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Archaeometry 54, 5 (2012) 868–892 doi: 10.1111/j.1475-4754.2011.00650.x

I D EN TI FI C AT ION, P ROCE SSING A N D U S E O F R ED PI G MEN TS


( H E M AT I TE AND CINNAB AR) IN TH E VA LEN C I A N EA R LY
NE OL IT HIC ( S PA I N ) *

I. DOMINGO†
ICREA Research Professor at Universitat de Barcelona/SERP, Departament de Prehistòria, Història Antiga i Arqueologia,
Montealegre, 6, 08001 Barcelona, Spain

P. GARCÍA-BORJA
Departament dePrehistòria i Arqueologia, Universitat de València, Avda. Blasco Ibáñez, 28, 46010 València, Spain

and C. ROLDÁN
ICMUV, Instituto de Ciencia de los Materiales, Universitat de València, P.O. Box 22085, 46071 València, Spain

The results of the first elemental and structural physicochemical analyses (SEM–EDX, TXRF,
XRD, FTIR, GC and EDXRF) of Early Neolithic red pigment samples from the region of
Valencia confirm one of the earliest uses of cinnabar (HgS) in Spain (5300 to 5000 cal BC).
They also inform on the storage of massive quantities of hematite and the development of
specific technologies of hematite-based paint production and use. The samples were recovered
at the three most significant Early Neolithic sites of the Mediterranean coast of Spain: Cova
de l’Or (Beniarrés, Alacant), Cova de la Sarsa (Bocairent, Valencia) and Cova Fosca (Vall
d’Ebo, Valencia), which together have provided the most important European collection of
Cardial ceramic ware (chronoculturally diagnostic of the Early Neolithic).

KEYWORDS: SEM–EDX, TXRF, XRD, FTIR, GC, EDXRF, EARLY NEOLITHIC, SPAIN,
HEMATITE, CINNABAR, PIGMENT ANALYSIS

INTRODUCTION

Red mineral colouring materials are common archaeological remains in prehistoric deposits.
They are often referred to as ochre, and used to discuss the antiquity of symbolic human
behaviour (e.g., Henshilwood et al. 2002; Marean et al. 2007; Soressi and D’Errico 2007;
Langley et al. 2008) or even rock art. They are also interpreted as evidence for ritual or
ceremonial activities, visual arts (rock art, body art and other forms of portable art) or burial
practices. However, ochre is just one among a wide variety of minerals with red colouring
properties available in natural deposits (hematite, heat-treated goethite and maghemite, among
others), and almost all of them have been used in the past for either symbolic or practical
purposes; for example, as fixatives for hafting tools (Beyries and Inizan 1982; Allain and Rigaud
1989; Wadley 2005; Lombard 2007), as natural abrasives for fine polishing of bone tools and
ornaments, as a natural antiseptic to tan leather (Audion and Plisson 1982; Adams 1988), to dry
tendons for different uses (such us bow strings or for attaching stone tools to the shafts), and
so forth.

*Received 25 February 2010; accepted 10 October 2011


†Corresponding author: email ines.domingo@ub.edu
© University of Oxford, 2012
Red pigments in the Valencian Early Neolithic (Spain) 869

Elemental and structural physicochemical analyses have previously been used to address
questions of types, sources, availability and accessibility, the process of manufacture and so
forth (see, e.g., Couraud 1978, 1987; Onoratini 1985; San Juan 1991; Bello and Carrera 1997).
This paper explores the use of red pigments in the Early Neolithic deposits of three renowned
Neolithic sites in the central Mediterranean region of Spain: Cova de l’Or, Cova de la Sarsa
and Cova Fosca (Fig. 1). Cova de l’Or and Cova de la Sarsa represent two of the most sig-
nificant sites for Early Neolithic studies, since together they have provided the most important
European collection of Cardial ceramic ware (the earliest Neolithic decorative style character-
istic of the Western Mediterranean and parts of Atlantic Europe, consisting of Cardium edule
shell imprints on the clay). Furthermore, although Cardial impressed decorations are mainly
non-figurative, the limited number of figurative Cardial decorations recovered at Cova de l’Or
and Cova de la Sarsa (including several human figures, a deer, a goat, a bull and a tree, among
others) represent the only portable parallels for post-Palaeolithic rock art of Mediterranean
Spain (see, e.g., Martí and Hernández 1988; Pérez 2001; Torregrosa and Galiana 2001; Martí
2006; Domingo et al. 2007), providing a minimum date for these World Heritage rock-art
traditions.
Despite the extraordinary discovery of nearly 1.75 kg of pulverized pigment stored in a vessel
at Cova de l’Or in 1952, as well as different fragments of red pigment and a significant number
of red-stained archaeological remains (including some red-stained Cardial vessels) at these three
sites, they have never been considered for analysis and have simply been referred to as ochre.
In this context, and as a first step in our project, this study aims to identify:
(1) The variety of minerals used as red colouring agents at these three Early Neolithic sites.
(2) Evidence of the processing of these materials, to determine whether the minerals were used
for dry application (direct application of the pigment, usually by crayons of iron compounds) or
if they were processed and transformed into powder and/or paint, and hence if different stages of
the processing (or chaîne opératoire) can be identified.

Figure 1 The geographical locations of the analysed sites.

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870 I. Domingo, P. García-Borja and C. Roldán

(3) The pigment composition of the red-stained archaeological artefacts recovered at these three
sites (ceramic wares, stone tools, grinding equipment, shells, bone tools, adornments and so
forth), to recreate the process of manufacture and to deduce the potential uses of the different raw
materials identified.

