 7D,
9D, 10D, 11E, 12E, 15F, 18G, 20H, 21H, 22I, 23I, 26J, 27J, 29K, 30K,
34M, 37O, 38O, 41Q, 42R, 45S, 46S, 49U).
The samples 1A, 17G, 31K and 44S are characterized by the
highest Ms and Hc values. To explain the higher range of Ms and Hc
values a higher equivalent ring temperature may be hypothesized
(up to 1000  C). This could be the result of a longer soaking time.
The incomplete oxidizing process during ring is responsible for
the high values of Hc and small Ms values and for the presence of
both magnetite and hematite. A reduced value of Ms may indicate
a shorter soaking time. These differences observed between Hc
values could be the result of the ring technique e alternation of
oxidationereduction periods, difference in ring temperature and/
or in soaking time e rather than to the initial ferrous composition of
the clay paste.
The differences observed between samples showing similar
mineralogical transformations (samples included in the second and

third group) are probably due to the use of a different ring technique with a different equivalent ring temperature (equal
temperature and different soaking time).
For some of the samples we have added the FORC distribution
analysis in order to see what supplementary details one can get
from this measurement.
One shows here only two such results. In Figs. 9 and 10 we show
the FORC diagram for the sample 5C and for a sample with a very
strange behavior (sample 19G).
For the sample 5C one can observe a clear Gaussian distribution
of coercivity (average coercivity Hc0 215 Oe; standard deviation of
coercivity distribution Hcs 358 Oe) and also a similar distribution
of interactions (average interaction eld Hi0 57 Oe; standard
deviation of interaction eld distribution His 261 Oe). The
asymmetry of the interaction eld distribution is not very large and
is certainly due to mean eld interactions with slight magnetizing
effect. The values of the distribution parameters are uniquely
associated to the sample and are linked to the particles coercivities
(due to the variation in volume and shape of the ferromagnetic
particles from the potsherd) and to the particles interactions (due
to the packing ration of particles in the sample and to the saturation
magnetization and the volumes of the particles, which may be
typical to the clay source).
In Fig. 10 one shows the FORC diagram of the sample 19G and
the result shows clearly that the coercivity distribution is bi-modal
corresponding to two types of ferromagnetic particles, one with an
average coercivity of Hc01 275 Oe and the second one with a much
higher coercivity of Hc02 6580 Oe. The standard deviation of the
interaction eld distribution is His 262 Oe (measured on the rst
peak).
The lower coercivity component can be easily associated with
the content of magnetite. A recent study of Yang et al. (2011) offers
a plausible explanation for the second peak in the coercive eld
distribution. In this article the authors report magnetic measurements at room temperature for a-Fe2O3 samples obtained from
magnetite through heat treatment in atmosphere of nitrogen and
oxygen. The hematite particles obtained in this thermal process
shown coercivities larger than 6 kOe, similar to the ones obtained in
our case.
5. Archaeological considerations and conclusions

215
Fig. 9. FORC diagram & major hysteresis loop for sample 5C.

Through magnetic properties, especially, rst order reversal

curve (FORC) measurements combined with quantitative mineralogical composition determination, an effective new method of
investigation has been identied, able to distinguish aspects related

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F. Matau et al. / Journal of Archaeological Science 40 (2013) 914e925

to ring technology. From this point of view three distinct ceramics

groups attributed to different ring temperatures have been
differentiated in a coherent grouping which supports this conclusion. The magnetic measurements results seem to be inuenced by
the soaking time, the modality of cooling, and by the clay composition and homogeneity.
The analysis of magnetic properties provides new information
which help understanding the mineralogical transformations due
to the ring process. In terms of pottery technology, the magnetic
measurements conrm the mineralogical transformations detected
by XRD analysis and suggest a certain degree of standardization in
the pottery production.
The magnetic measurements provide archaeologists with the
potential to test hypotheses concerning ceramic manufacture that
has not previously been achieved in traditional Cucuteni ceramic
studies. A larger database of both clays and shards from multiple
sites along with better chronological control is necessary to thoroughly take advantage of this potential.
The increased ring temperature is related to a large scale
production process. This was determined by a possible change in
the scale or mode of pottery production during the Chalcolithic
period, with possible shifts from household to workshop industry.
However, we consider it is too early to conclusively determine such
an issue on the basis of this study alone. What is clear at this stage is
that the pyro-technological abilities (use of high ring temperatures) seems to have remained quite the same, indicating a very
high technological skill and a very traditional potters technique,
with very little change occurring over time.
In the next stage of our research we hope to be able to more
explicitly relate these phenomena to changes in the social organization of the CucutenieTrypillia communities during the respective
periods. Such a study will also have to take into account other
aspects such as the distribution of the relevant pottery types,
production modes and technologies, something which is clearly
beyond the scope of this present study.
Acknowledgments
This paper is a result of the research project Physical methods
applied in archaeology which is nancially supported by the
Sectorial Operational Programme Human Resources Development
2007e2013 within the project Transnational Network for Integrated
Management of Postdoctoral Research in Communicating Sciences.
Institutional building (postdoctoral school) and fellowships program
(CommScie) e POSDRU/89/1.5/S/63663.
The authors would like to thank Dr. Neculai Bolohan and Dr. Dan
Monah for fruitful discussions. We would also like to express our
gratitude to Dr. Roxana Munteanu (Neamt County Museum),
Lacramioara Istina (Bacau County Museum), Dr. George Bodi, Dr.
Magda Lazarovici and Bogdan Minea (Institute of Archaeology,
Romanian Academy, Iasi Branch), dr. Aurel Melniciuc (Botosani
County Museum), Dr. Bogdan Niculica (Suceava County Museum),
Ciprian Lazanu (Vaslui County Museum) and Dr. Sandor Jozsef
Sztancsuj (Szekely National Museum, Sfantu Gheorghe, Covasna
County) for providing the pottery samples. The nal version was
improved within the valuable comments and suggestions of two
anonymous reviewers.
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