MOLECULAR AND ISOTOPIC DEMONSTRATION OF THE PROCESSING OF AQUATIC PRODUCTS IN NORTHERN EUROPEAN PREHISTORIC POTTERY*

A number of charred surface residues, adhering to ceramic containers, were obtained from various coastal and inland sites in north‐west Europe dating from the sixth to the fourth millennium cal bc . In order to investigate the use of these vessels and in particular to identify any marine products, the residues were subjected to carbon and nitrogen stable isotope analysis. Variation in carbon isotope ratios between different samples indicated that some vessels may have been used to process marine products. This analysis was corroborated by specific identification of aquatic products following structural and isotopic characterization of lipids extracted from selected samples.     

COMPOSITIONAL VARIATIONS IN AGED AND HEATED PISTACIA RESIN FOUND IN LATE BRONZE AGE CANAANITE AMPHORAE AND BOWLS FROM AMARNA,EGYPT*

This study examines resinous deposits from the interior surfaces of sherds of imported Canaanite amphorae and locally produced bowls from the 18th Dynasty site of Tell el‐Amarna, Egypt. Archaeological evidence indicates that the Canaanite amphorae were used for resin transport, whilst the bowls are associated with burning resin as incense. A number of characteristic triterpenoids identify all the resinous deposits from both vessel types as Pistacia spp. No other resins were observed and there was no evidence of mixing with oils or fats. The composition of the archaeological resins is more complex than that of modern pistacia resin, due to degradation and generation of new components. Experimental heating alters the relative abundance of the triterpenoid composition of modern pistacia resin. One component, the triterpenoid 28‐norolean‐17‐en‐3‐one, is produced by such heating; however, an increase in its relative abundance in ancient samples is not matched by the archaeological evidence for heating. It is therefore not possible to use this component reliably to identify heated resin. However, additional unidentified components with a mass spectral base peak at m/z 453 have been associated with seven (out of 10) bowls and are not observed in resins associated with Canaanite amphorae. It is proposed that these components are more reliable molecular indicators of heating.     

How Did Mississippians Prepare Maize? The Application of Compound‐Specific Carbon Isotope Analysis to Absorbed Pottery Residues From Several Mississippi Valley Sites

A newly developed compound‐specific stable carbon isotope technique allows the detection of maize in absorbed organic pottery residues. This method was applied to absorbed organic residues from a variety of Mississippi Valley potsherds, and successfully identified maize components. Maize was cooked in sampled vessels less often than expected, but otherwise fitted expected patterns of maize use derived from stable carbon isotope analysis of human bone from the region. Absorbed organic pottery residue analysis is useful in determining pottery use, particularly in concert with other analytical methods.     

EXPERIMENTAL EVIDENCE FOR THE PROCESSING OF MARINE ANIMAL PRODUCTS AND OTHER COMMODITIES CONTAINING POLYUNSATURATED FATTY ACIDS IN POTTERY VESSELS*

ω‐(o‐Alkylphenyl)alkanoic acids are known to form in vitro from triunsaturated fatty acids following protracted heating. These compounds have recently been identified in absorbed lipid extracts obtained from archaeological pottery vessels, providing a potentially valuable new class of indicator for the processing of commodities, such as marine oils, which contain high abundances of polyunsaturated fatty acids. Experiments were conducted to assess whether ω‐(o‐alkylphenyl)alkanoic acids form when pure compounds and complex triacylglycerol mixtures are heated with a fired clay. The results demonstrate that ω‐(o‐alkylphenyl)alkanoic acids are only produced following heating of unsaturated fatty acids (tri‐, di‐ and monounsaturated species) or complex unsaturated fatty acyl lipids at around 270°C. Heating saturated fatty acyl lipids does not yield ω‐(o‐alkylphenyl)alkanoic acids. Thus, when searching for evidence for the processing of marine derived animal fats in archaeological pottery vessels, it is essential that: ω‐(o‐alkylphenyl)alkanoic acids of carbon length C₁₈ and C₂₀ should be present, ideally with C₂₂ also detectable (if only in trace abundances), together with at least one of the three isoprenoid fatty acids (phytanic, pristanic or 4,8,12‐tetramethyltridecanoic acid).     

A PROVENANCE STUDY OF POTTERY FROM ARCHAEOLOGICAL SITES NEAR CANOSA,PUGLIA (ITALY)*

Studies have been carried out to assess the provenance of selected pottery excavated at archaeological sites near Canosa, Puglia (Italy). Sixty-six sherds, ranging in date from the mid-seventh century BC to the beginning of the third century BC, were analysed by atomic absorption spectroscopy and 16 elements were determined. The analysis data were subjected to multivariate classification procedures. Tests showed that the majority of the examined sherds came from ancient local kilns; a probable Ionian origin was established for some other sherds, while the rest were of unknown origin.     