MATERIALS AND METHODS

As a first step, eight pigment samples from three different Early Neolithic sites were considered
for analyses (SEM–EDX, TXRF, XRD, FTIR and GC) to identify the variety of minerals used as
red colouring agents, different stages of the processing of these minerals and the presence of
organic compounds. At a later date, once hematite and cinnabar had been identified as the two
main minerals (see the analytical results below), additional non-destructive analyses (EDXRF)
of new samples (several red-stained archaeological remains) were performed to detect traces of
mercury, and thus confirm whether or not cinnabar was associated with any specific type of
remains. The idea was to explore whether or not the two minerals were used for different
purposes.

The archaeological context and sample description


At an early stage in the project, only eight samples from the Early Neolithic levels of these three
archaeological sites were considered for analysis: Cova de l’Or (samples 1.1–1.6), Cova de la
Sarsa (sample 1.7) and Cova Fosca (sample 1.8) (Table 1).
Cova de l’Or (Beniarrés, Valencia) has one of the best Early Neolithic archaeological collec-
tions of the Iberian Peninsula, including a significant assemblage of Cardial ceramic ware,
polished axes, marine shell ornaments, hair needles, rings, bracelets, needles, spoons and so forth
(Martí 1977, 1980). Early excavations by V. Pascual and J. San Valero started in the 1950s, and
resulted in some early publications (Visedo 1962). More systematic excavations were con-
ducted after the 1970s (Martí 1977, 1980, 2000), providing a unique Neolithic sequence ranging
from the Early Neolithic or Neolithic IA and the Final Neolithic or Neolithic IIA (5500 to
4000 cal bc).
Cova de la Sarsa (Bocairent, Valencia) has been central in Neolithic debates since its early
attribution to the Bell Beaker culture (Ballester 1928), the later linking to the Hispanic–
Mauritanian culture of northern Africa (San Valero 1950) or the more recent ascription to the
Neolithic (Fortea 1973; Martí 2008). Major excavations at the site were conducted by F. Ponsell
in 1925 (Ponsell 1929), funded by the SIP (Service for Prehistoric Studies), and by M. D.
Asquerino (Asquerino 1978; Asquerino et al. 1998). The site has provided one of the most
significant collections of Cardial ware from the region of Valencia, as well as burial remains
(Casanova 1978) and some recent evidences of Schematic rock art (Miret et al. 2008).
The Cova Fosca (Vall d’Ebo, Valencia) site includes well-known Palaeolithic cave paintings
(Hernández et al. 1988). It was first excavated by Professor M. Hernández in 1981, and another
small pit was undertaken by López in 1992 (López Mira 1994), providing a long stratigraphic
sequence with Solutrean, Magdalenian, Epipalaeolithic, Early Cardial Neolithic, Middle Neolithic
(Neolithic IC), Calcolithic and possibly Bronze Age levels.

Samples 1.1 and 1.4 (Fig. 2) The samples of red powder preserved inside vessel 1 (Fig. 3) were
discovered in 1952 (Visedo 1962) at the Cova de l’Or site. The morphology of this hand-made
vessel (globular shape, spout-handle and prominent neck) point to an original use as a liquid

© University of Oxford, 2012, Archaeometry 54, 5 (2012) 868–892


Table 1 The description, provenance, analytical methods and results for samples 1.1–1.8

Number Description Analytical methods Analytical Museum collection


of sample results
SEM–EDX TXRF XRD FTIR GC

Cova de l’Or
1.1 Pulverized red Main elements: Main elements: Fe, Ca Hematite, Hematite (raw 17048. Museu Arqueològic
pigment O, Fe Minor elements: Zn, Pb calcite and mineral + quartz Municipal Camil Visedo Moltó
Trace elements: Mn, Cu, Al quartz as a charge) (Alcoi)
Iron oxides and calcium compounds
1.2 Finely ground Main elements: No further analysis were performed 17050. Museu Arqueològic
red pigment O, Fe, Ca Municipal Camil Visedo Moltó
(Alcoi)
1.3 Block of raw Main elements: Main elements: Fe, Ca Calcite and Hematite (raw 17050. Museu Arqueològic
matter O, Fe Minor elements: Zn, Pb hematite mineral) Municipal Camil Visedo Moltó
Trace elements: K, Mn, Cu, Al. Sr linked to (Alcoi)
Ca
Iron oxides and calcium compounds
1.4 Coarse Main elements: Similar to sample 1, so no further analysis Similar to sample 17048. Museu Arqueològic
particles O, Fe were performed. 1.1 Municipal Camil Visedo Moltó
from (Alcoi)
sample 1.1
1.5 Red paste Main elements: Fe, Ca Hematite, Non-organic Absence Hematite + quartz 9747. Museu Arqueològic
residues Minor elements: Zn, Pb calcite and compounds of drying and clay to Municipal Camil Visedo Moltó
Trace elements: Ti, Ni, Mn, Al, Si, P, K. quartz oils prepare a paint (Alcoi)
Iron oxides and calcium compounds
1.6 Fine red Hg and S Quartz and Cinnabar (raw Museu de Prehistòria
powder Traces of Fe and Ca cinnabar mineral) (Valencia)
Cova de la Sarsa
1.7 Fine red Main elements: Fe, Ca Quartz and Quartz, calcite and Museu Arqueològic Municipal
powder Minor elements: Si, K, Ti (Fe impurities) calcite iron oxide Vicent Casanova (Boicarent)
Trace elements: Rb (related with K), Sr (hematite)
Red pigments in the Valencian Early Neolithic (Spain)

(linked to Ca)
Iron oxides and calcium compounds

Cova Fosca
1.8 Block of raw Main elements: Fe, Ca Quartz, calcite Hematite (raw Museu del Centre d’Estudis
pigment Minor elements: Mn, Si, K, Ti and hematite mineral) Contestans (Cocentaina)
Trace elements: Pb
Iron oxides and calcium compounds
871

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872 I. Domingo, P. García-Borja and C. Roldán

Figure 2 The first analysed samples.

