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Material Evidence For The Use of Attic White-Groun
Material Evidence For The Use of Attic White-Groun
Material Evidence For The Use of Attic White-Groun
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Article history: White-ground lekythoi ceramics offer important evidence for funeral practices in Ancient Greece (5th
Received 18 August 2009 century BC). The images painted-on these oil containers provide the best visual narrative for the events
Received in revised form surrounding death, including indications that the vessels themselves were used as part of the funerary
6 November 2009
rites. However, until now, their specific function and treatment within the funeral ceremony was not well
Accepted 17 November 2009
understood. We present here material evidence that the vessels were ritually burned, together with the
body of the deceased, during cremation, as evidenced by a diffuse purplish-red discolouration found on
Keywords:
many white-ground lekythoi. Through EPMA and mXAS studies, we show that: (1) this characteristic
Egyptian blue
White-ground lekythoi purplish-red discolouration is due to the presence of metallic copper nano-particles embedded in
Purplish-red discolouration a glassy layer; (2) this metal-glass matrix formed as the result of a high temperature reaction between
Copper nanoparticles painted-on Cu-based pigments (e.g., Egyptian blue) and the white-ground ceramic slip; and (3) the
Attica reaction occurred under a reducing environment. Given the mortuary context for these vessels, we
Greece propose the reduction firing to which the vessels were exposed was that associated with the cremation
Cremation of the body. The observation of discontinuous formation of the purplish-red discolouration along
SEM adjoining fragments supports the hypothesis that the vessels were broken prior to being burned. The
EPMA
majority of lekythoi in museum collections lack information on their original archaeological context, and
XANES
our data suggest the presence of this purplish-red discolouration may serve as a visual marker for
EXAFS
cremation. As such, it is expected our findings will provide a new basis for interpreting how this
important class of ceramic, and associated iconographic imagery, relates to Athenian funerary practices
and the ancient Greek notion of death.
Ó 2009 Elsevier Ltd. All rights reserved.
1. Introduction well as the transfigurative journey of the deceased from the world of
the living into the afterlife (Nakayama, 1982; Garland, 1985). This
Evocative descriptions of death and its attendant rituals are painting is often colourful and carefully executed employing
found throughout ancient Greek mythology and in the Homeric a palette of green (malachite, CuCO3$ Cu(OH)2), blue (Egyptian blue;
poems (Kurtz and Boardman, 1971; Sourvinou-Inwood, 1995). Our mineral cuprorivaite, CaCuSi4O10), red (vermilion, HgS), and orange
understanding of the Greeks’ attitude toward the afterlife has (iron earths, coloured by Fe2O3) colours. Many of these pigments are
further been enhanced by archaeological excavations which have fugitive at typical firing temperatures, and thus must have been
provided extensive material evidence of funerary practice (Morris, applied to the vessels after their initial firing (Scott and Taniguchi,
1992). One of the most important object types excavated from graves 2002; Wehgartner, 2002).
dating to the 5th century BC is the white-ground lekythos (see In addition to these intentionally applied pigments, a distinctive
Fig. 1A). The white-ground slips of these ceramics were painted with purplish-red discolouration appears as diffuse fields and isolated
depictions of the basic events of the funeraldprothesis, procession, spatters of colour on the surface of many Attic white-ground
inhumation, and subsequent visitation of the grave by the livingdas lekythoi (see Koch-Brinkmann, 1999 for an indication of the
numbers of polychromed lekythoi with this discolouration).
Although lacking correspondence to decorative elements, this
* Corresponding author at: Getty Conservation Institute, Collections Research
discolouration frequently is found near areas painted with the
Laboratory, 1200 Getty Center Drive, Suite 700, Los Angeles, CA 90049-1684, USA. pigment Egyptian blue, as illustrated in Fig. 1B, where islands of
E-mail address: mwalton@getty.edu (M.S. Walton). vibrant blue colour can be seen within the large diffuse purple-red
0305-4403/$ – see front matter Ó 2009 Elsevier Ltd. All rights reserved.
doi:10.1016/j.jas.2009.11.026
M.S. Walton et al. / Journal of Archaeological Science 37 (2010) 936–940 937
Fig. 1. (A) Greek white-ground lekythos from the Antikensammlung Staatliche Museen zu Berlin (F 2683) showing purplish-red discolouration. (B) Detail showing purplish-red
discolouration associated with overlying Egyptian blue pigment. (For interpretation of the references to colour in this figure legend, the reader is referred to the web version of
this article).
2.3. mXANES, and mEXAFS therefore suggests a similar mechanism is responsible for this
distinctive colouration.