Lipid Residues from Low‐Fired Pottery

This paper assesses the fate of lipids associated with low‐temperature and pit‐fired pottery to determine to what degree organic compounds persist or are removed during short‐firing episodes below 800 °C. Three different types of clay were fired using contrasting techniques including at 400 °C for 4 h in a muffle furnace, and pit‐firing in which pottery was fired to higher temperatures but for shorter periods of time. Total lipid extracts obtained by solvent extraction of test sherds were screened using gas chromatography‐flame ionization detection (GC‐FID) to determine the lipid concentrations and gas chromatography–mass spectrometry (GC–MS) to identify the organic compounds present. The results showed that firing of clay removes all naturally occurring alkyl lipids; however, during pit‐firing, diterpenoid lipids were introduced into the clay as a condensate from pine ( Pinus spp.) wood used as fuel. These results confirm that alkyl lipids, e.g., fatty acids, can be reliably associated with the use of vessels, although caution is required when interpreting the origins of lipids that might derive from fuel used in firing.     

A COMPARISON OF METHODS FOR ESTABLISHING FATTY ACID CONCENTRATION GRADIENTS ACROSS POTSHERDS: A CASE STUDY USING LATE BRONZE AGE CANAANITE AMPHORAE*

Canaanite amphorae fragments in fabrics believed to be associated with the bulk transport of vegetable oils from the fourteenth‐century BC site of Amarna, Egypt, have been examined. A comparison is made between solvent extraction, saponification and the use of TMTFTH (m‐trifluoromethylphenyl)trimethylammomum hydroxide, used here for the combined extraction and derivatization of ceramic‐absorbed organic residues. Extracts were studied using gas chromatography and gas chromatography‐mass spectrometry. The extraction of fatty acids from small ceramic samples has established concentration gradients of absorbed organic matter from the inner to the outer surfaces of the sherds.     

CHEMICAL CHARACTERIZATION AND STATISTICAL MULTIVARIATE ANALYSIS OF ANCIENT POTTERY FROM MESSINA,CATANIA, LENTINI AND SIRACUSA (SICILY)*

This paper presents the chemical characterization of 79 fragments of Archaic and Hellenistic fine‐grained pottery from archaeological sites in Messina, Catania, Lentini and Siracusa (Sicily). The sherds were classified as ‘calcidian’, ‘banded’, ‘unvarnished’ and ‘black varnished’ pottery. The major and trace elements identified by X‐ray fluorescence (XRF) were statistically elaborated using the method proposed by J. Aitchinson in 1986 for the analysis of compositional data. From cluster analyses using element/SiO₂ log‐ratios, it was possible to group the pottery found in Catania, Lentini and Siracusa into highly linked clusters. Conversely, the Messina pottery was divided into two clearly distinct groups. With the aim of identifying any possible mineralogical differences between the two Messina groups, Fourier transform infrared (FT–IR) absorption measurements were made, showing only quantitative differences in plagioclase and muscovite. The specific groups of pottery with restricted chemical compositions are considered to be of local production, also on the basis of archaeological and petrographic evidence.     

CHEMICAL CHARACTERIZATION OF TIN‐LEAD GLAZED POTTERY FROM THE IBERIAN PENINSULA AND THE CANARY ISLANDS: INITIAL STEPS TOWARD A BETTER UNDERSTANDING OF SPANISH COLONIAL POTTERY IN THE AMERICAS*

Majolica pottery was the most characteristic tableware produced in Europe during the Medieval and Renaissance periods. Because of the prestige and importance attributed to this ware, Spanish majolica was imported in vast quantities into the Americas during the Spanish Colonial period. A study of Spanish majolica was conducted on a set of 186 samples from the 10 primary majolica production centres on the Iberian Peninsula and 22 sherds from two early colonial archaeological sites on the Canary Islands. The samples were analysed by neutron activation analysis (NAA), and the resulting data were interpreted using an array of multivariate statistical approaches. Our results show a clear discrimination between different production centres, allowing a reliable provenance attribution of the sherds from the Canary Islands.     

Chemical characterization of ancient pottery from sudan by x‐ray fluorescence spectrometry (xrf), electron microprobe analyses (empa) and inductively coupled plasma mass spectrometry (ICP–MS)*

Sixty‐four sherds and seven natural clays from prehistoric sites in northwestern Sudan have been submitted to petrological and chemical analysis using XRF spectrometry, EMPA and ICP–MS. According to their texture, the sherds form five different groups. The high contents of P₂O₅ (more than 0.5 wt%) discerned in 19 samples and the variation of the P₂O₅ content in two samples of the same vessel can be explained by post‐depositional processes or by the ancient organic contents (e.g., milk) of the vessel. Chemical classification of the pottery bulk suggests that vessels were made locally, as only sherds from the same area show homogeneity of data.     