Figure 3 Vessel 1, containing nearly 1.75 kg of pulverized red pigment.

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Red pigments in the Valencian Early Neolithic (Spain) 873

container (Gallart 1980) and dates it to the Early Neolithic or Neolithic I (Gallart 1980; Bernabeu
1989; García-Borja et al. 2011). When the spout-handle broke off, the vessel became a practical
container in which to store 1.75 kg of red pigment. Other archaeological remains recovered along
with the vessel, including several rings, bone tubes and antler fragments, confirmed this chro-
nology (Fig. 4) (Pascual-Benito 1998, 154; Martí et al. 2001) and suggested some potential uses
for the pigment at this specific site, as we discuss below.
The visual analysis of this pulverized pigment, with varying grain shapes, indicates a mechani-
cal pounding process, which should be confirmed with future experimental analysis. SEM–EDX
was used on these samples to compare the composition of both the fine (pulverized, sample 1.1)
and the coarse (not fine in texture and large) particles (sample 1.4). The results showed a uniform
composition, and thus further analyses were only performed on sample 1.1 (the fine powder) to
test whether it was ground mineral or a mixture of different raw materials.

Sample 1.2 This sample of red powder was preserved inside a test tube. According to the Museu
d’Alcoi records, it was stored in this test tube after being on display at the museum. It was likely

Figure 4 Archaeological remains located along with vessel 1 (photograph by Gonzalo Pla, 1952: Alcoi Museum
Archive).

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874 I. Domingo, P. García-Borja and C. Roldán

to be from Cova de l’Or, or even removed from the nearly 2 kg of the pigment originally stored
in vessel 1. To establish the reliability of this hypothesis, SEM–EDX was performed on this
sample and the results were compared to those obtained for samples 1.1 and 1.4 (García-Borja
et al. 2004).

Sample 1.3 This sample of colouring material was scraped off a 200 g tabular fragment of red
pigment (Fig. 2). This fragment was recovered along with vessel 1, either inside or around the
vessel. It was assigned a separate inventory number; hence we assume that it was likely to have
been found separately. SEM–EDX, TXRF and XRD were used on this sample to determine
whether or not the composition was similar to those of samples 1.1, 1.2 and 1.4, and therefore
whether they came from the same or different sources.

Sample 1.5 This sample of red paste residues was attached to the internal walls of a small
ceramic barrel with Cardial impressed decoration (impressions of Cardium edule shell) (Fig. 5).
The typology of the vessels dates it to the Early Cardial Neolithic or Neolithic IA (Gallart 1980;
Bernabeu 1989; García-Borja et al. 2011). Small containers fitted with asymmetric handles (such
as this one) are considered suitable for being suspended from a belt or strap worn around the
waist, and according to this, they have been previously interpreted as venom or paint containers
(Martí and Juan-Cabanilles 2002, 150). TXRF and XRD were used to determine the composition
of the sample (whether pulverized raw mineral or a compound of different raw materials to
prepare some sort of paint). FTIR and GC were also used to test the presence of lipid-binding
substances, usually required to form a smooth medium to produce paint.

Sample 1.6 This sample of fine red powder was preserved inside a Glycymeris sp. shell (Fig. 2).
It was recovered in 1957 along with several ceramic vessels with non-Cardial impressed

Figure 5 The small barrel containing red paint residues.

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Red pigments in the Valencian Early Neolithic (Spain) 875

decorations. In a previous publication, they were dated to the Early Postcardial Neolithic or
Neolithic IB—or, more precisely, between 5200 and 4500 cal bc (García-Borja et al. 2006),
according to Bernabeu’s chronological sequence (Bernabeu 1989). However, a recent review of
a significant part of the ceramic fragments recovered at layer 4, sector H2 of the Cova de l’Or site
demonstrated that most of the ceramic fragments found in this context had, in fact, Cardial
impressed decorations, while some others were decorated with a toothed chisel or a single-point
tool. According to these decorations, slightly older dates are suggested for this find: 5300 to
5000 cal bc. TXRF and XRD were used on this sample to determine whether or not the raw
mineral was similar to that of the previous samples, indicating a common source; and whether the
fine powder was ground pure pigment or a mixture of different raw materials.

Sample 1.7 This sample of fine red powder was preserved inside a shell (Glycymeris sp.)
(Fig. 2). When discovered in 1976, a white coating was covering the red pigment, which was
taken into consideration when interpreting the results of the analyses. Despite the lack of
stratigraphic context, it was recovered along with Cardial Ware, and thus dated to the Early
Cardial Neolithic or to a context with impressed ware but a low presence of the Cardial style
(5600 to 5000 cal bc). TXRF and XRD were used to identify the type of pigment, and to explore
whether the fine powder was ground pure pigment or a mixture of different raw materials.

Sample 1.8 This sample was scraped off a fragment of tabular red mineral (Fig. 2). According
to the stratigraphic context (stratum IIp), it also belongs to the Early Cardial Neolithic (5600 to
5200 cal bc) (García-Borja 2005). TXRF and XRD were used on this sample to identify the raw
mineral.
Additional sample analyses (by means of EDXRF spectrometry) were conducted during 2010 in
a selection of red-stained archaeological remains from Cova de l’Or (samples 2.1–2.7), with the
aim of completing previous analyses and discriminating between the pigments used. Only samples
from Early Neolithic levels, or fragments of impressed ware (Early Neolithic decorations), were
considered for analysis (Fig. 6 and Table 2).