X-ray absorption spectroscopy (XAS) measurements were per- To evaluate the chemical relationship between the aluminum-
formed on the hard X-ray microscope located at beam line 2–3 at the rich illite slip layer, the glass layer and the copper-rich particles,
Stanford Synchrotron Radiation Lightsource (SSRL). Beam line 2–3 a series of electron probe micro-analyses were acquired (dotted line
utilizes Pt-coated mirrors in a Kirkpatrick–Baez configuration to Fig. 2A) starting in the EB layer, scanning across the glass layer and
focus the incident beam to a 2 2 mm spot size. The incident beam a relatively large copper-rich particle, and terminating in the slip
energy was tuned using a Si(220) monochromator. Samples were layer. Fig. 2B shows the concentrations of Ca, Al and Cu, the
attached to a high precision XYZ stage oriented 45 to the incident elements that demonstrate the most significant variations, as
beam. The X-ray absorption signal was detected at 90 to incident a function of position. The concentrations of both Cu and Ca are
beam using either a Vortex silicon drift detector or a 3 element Ge highest in the EB and gradually decrease across the glass layer. The
detector. Cu K-edge (8979 eV) mXANES and mEXAFS were collected slight bump in Cu content near the glass-ceramic slip interface
by scanning through the XANES at step sizes of 0.35 eV and EXAFS corresponds to the location of the Cu-rich particle. By contrast, the
regions at step size of 0.05 1/Å . For all experiments, a Cu foil standard Al profile exhibits the opposite trend: the lowest concentration is
was used to calibrate the beam energy to 8979 eV. found in the EB, with a gradual increase across the glass layer, with
the highest concentration found in the ceramic slip. These data
indicate a bi-directional diffusion into the glass layer: Al in the
3. Results ceramic slip has undergone dissolution (Chakraborty et al., 1995)
and diffusion into the glass layer, while Cu and Ca, associated with
A backscatter electron image (BEI) of a representative cross- the EB pigment, have similarly diffused into the glass layer from the
section taken from a purplish-red area with overlying Egyptian blue pigment layer. Similar diffusive interaction between ceramic bodies
(EB) pigment is shown in Fig. 2A. In this image, a thin layer (5– and glass is well known from research on glazes (Molera et al.,
10 mm) of glass (appearing as a solid mid-grey tone in the BEI) can 2001; Walton and Tite, in press). Based on the diffusive behaviour
be seen separating the EB (seen to be composed of stacked lathes) observed in Fig. 2B, we conclude the vessel must have been heated
from the ceramic slip. EPMA of this glass layer found it to be rich in to 900–1000 C (melting temperature range of the glass) and
silica, with a total alkali (Na þ K) content of about 3 wt%, which is at maintained there for sufficient time to initiate slip dissolution and
the lower end of previous analyses of the interstitial glass which achieve significant diffusion driven mass transfer. EB would have
forms during the manufacture of EB (Hatton et al., 2008). The been applied to the surface only after the illite clay white-ground
relatively low alkali content of this glass layer is consistent with our vessel had been fired in a kiln (Scott and Taniguchi, 2002; Weh-
findings (discussed in depth below) that these values are lower gartner, 2002). Therefore, our observation of diffusion of Ca and Cu
than expected due to interaction with the underlying ceramic slip. from EB into the glass indicates the vessel must have been sub-
However, the most significant features in this image are the small, jected to a subsequent, secondary firing, not associated with its
spherical, high Z-contrast particles lying at and just below the manufacture. Furthermore, the inconsistent appearance of the
glass/ceramic slip interface, determined by EPMA to be copper-rich. purplish-red discolouration across the vessel suggests this firing
The diameter of these spheres ranges between 50 nm and 400 nm, was not carefully controlled.
with the majority falling between 80 nm to 100 nm (see inset in In order to identify the mineral form of the Cu-rich nano-parti-
Fig. 2A). These Cu-rich nano-particles resemble, in both size and cles and better understand the chemical nature of the secondary
shape, metallic structures that have been identified in Roman firing that formed them, Cu K-edge mXANES spectra, shown in
period dichroic glass (Barber and Freestone, 1990) and Islamic Fig. 3A, were collected from a Cu foil standard, the Cu-rich particles,
period ceramic luster decoration (Pradell et al., 2005; Roque et al., the interstitial glass layer, and the EB. The position of the absorption
2006). Colour in these nano-particulate materials is caused by the edge of the XANES spectrum for the Cu-rich particles is identical to
absorption of light at their respective surface plasmon resonances that of the copper foil standard (8979 eV), indicating the Cu-rich
(Pradell et al., 2008). Our discovery of copper-rich nano-particles particles are present in the metallic state (Cuþ0). Furthermore, the
within the purplish-red discolouration on white-ground lekythoi similarity of the modulations at higher energy suggests very similar
A B 18
16 Egyptian blue ceramic
14
Cu
12
Al
10
wt%
Ca
8
6
4
2
0
0 2 4 6
Distance µm
Fig. 2. (A) SEM backscatter electron image of a cross-section of Egyptian blue (EB) and underlying copper particles at interface between glass phase and ceramic. Inset shows high
magnification image of copper particles. (B) Quantitative electron microprobe line scans of Cu, Al, and Ca starting from the EB (D ¼ 0 mm) and terminating in the ceramic (D ¼ 5 mm).