MODIFIED MAHALANOBIS FILTERS FOR GROUPING POTTERY BY CHEMICAL COMPOSITION*

A statistical procedure for grouping pottery in provenance studies by chemical data is presented, which now is routinely in use in our laboratory. It is based on the Mahalanobis filter method and X² -statistics, and can be used for both establishing groups and assigning single sherds to already known groups, thus replacing principal components analysis or cluster analysis and avoiding their problems in grouping pottery. The new method is able to consider correlations, uncertainties of measurement and constant shifts of the data in case of dilution. In particular, considering dilution effects results in both a better assignment to and separation of reference groups and is also equivalent to the compositional data approach, if log-transformed data are used. Other distortions of data (e.g., mixing of clays) can also be considered.     

CAMPANIAN POTTERY FROM ANCIENT BRUTTIUM (SOUTHERN ITALY): SCIENTIFIC ANALYSIS OF LOCAL AND IMPORTED PRODUCTS*

One hundred and fifty-seven sherds of Campanian pottery were analysed by inductively coupled plasma optical emission spectroscopy (ICP-OES) and flame emission spectroscopy (FES). The sherds were found in the course of archaeological excavations carried out at the sites of Sibari, Cosenza, Crotone, Locri, Reggio and Oppido Mamertina in southern Italy (ancient Bruttium, today Calabria). Analyses were carried out on dissolved samples, determining 15 elements per sample (Al, Fe, Ca, Mg, Ti, Mn, Sr, Ba, Cr, Cu, Y, La and Sc by ICP-OES, and Na and K by FES). Analytical data were subject to multivariate statistical treatment by hierarchical cluster analysis and principal components analysis. Results indicated different compositional groups, allowing one to separate suspected imports from Campania, Etruria and Sicily from each other and from likely local products. The latter could be further classified into different groups, comprising imitations of foreign forms as well as original local products.     

A NEW METHOD FOR EXTRACTION,ISOLATION AND TRANSESTERIFICATION OF FREE FATTY ACIDS FROM ARCHAEOLOGICAL POTTERY

This paper presents evidence for increased recovery of organic residues from archaeological pottery through use of a microwave‐assisted liquid chromatography protocol. C_16:0 and C_18:0 saturated fatty acids were obtained from archaeological potsherds recovered from nine Neolithic settlements in the Middle East dating between 4700 and 7300 cal bc , including materials that had not produced evidence for the survival of any lipid species through use of ‘conventional’ solvent extraction techniques. Compound‐specific isotopic analyses of C_16:0 and C_18:0 fatty acids in potsherd extracts subsequently revealed δ¹³C/δ¹²C compositions consistent with modern subcutaneous fats of wild boar and goats pastured on lands adjacent to the Jordan Valley, and residues from a modern pottery vessel used in the manufacturing of butter, cheese and yogurt in central Turkey. These results are presented as an illustration of capabilities of the microwave‐assisted recovery protocol. The reclamation of saturated and unsaturated fatty acids from archaeological pottery fragments recovered from a number of the earliest ceramic horizons in the Middle East is herewith reported, and the extraction methods and instrumental analytical techniques are described.     

NUCLEAR MAGNETIC RESONANCE SPECTROSCOPIC AND ISOTOPIC ANALYSIS OF CARBONIZED RESIDUES FROM SUBARCTIC CANADIAN PREHISTORIC POTTERY

Late prehistoric pottery is found in abundance at archaeological sites around Southern Indian Lake. Black residues, found on the two dominant vessel forms, flat plates and round pots, are presumed to be the remains of prehistoric meals. ¹³C cross-polarization magic-angle-spinning nuclear magnetic resonance spectroscopy (CPMAS NMR) and¹³C and¹⁵ N isotopic ratios and C/N ratios are used to reconstruct prehistoric diet and to shed light on possible uses for the plates. Samples of foods were cooked in clay pots, on a wood fire, to simulate the conditions of burning that could have produced the residue. Decomposition of carbohydrates, protein, and fat during cooking is studied with ¹³C CPMAS NMR, and the effect of cooking on isotopic and C/N ratios documented. Predominantly fish and fat were cooked in the pots, whereas the residues from plates contain a greater proportion of fat and could have been used as frying pans or possibly as fat-burning lamps placed on the ashes of a wood fire.     

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.     