Sample 2.1 This red paste was found filling the toothed chisel impressed decorations of a
ceramic fragment located at Crack F, with no stratigraphic context. The decoration reproduces an
anthropomorphic figure, with a rounded head, a rectangular body with zigzag infill and raised
arms represented by parallel lines (Martí and Hernández 1988).

Sample 2.2 This is an awl made of sheep/goat metapodial bone, with red stains on the epiphysis.
The awl was located at layer 6, square H4; which according to Juan-Cabanilles (the museum
curator) is the oldest archaeological level at this cave (level VI).

Sample 2.3 This pebble was used as grinding handstone for red pigments. It was found at layer
5, square H2 of this cave, which according to Juan-Cabanilles is a Cardial level, or level V.

Sample 2.4 This sample is a Bos sp. femur head with a lateral perforation. It was used as a
container for red pigment.

Sample 2.5 This is a ceramic fragment with partial remains of red engobe coating (a clay slip
consisting of a suspension in water of clay and/or other materials as colorants used in the
production of ceramic ware and applied on the clay body surface before firing the vessel) and

© University of Oxford, 2012, Archaeometry 54, 5 (2012) 868–892


876 I. Domingo, P. García-Borja and C. Roldán

Figure 6 Additional red-stained archaeological remains were analysed to discern traces of mercury.

Cardial decorations combined with other impressions made with a single-point tool. This
fragment was found at the same layer and sector as sample 1.6 (layer 4, sector H2).

Sample 2.6 This is a fragment of a small ceramic bottle, with Cardial decorations and a
red-stained internal surface, found at the superficial stratum of the cave.

Sample 2.7 This is a fragment of a small ceramic bottle with Cardial decorations and a
red-stained internal surface, with no stratigraphic context.

Analytical methods
As previously described, different methods (SEM–EDX, TXRF, XRD, FTIR, GC and EDXRF)
were employed on the different samples to investigate the questions addressed in this study. The
analyses were performed at the Instituto de Ciencias de los Materiales at the University of
Valencia (ICMUV).
Microanalyses combining scanning electron microscopy with energy-dispersive X-ray spec-
trometry (SEM–EDX) were performed on samples 1.1–1.4, to characterize the mineralogical
composition and to test the homogeneity of the samples. The SEM–EDX microanalyses were

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Red pigments in the Valencian Early Neolithic (Spain) 877

Table 2 The description, provenance, analytical methods and results for samples 2.1–2.7 from Cova de l’Or

Number Description of sample EDXRF Interpretation Museum collection

2.1 Red paste filling impressed Main elements: Fe Iron oxide 5294. Museu de Prehistòria
decorations of a ceramic Minor elements: Ca (València)
fragment
2.2 Bone awl with red stains Main elements: Fe Iron oxide Museu de Prehistòria (València)
Minor elements: Mn
2.3 Red-stained handstone pebble Main elements: Fe Iron oxide 5340. Museu de Prehistòria
Minor elements: Ca, K (València)
2.4 Red-stained Bos sp. femur head Main elements: Fe Iron oxide 5341. Museu de Prehistòria
Minor elements: Ca (València)
2.5 Fragment of Cardial Ware with Main elements: Fe Iron oxide 107.304. Museu de Prehistòria
red engobe covering Minor elements: Ca, K (València)
2.6 Fragment of small bottle with Main elements: Fe Iron oxide Museu de Prehistòria (València)
Cardial decoration and Minor elements: Ca, K
red-stained internal surface
2.7 Fragment of small bottle with Main elements: Fe Iron oxide 9763. Museu Arqueològic
Cardial decoration and Minor elements: Ca, K Municipal Camil Visedo
red-stained internal surface Moltó (Alcoi)

carried out on an environmental Philips XL-30 ESEM microscope, equipped with an EDAX PV
9760 system operating at 20 kV. The samples were mounted on stubs with conductive carbon
tape, but they were not coated with gold prior to microscopic observation.
TXRF (total reflection X-ray fluorescence spectrometry) was used to identify the elemental
constituents of samples 1.1, 1.3 and 1.5–1.8. TXRF was performed using a PicoTAX spectrom-
eter, with a molybdenum X-ray tube (30 kV and 0.5 mA) and a Si-PIN thermoelectrically cooled
detector with an energy resolution of 160 eV (FWHM at 5.9 keV).
The mineralogical composition of samples 1.1, 1.3 and 1.5–1.8 was determined by X-ray
diffraction spectrometry (XRD). The identification of the crystalline phases was performed over
samples manually ground in an agate mortar using a Seifer XRD 3003 TT diffractometer,
equipped with a Cu X-ray tube with a primary monochromator and a MBraun PSD-500 position
detector. The diffractometer was operated at 40 kV and 40 mA, covering an angular interval of
2q, range 2°–70°, with an interval of pass of 0.08°. The identification of phases was achieved by
comparison with a database based on JCPDS patterns.
FTIR (Fourier transform infrared spectrometry) and GC (gas chromatography) were used
on sample 1.5 to detect organic binders (lipids). The analyses were performed using a FTIR
BRUKER spectrometer and a HP5896 Chromatograph equipped with a non-polar capillary
column with a capillary injector, with a flow divisor and a flame ionization detector.
Finally, EDXRF (energy-dispersive X-ray fluorescence spectrometry) analyses of samples
2.1–2.7 were aimed at the detection of mercury traces to identify potential uses of cinnabar at the
Cova de l’Or site. The portable EDXRF spectrometer, developed and assembled at the ICMUV,
includes a silver X-ray tube (Eclipse-II, Oxford Instruments) operating in transmission mode
with a maximum voltage of 30 kV and a maximum current of 0.5 mA. A Si-PIN thermoelectri-
cally cooled detector (Amptek, Inc.), with an energy resolution of 180 eV (FWHM at 5.9 keV),
was used to detect the fluorescent beam emitted by the samples. The analysis compared the
EDXRF spectra of red-stained areas with non-pigmented areas.

