NEOLITHIC ZOOMORPHIC VESSELS FROM EASTERN MACEDONIA,GREECE: ISSUES OF FUNCTION*

Five fragments of Late Neolithic clay zoomorphic vessels from northern Greece have been analysed for organic residues by gas chromatography – mass spectrometry. The results showed that the containers had been used in connection with a number of substances, in particular lower terpenoids, an oil or fat, possibly fossil fuel and in one case possibly beeswax. The paper considers likely interpretations of such combinations of materials in relation to possible functions of these symbolically enhanced artefacts. It appears that substances may have been used in the vessels because of their aromatic and/or medicinal and combustible properties, possibly in order to produce light, fragrance and/or smoke.     

THE CHARACTERIZATION OF PAINTS AND WATERPROOFING MATERIALS FROM THE SHIPWRECKS FOUND AT THE ARCHAEOLOGICAL SITE OF THE ETRUSCAN AND ROMAN HARBOUR OF PISA (ITALY)*

This work presents the results of a diagnostic survey on the shipwrecks from the archaeological site of the ancient harbour of San Rossore (Pisa, Italy). The original waterproofing, caulking and painting materials were characterized by Fourier transform infrared spectroscopy (FTIR), gas chromatography – mass spectrometry (GC–MS), energy‐dispersive X‐ray microanalysis (EDX) and X‐ray diffraction (XRD). The major constituents of the waterproofing and caulking materials detected on the planks were tricyclic abietanes showing a high degree of aromatization. These compounds are indicative of a pitch obtained from the wood of trees of the Pinaceae family. The analysis of the organic components of the paint samples revealed diterpenoid acids characteristic of Pinaceae resins together with linear long‐chain alcohols and fatty acids, highlighting the presence of beeswax. Noticeably, the characteristic odd carbon number alkanes that are normally present in beeswax were not detected. The EDX and XRD analyses showed that hematite, calcite, cerussite and kaolinite were employed as pigments to paint the ships’ hulls.     

The contents of unusual cone-shaped vessels (cornets) from the Chalcolithic of the southern Levant

Cornets are cone-shaped ceramic vessels, characteristic of the Chalcolithic period (ca. 4700–3700 BC) in Israel and Jordan. Their contents and use are unknown. Gas chromatography with flame ionization and mass-selective detection, showed that extracts of cornets from five different sites with different related activities (domestic, habitation cave and a cultic complex) all contain the same assemblage of mainly n-alkanes adsorbed within their walls. This assemblage differs from those found in other types of ceramic vessels from the same sites, as well as from the residues found within the associated sediments. The assemblage of odd and even-numbered n-alkanes found in the cornets is almost identical to that found in the residues of beeswax heated on modern ceramic fragments, as well as in a beehive from the Iron Age IIA strata at Tel Rehov, Israel. Thus the cornets are most likely to have contained beeswax. The presence of beeswax in the cornets contributes to our understanding of the Chalcolithic period; a time when secondary products such as milk, olive oil and wine are thought to have come into use.     

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.     

Discovery of Beeswax as binding agent on a 6th-century BC Chinese Turquoise-inlaid Bronze sword

Recent archaeological field surveys and excavations at Qiaojiayuan, a platform 40 km west of the Yun County in present-day northwestern Hubei Province (central China), revealed four tombs (M₃, M₄, M₅ and M₆) dating back to around 6th to 5th century BC. The grave's layout, artifact assemblages and burial practice indicate that the owners of these four graves were aristocrats of the Chu state. Five turquoise-inlaid bronze artifacts (two swords and three dagger-axes) were excavated. The sword from M₄, imbedded with pieces of well-cut and finely-polished turquoise on its handle, was in a very bad state of preservation and underwent conservation treatment. Some sticky, whitish pastes were exposed when the inlaid turquoises dropped off. The pastes were supposed to be residues of unknown binding agents. Samples of the pastes were collected for FTIR (Fourier Transform Infrared Spectroscopy) and XRD (X-Ray Diffraction) analyses to determine the chemical component(s). The results revealed that the pastes were composed of almost pure beeswax. This indicated that beeswax was used as binding agent in turquoise-inlaid bronzes as early as the 6th to 5th century BC in China. Review of recent technical studies suggested that beeswax was used in early China in several different regions (mostly southern part of China) for at least two different purposes (binding agent and lightening).     

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.     