AN EVALUATION OF ANALYTICAL AND INTERPRETATIVE METHODOLOGIES FOR THE EXTRACTION AND IDENTIFICATION OF LIPIDS ASSOCIATED WITH POTTERY SHERDS FROM THE SITE OF SAGALASSOS,TURKEY*

Three lipid analysis methods were applied to extracts of archaeological potsherds from the ancient city of Sagalassos, south‐west Turkey. In the fatty acid methyl ester fraction, obtained by selective transesterification of acylglycerols, the ratio of methyl palmitate to methyl stearate was determined. Secondly, by means of gas chromatography– combustion–isotope ratio mass spectrometry (GC–C–IRMS), stable carbon isotope ratios were measured for the same methyl esters. Finally, triglyceride composition was determined via high‐performance liquid chromatography–mass spectrometry (HPLC–MS). All three methods can be used to trace the origin of animal fat. Agreement between them is reasonable, especially in recognizing ruminant adipose fat. One sample was found to be of dairy origin using both GC–C–IRMS and HPLC–MS. The advantages of the various methods are discussed. Variations in lipid composition were observed between samples from different periods and excavated in diverse areas within the city of Sagalassos.     

AN ANALYSIS OF THE GEM‐BLUE GLAZE OF YE WANG'S KOJI POTTERY*

Koji pottery is a glazed ceramic art used widely for figurines. In early Taiwan, it was employed in temple construction for decorative purposes. Ye Wang (1826–87) is the first historically documented Koji artist of Taiwan and also the most prominent Koji pottery artist, noted for his modelling and glazing skills. Unfortunately, his unique technique was lost following his death in 1887. In order to provide vital information for ongoing conservation work on Koji pottery, this study analysed the physical and chemical characteristics of Ye Wang's gem‐blue glaze, to discover the glaze formula. DSC combined with the two‐thirds rule revealed that the firing temperature of Ye Wang's works of art was most probably around 878–923°C. EPMA revealed that the gem‐blue glaze has high alkali levels, and belongs to the PbO–K₂O–B₂O₃–Na₂O–SiO₂ system, deriving its unique colour from copper, iron, manganese and cobalt. This study found high potassium levels in the gem‐blue glaze, which are generally a characteristic of traditional Chinese glazes. In addition, a unique discovery of boron, commonly used in famille rose, was also identified in the glaze. By comparing spectra of historical and reconstructed glazes and adjusting the proportion of chromophoric elements, this study found a glazing formula with colours close to those of Ye Wang's gem‐blue glaze.     

LEAD ISOTOPIC ANALYSIS FOR THE IDENTIFICATION OF LATE BRONZE AGE POTTERY FROM HALA SULTAN TEKKE (CYPRUS)

Lead isotopic compositions were measured for 65 sherds from five pottery wares (Plain White, Coarse, Canaanite, White Slip and Base‐ring) excavated from the Late Bronze Age site of Hala Sultan Tekke (Cyprus). The elemental composition and isotopic signature of the sherds were compared with those of 65 clay samples collected in south‐east Cyprus, mainly in the surroundings (<20 km) of Hala Sultan Tekke. This work shows the effectiveness of using lead isotopic analysis in provenance studies, along with other analytical techniques, such as X‐ray diffraction (XRD) and a scanning electron microscope (SEM) equipped with an energy dispersive X‐ray detection (EDX) facility, to identify the composition of pottery wares and the clay sources used for pottery ware production.     

CHARACTERIZATION AND PROVENANCE OF LATE ANTIQUE WINDOW GLASS FROM THE PETRA CHURCH IN JORDAN*

Fifth‐ to seventh‐century window glass fragments from the Petra Church in Jordan were analysed by EPMA and spectrophotometry to characterize their optical properties and chemical composition. The objective of this study was to determine the provenance of the raw glass and the secondary production procedures of the window‐panes. Judging from the material evidence, both the crown window‐panes and possibly the rectangular samples were produced through glass‐blowing techniques. The chemical data show that the assemblage forms a homogeneous group of soda–lime–silica glass of the Levantine I type. The green glass, however, has higher silica and lower soda contents than the aqua‐blue fragments. The composition of one sample suggested the recycling of Roman glass. Our results confirm the trade of glass between the Levantine coast and Petra during Late Antiquity. No colouring agents other than iron were detected. Spectrophotometry confirmed the presence of iron and showed that the window fragments absorbed light relatively equally across the visible part of the spectrum. The windows thus seem to have provided an almost colourless illumination for the sacred interior.     

Geochemical Characterization of Lapita Pottery Via Inductively Coupled Plasma–mass Spectrometry (ICP–MS)

We have obtained high‐resolution elemental data on Lapita ceramics (3200–2700 cal year bp ) from Fiji, Tonga and New Ireland using chemistry‐based inductively coupled plasma–mass spectrometry (ICP–MS). These data show clear elemental distinctions between Lapita pottery manufactured in Fiji, Tonga and New Ireland, and demonstrate significant elemental variation in Fijian ceramics collected from settlements in close proximity to one another. Therefore, we anticipate that ICP–MS will become an effective technique for tracking the transfer of Lapita pottery within and between different island groups in Oceania.