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878 I. Domingo, P. García-Borja and C. Roldán

ANALYTICAL RESULTS

The analytical techniques used in this work are a qualitative approximation that show the
chemical elements or compounds present in the analysed samples (see Tables 1 and 2). In this
case, the lack of quantification is not a big drawback in their characterization, since the samples
should be characterized by the presence of some single inorganic element or by the identified
chemical compound.

Microanalysis (SEM–EDX) (Fig. 7) SEM–EDX analyses of samples 1.1 and 1.4 (the pigment
stored in vessel 1) and sample 1.3 (the piece of raw mineral) show a similar EDX spectrum,
pointing to a unique source (Fig. 7). While elemental fingerprints are useful to confirm this
common provenance, the true mineral identification requires structural identification using
other analytical techniques, such as diffraction. Therefore, further analyses of sample 1.1 were
necessary to identify the mineral used, as well as to determine whether the ground pigment
contained was in a pure state or was a combination of minerals to prepare a compound for
specific purposes.
On the other hand, although sample 1.2 was originally assumed to come from the 1.75 kg of
pigment stored in vessel 1, and despite the similarities with the elemental composition of the
other samples stored in this vessel (samples 1.1, 1.3 and 1.4), the high value of the Ca/Fe
fluorescence peak ratio leads us to consider different raw materials. These differences are
probably related to contemporary manipulation processes, causing potential contamination of the
sample prior to its display in the Camil Visedo Moltó Museum (Alcoi).

TXRF (Fig. 8) TXRF spectra obtained from samples 1.1, 1.3, 1.5, 1.7 and 1.8 are shown in
Figure 8. In all spectra, Fe and Ca are the main elements. Minor and trace elements such as
manganese (Mn), copper (Cu), lead (Pb), zinc (Zn), titanium (Ti) or nickel (Ni) are, probably,
impurities linked to the basic raw materials: iron oxides with calcium compounds. The identifi-
cation of aluminium (Al), silicon (Si) and potassium (K) in the samples is compatible with the
presence of quartz and clay raw materials. The presence of strontium (Sr) and rubidium (Rb) in
several samples is linked, respectively, to the presence of potassium and calcium minerals. TXRF
spectra of all these samples are compatible with pigments based on red iron oxide. On the
contrary, the main elements in the TXRF spectra of sample 1.6 are mercury (Hg) and sulphur (S),
and are related to the use of cinnabar (HgS) as a raw material.

XRD (Fig. 9) X-ray diffraction analyses have provided diffractograms with information about
the crystalline phases present in the samples (Fig. 9). Calcite (CaCO3) and hematite (a-Fe2O3) are
the main mineral phases in samples 1.1, 1.2, 1.3 and 1.5 from the Cova del’Or, although samples
1.1 and 1.5 also include quartz (SiO2), with a more significant presence in sample 1.5. According
to these results, and considering that sample 1.3 has been identified as a block of raw matter, we
can postulate that, probably, samples 1.1 and 1.5 have been processed from a raw material similar
to sample 1.3, but with the addition of quartz as an extender to give them body and to augment
their weight The diffractogram of sample 1.6 shows the diffraction patterns of quartz and
cinnabar (HgS). It is therefore a red colouring material made out of cinnabar, a soft red mercury
sulphide mineral. The results do not indicate the presence of added extenders. Thus, the cinnabar
ore was only transformed into powder on its own.
XRD analysis of sample 1.7 from the Cova de la Sarsa shows the presence of quartz and
calcite, with a predominance of calcite. Crystalline phases related to iron have not been detected,

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Red pigments in the Valencian Early Neolithic (Spain) 879

Figure 7 Microanalyses for samples 1.1, 1.2, 1.3 and 1.4.

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880 I. Domingo, P. García-Borja and C. Roldán

Figure 8 TXRF spectra for the analysed samples.

but the TXRF spectrum of this sample (Fig. 8) suggests a mixture of iron oxide, a calcium
compound and quartz. Red iron oxides may correspond to a poorly crystallized hematite hidden
by the high levels of calcite. In this case, the addition of calcite as an extender could not be
directly assumed, since at the time of sampling a white crust covering the red pigment was
detected, and it probably contaminated the sample. However, this deliberate addition of calcite
could not be rejected either, as demonstrated by the analysis of the Cova de l’Or samples. The

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Red pigments in the Valencian Early Neolithic (Spain) 881

Figure 9 XRD spectra for the analysed samples.

fine-grained pigment preserved in the shell was probably the result of a grinding or scraping
process, although it is difficult to determine if it was followed by a sifting process.
Finally, XRD analysis of sample 1.8 recovered at Cova Fosca shows diffraction patterns of
quartz, calcite and hematite.
The diffractograms of the above samples do not include mineral phases related to the minor
and trace elements identified in the TXRF analyses. Hence, we deduce that they either do not
present diffraction patterns or that they are below the detection limit of the diffractometer
employed.

