FIRING ANALYSIS OF SOUTH-EASTERN MISSOURI INDIAN POTTERY USING IRON MÖSSBAUER SPECTROSCOPY*

The Mössbauer spectra of prehistoric pottery and clay from the Malden Plain of south-eastern Missouri, USA, were examined. The pottery dates from AD 500 to 1400. The earlier sherds were tempered with sand and the later ones with shell. The sherds and clay contain a mixture of illite, smectite, and kaolinite. Most samples of clay and sherds contained both ferric and ferrous species. The spectral parameters for the ferric species were %DLE_Q～0. 7—1.1 mms^-1 and δ～0.0–0.3 mms^-1 for the ferrous species, ΔE_Q～2.1–2.7mms^-1 and δ～0.7–1.0mms^-1. The ferric to ferrous ratio is more accurately determined from the spectra than from consideration of the colour or the firing core of the sherds, which are not always related to the iron species ratio. Differences among sherds in the ferrous ΔE_Q can be related to original temperature of heating but with low precision.     

MÖSSBAUER SPECTRA OF IRON IN CERAMICS AND THEIR RELATION TO POTTERY COLOURS

The chemical states of iron in a few selected clays and ceramics have been ascertained employing the technique of Mössbauer absorption. The effects upon the iron in firing the clays under different conditions have also been measured. Colour changes are correlated with the various chemical states of iron before and aftefiring.     

MICRO‐RAMAN SPECTROSCOPY CHARACTERIZATION OF DELLA ROBBIA GLAZES*

Micro‐Raman spectroscopy and the laser‐induced transformation technique were used for systematic study of five coloured glazes on Saint John the Baptist (29 inch tondo), a majolica terracotta relief attributed to Luca Della Robbia and on permanent exhibit in The John and Mable Ringling Museum of Art. We suggest that ions in a lead silicate matrix, called ‘lead ultramarine’, could contribute to the famous Della Robbia blue colour, in addition to the effect of Co atoms as suggested previously by Pappalardo et al. (2004 ). The original yellow glaze contains lead(II) antimonate. The green is a mixture of the yellow and blue pigments, the brown contains hematite, and the white glaze contains tin dioxide as an opacifier. The use of lead oxide as a main fluxing agent is confirmed by laser‐induced micro‐crystallization.     

CHEMICAL CHARACTERIZATION OF ANCIENT MESOAMERICAN ‘COPAL’ RESINS: PRELIMINARY RESULTS*

So‐called ‘copal’ resins from nine Aztec/Mixtec turquoise mosaics have been subject to analysis by gas chromatography – mass spectrometry to examine their higher terpenoid composition with a view to botanical identification. Botanical specimens and modern commercial ‘copal’ resins were analysed for reference. A range of botanical sources for the resins was identified, including pine, Protium and possibly Bursera. The data reinforce the ambiguity in the use of the term ‘copal’ and demonstrate the need for further work on characterization of ancient Bursera resins.     

THE APPLICATION OF TIME‐OF‐FLIGHT SECONDARY ION MASS SPECTROMETRY (ToF‐SIMS) TO THE CHARACTERIZATION OF OPAQUE ANCIENT GLASSES*

Time‐of‐flight secondary ion mass spectrometry (ToF‐SIMS) has been used, for the first time, for the characterization of opaque ancient glasses. Isotope‐specific chemical imaging with sub‐micron resolution enabled the separate analysis of opacifiying inclusions and the surrounding glass matrix. Phase identification has been demonstrated and quantification of the matrix composition has been investigated by use of Corning Glass Standard B as a model. Trace element detection limits are typically in the range 0.5–5.0 ppm atomic—in favourable cases down to 0.01 ppm. For the analysis of inclusions in particular, this has the potential to provide new information of use in establishing provenance and trade routes by ‘fingerprinting’ as well as the investigation of manufacturing techniques, as demonstrated by comparisons between glasses and with EDX data from the same samples.     

ON THE ORIGIN OF GREY AND BLACK ‘COLOURS’ OF ANCIENT POTTERY: ROLE OF Fe AND Ti4+ IONS

It is shown, from comparisons with the optical absorption of minerals, that the black and grey colours of pottery can arise from Fe²⁺ Fe³⁺ and Fe²⁺ Ti⁴⁺ charge-transfer (or electron-hopping) processes, the cations being located at the centres of adjacent edge-sharing octahedra.     

THE STUDY OF NABATAEAN ORGANIC RESIDUES FROM MADÂ’IN SÂLIH,ANCIENT HEGRA,BY GAS CHROMATOGRAPHY – MASS SPECTROMETRY*

Four Nabataean samples collected in some of the monumental tombs of Madâ’in Sâlih, ancient Hegra, in Saudi Arabia, have been studied by gas chromatography coupled with mass spectrometry. These samples are textile fragments that are either covered with a black layer or bound together with some black amorphous substance. Fatty acids and triterpenoic compounds were detected. Eight triterpenic compounds were identified: ursa‐9(11),12‐dien‐3‐ol, ursa‐9(11),12‐dien‐3‐one, olean‐9(11),12‐dien‐3β‐ol, β‐amyrone, β‐amyrin, α‐amyrone, α‐amyrin and lupeol. The resinous chemical composition and these pentacyclic alcohols, in considerable proportion, indicate a resin of the Burseraceae family, possibly of the genus Canarium.     

PROVENANCE DETERMINATION OF MYCENAEAN IIIC VESSELS FROM THE 1934–1939 EXCAVATIONS AT TARSUS‐GÖZLÜKULE BY NEUTRON ACTIVATION ANALYSIS

Neutron Activation Analysis (NAA) has been carried out in order to determine the provenance of a selected set of 30 sherds of Mycenaean style excavated at Tarsus‐Gözlükule. The provenance could be established or made feasible in 80% of the samples. The results confirm the current status of research, namely that in the LH IIIC phase trade patterns changed and Mycenaean wares, which used to be exported to the Near East, were now produced locally. At Tarsus, the LH IIIC imports came from Cyprus and the eastern Aegean.