(For interpretation of the references to colour in this figure legend, the reader is referred to the web version of this article).
M.S. Walton et al. / Journal of Archaeological Science 37 (2010) 936–940 939
A
coppe r foil standard
20
B
Normalized Absorption
15
10
coppe r-rich particle s
5
K3 Chi(k)
0
inte rstitial glass
-5
-10
Fig. 3. (A) Cu K-edge XANES spectra of the Cu foil standard, Cu-rich particles, glass layer, and EB from the cross-section shown in Fig. 2. (B) EXAFS spectrum of Cu particle (open
circles) compared to Cu foil demonstrating that copper particles have a bulk metallic structure.
local chemical environments. These findings are further strength- particles produced in controlled laboratory conditions necessitates
ened by the mEXAFS spectrum of the Cu-rich nano-particles, shown the consideration as to whether it might be a pigment deliberately
in Fig. 3B, which shows nearly exact correspondence to that of a Cu produced by reduction of a copper salt. This hypothesis was put forth
metal foil, indicating that the first several coordination shells around by Noll et al. (1975, 1974) who mentioned the purplish-red material
the Cu atom in the Cu-rich particles are indistinguishable from found on lekythoi in two surveys on painting on ancient ceramics.
coordination shells observed in metallic Cu foil. Other than its presence on the described Attic white-ground leky-
The Cu K-edge mXANES spectrum from the interstitial glass layer thoi, a nano-particulate Cu red pigment used to decorate ceramics is
shows a large pre-edge peak similar to those typically associated completely unknown prior to the 8th century AD (Pradell et al.,
with Cuþ1 species. However, the energy at which this peak appears 2008), casting considerable doubt on its intentional application
(near 8986 eV) is at the high end of the range reported in the here. Furthermore, the appearance of the discolouration on the
literature of between 8983 eV and 8986 eV (Kau et al., 1987; vessels is inconsistent with it having been deliberately applied.
Gonella et al., 2005; Lamberti et al., 1998, 2003). The intensity and These anecdotal arguments however are substantiated by the
position of this peak, attributed to the dipole allowed 1s / 4p diffusion and chemical state information presented here, which
electronic transition, has been shown to correlate with the coor- provides material evidence this purplish-red discolouration
dination number (Kau et al., 1987). Peak positions above 8985 eV occurred as a result of the vessels having been subjected to pro-
are associated with 4-coordinate Cuþ1 complexes, but typically longed secondary reducing atmosphere firing at high temperatures
have significantly lower amplitude than the white line, in contrast around 1000 C. Taken together with the fact that white-ground
to the peak observed in the spectrum shown in Fig. 3A. Therefore, lekythoi were associated exclusively with funerary rituals, this
although the XANES spectrum of the interstitial glass layer suggests suggests that the secondary firing of these vessels must have been in
the Cu atoms are present in a valence state of þ1, further study is a smoke-filled, and thus reducing, fire at the grave site.
necessary to understand the significance of the observed shift in Archaeological excavations supplement this analytical conclu-
the position of the prominent pre-edge feature. sion with ample evidence of cremation at the grave coming from
The position of the Cu K-edge and the general shape of the the Keremeikos region of Athens (Kurtz and Boardman, 1971). Fine
spectrum taken from the EB is similar to previously published ceramicsdincluding white-ground lekythoidtypically found in
XANES spectra of Egyptian blue, and other Cuþ2 oxides, in terms of association with cremations were burned in offering trenches
absorption edge energy, shape and position of the white line at adjacent to graves that also contained charred items typically
8996 eV (Pages-Camagna et al., 2006; Shimizu et al., 2001; Kau associated with banquet services (Hampe, 1960; Noble, 1985;
et al., 1987). Additionally, the XANES spectrum shows a pre-edge Houby-Nielsen, 1992, 1996). Interestingly, archaeologists have
feature near 8980 eV, attributed to the 1s / 3d electronic transi- noted a variability in the soot deposits found on sherds, from which
tion and one of the diagnostic features of Cuþ2 species (Kau et al., they conclude the pottery found in these trenches was ostensibly
1987; Shimizu et al., 2001). deliberately broken and then burned (Houby-Nielsen, 1992, 1996),
Similar to the mechanism by which metallic nano-particles are consistent with our assertion that the differential appearance of the
formed in modern silicate glass materials (Roque et al., 2006), our purplish-red discolouration on adjoining sherds reflects the vessel
findings indicate that reduction of the Cuþ1 dissolved in the glass layer having been broken prior to burning. Our data provide the first
resulted in the formation of the metallic copper nano-particles. Taken material evidence linking the appearance of the purplish-red dis-
together with the diffusion data presented above, this suggests that colouration with the deliberate breaking and burning of the vessel
the uncontrolled, secondary firing to which the white-ground leky- as part of a cremation ceremony. Therefore, the presence of this
thoi were subjected, also occurred in a reducing environment. purplish-red discolouration alone may serve as a diagnostic marker
that a particular white-ground lekythos was used in a cremation.