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882 I. Domingo, P. García-Borja and C. Roldán

FTIR and GC (Fig. 10) Fourier transform infrared spectrometry (FTIR) and gas chromatogra-
phy (GC) were used on sample 1.5 to detect the use of lipids as binder/vehicle to produce paint.
FTIR indicates that the material covering the internal part of the vessel is inorganic, with the
presence of hematite (iron oxide, a-Fe2O3), calcite (calcium carbonate, CaCO3) and quartz, and
an absence of organic compounds. According to Maniatis and Tsirtsoni (2002), the presence of
organic compounds would have produced sharp lines close to 3000 cm-1 in the spectral region.
Gas chromatography (GC) indicates the absence of drying oils, although the presence of animal
fat at a trace level cannot be discarded, even though it has not been detected. Therefore, the FTIR
results show the absence of organic compounds in sample 1.5, while corroborating the presence
of calcium carbonate, quartz and hematite.

EDXRF Energy-dispersive X-ray fluorescence was used on samples 2.1–2.7 to identify traces of
mercury on several red-stained archaeological remains. However, all of the samples have iron as
the main element, and calcium as minor element. In samples 2.3, 2.5, 2.6 and 2.7, potassium was
also detected, whereas sample 2.2 contains manganese as oxide impurities. These results confirm
that iron oxide is the main pigment used at Cova de l’Or. On the contrary, mercury, and thus
cinnabar, are not detected, and cannot be associated with any red-stained archaeological remains.
A summary of the analytical results is shown in Tables 1 and 2.

DISCUSSION AND DATA INTERPRETATION

The elemental and structural physicochemical analysis of eight red pigment samples from the
Cova de l’Or, Cova de la Sarsa and Cova Fosca de la Vall d’Ebo sites confirm the use and
processing of two different red pigments during the Early Neolithic: hematite and cinnabar. The
characteristics and geographical distribution of the natural sources for these two minerals refer to
different resource acquisition and use strategies. Furthermore, the structural composition of the

1.0

0.9

0.8 α Fe2O3
0.7 H2O
SiO2
Transmittance

0.6
CaCO3
0.5

0.4

0.3
CaCO3
0.2 FTIR
0.1

0.0
4000 3500 3000 2500 2000 1500 1000 500 0
-1
Wave number (cm )

Figure 10 The FTIR spectrum for sample 1.5.

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Red pigments in the Valencian Early Neolithic (Spain) 883

samples containing hematite from Cova de l’Or reveal different stages of the manufacturing
sequence of this pigment, and thus the development of specific technologies of pigment use and
paint production during the Early Neolithic (Fig. 11).
Hematite has been identified in seven of the eight initial samples, becoming the most abundant
and widespread pigment used. The highest amount of this colouring material comes from Cova
de l’Or, as a fragment of raw mineral (sample 1.3), as 1.75 kg of a mixture of the ground mineral
and quartz (samples 1.1 and 1.4) or made into paint combining quartz and clay (sample 1.5).
Similarly, the results of the additional sample analysis of red-stained archaeological remains from
Cova de l’Or (Table 2) demonstrate that iron oxides were the only colouring agent directly used
on this site, whereas cinnabar appears as an exceptional raw material, with only a small sample
of finely ground pure mineral preserved inside a shell, and unconnected to other archaeological
remains that inform about the potential uses of this raw material.
A small amount of a very finely ground hematite was also preserved at Cova de la Sarsa,
whereas at Cova Fosca only a small piece of the raw mineral has been identified.
During the Early Neolithic, pigment procurement could be autonomous or secondary
(exchange or trade). Information about this specific stage of the pigment manufacture is not
available for the studied area, since the identification of sources was not a priority in the initial
stages of this project. Nevertheless, some preliminary information is available through the
literature, indicating that hematite is common in the region, in either cavities (Plá and Pavía
2003a,b) or superficial and tabular outcrops, and therefore the procurement could have been
local. On the contrary, cinnabar is more labour-intensive to procure, since cinnabar deposits occur
at relatively few locations in the Iberian Peninsula and mining is involved. There is a well-known
cinnabar mining locality in Ciudad Real (Spain): Almadén, the largest known concentration of
cinnabar in the world. Mining activities in Almadén have been recorded at least from the Roman
period, according to Pliny the Elder in his Natural history and Vitruvius (Edwards et al. 1999).
Previous activities, such as the possible supply of Andalusian megalithic tombs (Ramos et al.
1997), has also been suggested. More recently, contrasting lead isotope analysis of archaeological
(Casa Montero, Madrid) and natural cinnabar samples has suggested an exploitation of Almadén
district deposits as early as the sixth millennium bc (5300 bc: Hunt et al. in press). However, as
acknowledged by the authors, their analysis only considered a small sample (three mining
deposits) and thus, further analyses are required to confirm this initial hypothesis. The prov-
enance of the cinnabar from Cova de l’Or is still uncertain, since provenance analysis has not yet
been conducted. At this stage, Almadén—located more than 450 km from Cova de l’Or—cannot
be rejected as a potential source, since exchange of other raw materials and archaeological
remains between the Valencian territory and other Spanish distant localities is well documented
during this period (see, e.g., Orozco 2000). However, there are other minor cinnabar occurrences
in the Valencian territory. El cerro del Oriolet (Orihuela, Alicante province) is 116 km from Cova
de l’Or. Castellón province has several mines at Sierra de Espadán: Chovar, Eslida, Artana and
Alfondeguilla, about 150 km distant. Valencia province has two cinnabar deposits in Cullera
(57 km distant) and Siete Aguas (110 km distant: Casanova and Canseco 2002). Other deposits in
close proximity have also been located in Murcia (Mazarrón, 195 km distant) and Almería (Sierra
Cabrera, 310 km distant). Thus, future provenance studies should also consider these closer
deposits as potential sources, even though there is no evidence of their use prior to medieval
times.
The differences in pigment procurement and availability between these two minerals suggest
that the choice of cinnabar had some value beyond its colour, since hematite was easily avail-
able in the surroundings. References to the use of cinnabar during the Early Neolithic in Spain

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884 I. Domingo, P. García-Borja and C. Roldán

Figure 11 The proposed chaîne opératoire of pigment and paint production and use for the Cova de l’Or site.