The Preservation of Invertebrates in 16th‐Century Cesspits at St Saviourgate,York*

The taphonomy of invertebrates from 16th‐century cesspits at St Saviourgate, York, was investigated. Earthworms, fly larvae and puparia are preserved through replication in calcium phosphate, a process facilitated by acidic cesspit pore water and by the presence of abundant organic matter, bones and shells. Features preserved by mineralization include muscles, blood vessels and setae. Non‐mineralized invertebrate remains include puparia and beetles. Py–GC/MS (flash pyrolysis–gas chromatography/mass spectrometry) revealed a very high level of preservation of structural biomolecules, with all the protein and chitin markers that are evident in the living forms still being detectable in the divalent remains.     

QUANTIFICATION AND DISTRIBUTION OF LIPID IN ARCHAEOLOGICAL CERAMICS: IMPLICATIONS FOR SAMPLING POTSHERDS FOR ORGANIC RESIDUE ANALYSIS AND THE CLASSIFICATION OF VESSEL USE

Organic residue analysis has been performed on 62 reconstructed vessels from a single archaeological site (Rounds, Northamptonshire, U.K.). In order to establish regions of lipid accumulation within a vessel, sherds were sampled from different parts of a vessel, for example base, body and rim, and submitted to lipid extraction procedures. The techniques of high-temperature gas chromatography (GC) and GC/mass spectrometry (GC/MS) were then used to analyse the sherd lipid extracts. The quantitative results obtained show differential accumulation and preservation of lipid in various parts of the same vessel. This latter observation has serious implications for the sampling of potsherds for organic residue analysis. Furthermore, the amount of absorbed lipid varies quite considerably between vessel types. On this basis, a new method is proposed for classifying vessel use by comparing the concentration of lipid present in different parts of individual vessels.     

FIELD AND LABORATORY MULTI‐TECHNIQUE ANALYSIS OF PIGMENTS AND ORGANIC PAINTING MEDIA FROM AN EGYPTIAN COFFIN (26TH DYNASTY)

This paper describes the physico‐chemical analyses performed on an Egyptian wood coffin on the occasion of its restoration in the hall of the National Archaeological Museum of Parma (Italy), with the aim of investigating the pigments and organic materials originally used. Pigment determination was performed both in situ by a portable energy‐dispersive X‐ray fluorescence (EDXRF) spectrometer and in the laboratory using a micro‐Fourier‐transform‐infrared (micro‐FTIR) and a Fourier‐transform (FT) Raman spectrometer. The identification of organic materials was performed through gas chromatography – mass spectrometry (GC–MS) and micro‐FTIR analysis. Amongst the pigments, special attention was paid to the green, which appeared to be severely degraded and was examined using powder X‐ray diffraction (XRD) and scanning electron microscopy – energy‐dispersive X‐ray (SEM–EDX) in addition to the above‐cited techniques. Other materials used in the polychromatic decorations are Egyptian blue, cinnabar and possibly orpiment, while calcium carbonate was used for the ground layer. The organic materials were identified as beeswax, mastic and gum arabic, sometimes as mixtures.     

Chemical Alteration and Use of Beeswax Through Time: Accelerated Ageing Tests and Analysis of Archaeological Samples from Various Environmental Contexts

In order better to interpret the chemical composition of ancient organic residues and artefacts containing beeswax, the degradation of this raw material was accelerated in the laboratory by controlled heating. During the course of degradation, deposits were condensed above the beeswax. Both degraded beeswax and these deposits were analysed. These experiments definitively proved that n‐alkane depletion is due to a sublimation process that depends on the molecular weight of these hydrocarbons. The formation of benzoic and cinnamic derivatives due to the degradation of flavonoid precursors initially present in beeswax has also been highlighted for the first time. The analysis of samples from Neolithic and Roman periods led to the identification of beeswax characterized by different degradation patterns linked to their environmental context.     

Identification of the Residue in the Bolgar Medieval Sphero‐Conical Vessel by Gas Chromatography – Mass Spectrometry

The Golden Horde sphero‐conical vessel retrieved from the ruins of the medieval city of Bolgar (Russia, Republic of Tatarstan) during archaeological excavations, which contained residue in the form of encrustation on the bottom and the wall, was analysed in the NRC ‘Kurchatov Institute’ by X‐ray phase analysis and high‐performance liquid and gas chromatography with MS detectors (HPLC–MS, GC–MS). The GC–MS method established that the residue from the sphero‐conical vessel was comprised primarily of abietic acid derivatives (around 46%) and retene, which is polycyclic aromatic hydrocarbon (around 27%); this means that turpentine exuded from the stems of certain species of coniferous trees, called resin and subsequently heat‐treated, was poured into the vessel. Researchers have been trying to decipher the function of these mysterious vessels for 200 years, and this is the first time that resin stored in a sphero‐conical vessel has been documented. Potentially, this vessel was probably used as a personal ‘medical kit’.     