4. Discussion and archaeological implications Unfortunately, the majority of lekythoi in museum collections were
not archaeologically excavated under controlled conditions, and
The structural and chemical similarity of the purplish-red dis- thus any direct link associating them with a funeral ritual has been
colouration found on white-ground lekythoi to metallic nano- lost. However, the evidence presented here provides a new means
940 M.S. Walton et al. / Journal of Archaeological Science 37 (2010) 936–940
by which this class of ceramic may be directly linked with the Houby-Nielsen, S., 1996. The archaeology of ideology in the Kerameikos: new
interpretations of the ‘Opferrinnen’, in: Hagg, R. (Ed.), The Role of Religion in
cremation process, thereby enabling archaeologists and art histo-
the Early Greek Polis, Proceedings of the Third International Seminar on
rians to confidently include a much a larger number of these Ancient Greek Cult 1992, Svenska Institutet i Athen, Stockholm.
objects in their analysis, which in turn has the potential to Kau, L., Spira-Soloman, D.J., Penner-Hahn, J.E., Hodgson, K.O., Solomon, E.I., 1987. X-
dramatically change our understanding of Athenian funerary ritual. ray absorption edge determination of the oxidation state and coordination
number of copper: application to the type 3 site in Rhus vernicifera laccase and
its reaction with oxygen. Journal of the American Chemical Society 109, 6433–
5. Conclusions 6442.
Koch-Brinkmann, U., 1999. Polychrome Bilder auf weissgrundigen Lekythen. Biering
and Brinkmann, Munich.
In summary, our findings provide the physical evidence linking Kurtz, D., Boardman, J., 1971. Greek Burial Customs. Cornell University Press, Ithaca.
the purplish-red discolouration found on white-ground lekythoi Lamberti, C., Bordiga, S., Zecchina, A., Salvalaggio, M., Geobaldo, F., Otero
Areán, C., 1998. XANES, EXAFS and FTIR characterization of copper-exchanged
with ritual activities associated with cremation. These data provide Mordenite. Journal of the Chemical Society, Faraday Transactions 94 (10),
new and specific information on Athenian funerary practices, in 1519–1525.
particular that lekythoi were not simple burial gifts but were Lamberti, C., Bordiga, S., Bonino, F., Prestipino, C., Berlier, G., Capello, L., D’Acapito, F.,
Llabrés i Xamena, F.X., Zecchina, A., 2003. Determination of the oxidation and
vessels richly embellished by potters with the sole purpose of being coordination state of copper on different Cu-based catalysts by XANES spec-
broken and burned in a funerary ritual. Based on these chemical troscopy in situ or in operando conditions. Physical Chemistry Chemical Physics
and archaeological data, we now have a more complete under- 5, 4502–4509.
Molera, J., Pradell, T., Salvadó, N., Vendrell-Saz, M., 2001. Interaction between clay
standing of how white-ground lekythoi were used in the ritual
bodies and lead glazes. Journal of the American Ceramic Society 84, 1120–1128.
setting and the unusual conditions in which the purplish-red Morris, I., 1992. Death-Ritual and Social Structure in Classical Antiquity. Cambridge
discolouration formed. University Press, Cambridge.
Nakai, I., Numako, C., Hosono, H., Yamasaki, K., 1999. Origin of the red color of
Satsuma copper-ruby glass determined by EXAFS and optical absorption
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Kaestner of the Antikensammlung Staatliche Museen zu Berlin and Noll, W., Holm, R., Born, L., 1975. Painting of ancient ceramics. Angewandte Chemie
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of the J. Paul Getty Museum. Also we thank Giacomo Chiari, and Pradell, T., Molera, J., Roque, J., Vendrell-Saz, M., Smith, A.D., Pantos, E., Crespo, D.,
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