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Red pigments in the Valencian Early Neolithic (Spain) 885

are still rare. At Casa Montero (Madrid) a flint lamina with traces of cinnabar affixed, dating
to c. 5300 to 5200 cal bc, has been interpreted as a votive offering (Hunt et al. in press). In
Murciélago de Zuheros cave (Córdoba), the red pigment filling the grooves of one potsherd
and two marble bracelets, and covering the internal walls of a vessel, has been identified as
cinnabar (Martínez et al. 1999). However, at the same site, Almagra wares were decorated with
hematite, suggesting a peculiar and maybe symbolic use of the artefacts decorated with cin-
nabar. The main difference between the Cova de l’Or and Murcielago de Zuheros sites is that
whereas in the latter cinnabar is mixed with other minerals (hematite, quartz, calcite and
feldspar), at Cova de l’Or cinnabar has only been pulverized, but no additives have been
identified. The use of this mineral might be related to the knowledge of its antiseptic (Delibes
2000) or preservative (Blas 2003) attributes, or the symbolic value assigned to those materials
that are rare or difficult to obtain. Although Cova de l’Or was mainly used as a residential
location, the recovery of some human remains may suggest an occasional use as a burial place.
Small caves were the most common burial place during the Early Cardial Neolithic. Never-
theless, it is likely that some select members of the community were buried in larger caves
(Bernabeu et al. 2001, 31–3). In this context, the presence of cinnabar in Cova de l’Or could
have been related with the preparation of funerary goods to be used either in situ or somewhere
else. The relation of cinnabar and Neolithic burial practices is not exclusive to Spain, since
cinnabar was also used for painting skeletons at Çatal Hüyük (eighth millennium bp: Mellaart
1967, 208), and another skull with cinnabar traces from the Pre-Pottery Neolithic B (PPNB)
was recovered at Tell Abu Hureyra, northern Syria (Molleson et al. 1992). Similarly, cinnabar
was also used as paint on a PPNB plastered skull from Kfar HaHoresh (Lower Galilee) (ninth
millennium bp: Goren et al. 2001).
Pigment (hematite) manipulation, direct use and transformation into powder and/or paint
probably took place within these three sites, since different stages of the transformation
process, as well as all sorts of transformation tools, storage and use containers, have been
recovered.
Fragments of hematite (samples 1.3, Cova de l’Or; and 1.8, Cova Fosca) were transported
to the cave prior to processing. Once at the cave, the mineral was directly used or transformed
into powder and/or pigment. Jardon’s use-wear analysis (40¥ binocular lenses) of the Cova de
l’Or pigment fragment (conducted at an early stage of this project) suggests a double use:
whereas the parallel grooves near one of the edges formed when directly rubbed over a hard
surface (some sort of rock), the polished ridges are characteristic of its use over a soft material
(perhaps to produce body paintings) (García-Borja et al. 2004). Hematite was later transformed
into powder, either by rubbing the raw mineral against a grinding stone or by pounding it
with a handstone (such as that of sample 2.3, a red-stained handstone pebble with iron oxide
residues).
At Cova de l’Or, red pigment impregnates the edges of seven blades and bladelet fragments,
a handstone (sample 2.3), the apophysis of several sheep/goat metapodials used to made bone
awls or hair pins (such as sample 2.2), the decorations of several bone rings, a wooden spoon,
several adornments, the proximal groove of a wooden-toothed chisel used to design ceramic
decorations, as well as for colour application (Pascual-Benito 1998); and, finally, the external
walls and decorations of several Cardial impressed vessels (such as samples 2.1, 2.5, 2.6 and
2.7).
Jardón’s use-wear analysis of the seven blades and bladelet fragments revealed that none of
them were used for pigment processing, and only in two cases could the pigment stains be related
to fixatives used for hafting purposes (Fig. 12). Similar analysis on the handstone indicated its use

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886 I. Domingo, P. García-Borja and C. Roldán

to crush pigment by pounding and to pulverize it by grinding (for further details, see García-Borja
et al. 2004), confirming an in situ processing of the raw mineral.
The pulverized hematite was then likely to have been mixed with quartz to control the fluidity
and colour of the pigment, and stored in vessel 1. A lack of sifting is deduced from the different
grain shapes of the sample. The storage in massive form of hematite probably indicates antici-
pation of future needs rather than a sporadic gathering for immediate use. It is likely to be related
to the other archaeological remains recovered at the same deposit and providing evidence of the
manipulation of this raw material: wooden spoons, bone awls, lithic tools and so forth. Similarly,
the presence of decorated adornments and some ceramic vessels with red and white pigment
filling the incised decorations reveals an in situ use of this pigment. Hence, the stored pigment
could have been used to haft lithic tools, to tan leather, to decorate ceramic wares and adorn-
ments, to polish bone tools or to produce paint. The analytical results of sample 1.5 (the red paste)
confirm a new stage in the hematite processing, the addition of clay to increase the consistency
and adherence, and a probable sifting to select the fine particles to obtain a more refined paste.
FTIR and GC identified no fatty binder. Nevertheless, the small size of the sample and the general
difficulty in identifying those components in paints prevent the rejection of this hypothesis. The

Figure 12 Red-stained blades and handstone from Cova de l’Or.

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Red pigments in the Valencian Early Neolithic (Spain) 887

resulting paste could be used for either body painting or rock art production, since the amount is
too small for ‘Almagra’ or ‘engobe’ pottery decoration.
Hematite would probably follow a similar process in the Cova de la Sarsa and Cova Fosca de
la Vall d’Ebo sites, although evidence of the technological process of manipulation and use of this
pigment are rare at these two sites.
At Cova de la Sarsa, the pulverized hematite was preserved inside a Glycimerys shell, which
probably served for pigment transportation or manipulation (similar to Cova de l’Or). Early
publications about this site do not mention colouring materials (Ponsell 1929; San Valero 1950;
Pérez 1999; Pascual-Beneyto and Ribera 1999). However, Asquerino’s more recent excavations
refer to a red-stained handstone, which was recovered along with other Early Cardial Neolithic
remains (Asquerino et al. 1998). During the revision of the archaeological remains currently
being curated at the Museu de Bocairent, another red-stained handstone and a new fragment of
raw mineral were identified (Fig. 13). Similarly, some of the early recorded Cardial Ware (San
Valero 1950) is likely to have red paste residues preserved inside, and may have a similar
function to the small barrel from Cova de l’Or. To test this hypothesis, further analysis would
be required.
The Early Cardial deposits of Cova Fosca (5500 to 5200 cal bc according to the Valencian
sequence: Bernabeu 1989; Juan-Cabanilles and Martí 2002) provided a red-stained grinding
stone and a handstone (Fig. 14). The grinding stone surface is polished, with several striations
resulting from abrasion. As described by Dubreuil (2004) the abrasive properties of ochre smooth
the rock surface. Hence the red stains could be either related to the pounding and pulverizing of
the hematite for different purposes, or with the use of the hematite to increase the abrasive
properties of the grinding stone, facilitating the polishing, regularizing and embellishment of
bone or stone tools (García-Borja et al. 2006).

Figure 13 Red-stained handstone from Cova de la Sarsa.

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888 I. Domingo, P. García-Borja and C. Roldán

Figure 14 Red-stained grinding stone and handstone from Cova Fosca de la Vall d’Ebo.

To summarize, the presence of red-stained grinding tools at these two sites suggests the parallel
development of an in situ technology for hematite manipulation and transformation, despite the
substantially lower recovery of red pigment when compared to Cova de l’Or.

CONCLUSIONS

The results of this research are archaeologically significant for Early Neolithic studies on the
development of technologies of pigment manipulation and paint production, since two different
types of red pigments (hematite and cinnabar), as well as different steps in the processing and
subsequent use of these pigments, have been identified. Furthermore, the identification of cin-
nabar in an Early Neolithic deposit (5300 to 5000 cal bc) indicates that the use of this pigment
in Spanish prehistory starts earlier than previously recorded (see, e.g., De la Peña and Rodríguez
1976; Domínguez and Morata 1995; Martín-Gil et al. 1995; Bello and Carrera 1997; Martínez

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Red pigments in the Valencian Early Neolithic (Spain) 889

et al. 1999; Delibes 2000). Only recently, a similar date has been confirmed for the Early
Neolithic site of casa Montero (Madrid) (Hunt et al. in press).
Elemental and structural physicochemical analyses of red pigment samples from three Early
Neolithic sites in the central Mediterranean region of the Iberian Peninsula (Cova de l’Or, Cova
de la Sarsa and Cova Fosca) have been central for understanding the ancient pigment choices and
technologies of the Early Neolithic populations of the region. Hematite was selected as the
main colouring material, while the use of cinnabar is rare. These two pigments refer to different
procurement strategies and different potential uses. The presence of cinnabar at Cova de l’Or,
together with the recent detection of this mineral at Casa Montero site (Madrid), constitutes the
earliest evidence of the use of this pigment in Spanish prehistory.
The identification of different stages of hematite processing and paint production reveals that
the Early Neolithic populations from Cova de l’Or had developed a paint production technology,
which involved local pigment procurement, in-situ direct use or transformation into powder and
paint, massive storage and a significant range of potential uses.
The use of two different raw minerals as red pigment confirms that the Early Neolithic people
were not constrained by the environmental availability of easily accessible pigments. While
hematite is locally available, cinnabar requires a greater input of time and energy, since it involves
mining and middle- to long-distance procurement or exchange (which should be confirmed
with future provenance analysis). It is generally accepted that culturally expensive materials
(those that are rare or energy expensive) usually carry prestige (Gero 1989, 93) or some sort of
symbolism. But it would also be likely that these Early Neolithic populations were aware of the
specific properties of each mineral, revealing a cultural choice of particular pigments according
to specific function.

ACKNOWLEDGEMENTS

The authors are grateful to the Servei d’Investigació Prehistòrica and the Museu de Prehistòria
(Diputació de València), the Museu Arqueològic Municipal Vicent Casanova (Bocairent), the
Museu Arqueològic Municipal Camil Visedo Moltó (Alcoi) and the Centre d’Estudis Contestans
for their support and help in accessing their collections. They are also grateful to the editor of this
journal and to the two external reviewers for their comments and suggestions, which have
certainly improved the quality of this paper. The analyses were funded by the BHA2003-05800
and Grupos 03/192 projects (Ministry of Science and Technology and the Valencian Bureau for
Science and Technology). The authors are also grateful to Drs Emili Aura, Joaquin Juan
Cabanilles, Bernat Martí and Josep Lluís Pascual for their advice and comments at different
stages of this project.

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