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.     

ANOMALOUS CARBON-13 VALUES FOR FIBRE TEMPER IN CERAMICS*

Ceramic vessels from Later Stone Age sites in the Seacow river valley, South Africa, were heavily tempered with C4 grasses. However, most δ¹³C values of the temper fall between the known δ¹³C ranges for C4 and C3 grasses. Among possible C3 additives that could skew the signal, ground bone, animal dung, alpine grass, Karoo scrub ash, and humic acid contamination are eliminated. The sherd surfaces yield fatty chars with C3-like values. Although these are not enough to account for all the skewing, they represent only the final cooking event. They were preceded by many such events in which fat was absorbed into the C4 grass then charred to soot by later periods in the fire. Thus organic carbon with the isotope composition of the fat built up while the vessel remained in use.     

RADIOCARBON DATES FOR BEESWAX FIGURES IN THE PREHISTORIC ROCK ART OF NORTHERN AUSTRALIA

Accelerator mass spectrometry radiocarbon ages have been taken for a test suite of small samples of material removed from some of the ‘beeswax’art figures found in rock shelters in northern Australia. The results indicate that we can reliably date this unique form of rock art with no noticeable damage. We had not expected to find figures of any great antiquity, and so we were surprised to find that the ages obtained spanned the time period from the recent past to about 4000 BP.     

RECONSTRUCTING ANCIENT YEMENI COMMERCIAL ROUTES DURING THE MIDDLE AGES USING STRUCTURAL CHARACTERIZATION OF TERPENOID RESINS*

Following the discovery of items that look like resins at the medieval site of Sharma (Hadramawt coast, Yemen, c. 11th century ad ), chemical investigations were carried out in order to determine their nature and geographic origin. By combining visual observation, infrared spectroscopy, direct inlet electron ionization – mass spectrometry (DI EI–MS) and pyrolysis gas chromatography – mass spectrometry (Py GC–MS) or gas chromatography – mass spectrometry (GC–MS) analyses, it was demonstrated that 84% of the samples were harvested from Hymenaea trees growing in Madagascar and East Africa. Contrary to what was thought previously, frankincense, identified with certainty in only two samples, was thus not the main resin exploited at Sharma. These results are of prime importance for reconsidering the trading routes of resins passing through Sharma, a site that was obviously strongly connected with Africa during the Middle Ages.     

Adhesive Production and Pottery Function During the Iron Age at the Site of Grand Aunay (Sarthe,France)*

A combination of elemental, functional and molecular analyses performed on amorphous organic residues dating from the Iron Age was developed in order to identify these remains and to understand their relationship with ceramic vessels in which some of them were found. These analyses made it possible to distinguish between ceramic vessels used for the production or storage of adhesive materials, mainly birch bark tar, and those dedicated to the preparation of culinary commodities, which contained animal fats. The organization of the production of adhesives is described and the addition of beeswax to birch bark tar is reported for the first time. The use of birch bark tar for coating ceramic vessels is also discussed.     

Tracking 800-year-old Shipments: An Archaeological Investigation of the Mado Shipwreck Cargo, Taean, Korea

This paper examines cargo from an 800-year-old shipwreck and discusses its implications in relation to the exchange networks and maritime transportation of the Goryeo period (A.D. 918–1392) in Korea. In 2007, two local fishermen fortuitously discovered porcelain vessels from a Goryeo-period shipwreck off the mid-western coast of the Korean peninsula. Underwater excavation conducted by the National Research Institute of Maritime Cultural Heritage (NRIMCH) revealed that the ship was carrying a myriad of cargoes destined for Gaegyeong, the capital of the Goryeo dynasty. Excavation indicates that the main body of the cargo was porcelain vessels produced in the southern part of the peninsula. Archaeobotanical investigation of the wreck deposits revealed that the ship was carrying crops such as rice (Oryza sativa L.), broomcorn millet (Panicum miliaceum L.), foxtail millet (Setaria italica (L.) P. Beauv.), and buckwheat (Fagopyrum esculentum Moench) bound for the capital. Among the recovered objects were 73 wooden cargo tags with Chinese letters. These tags, equivalent to the modern day air bill, contained detailed information about the senders, recipients, and shipped goods. These findings indicate that during the Goryeo period maritime transportation played an important role in the interpersonal exchange of products over long distances.     

FROM SUSA TO ANURADHAPURA: RECONSTRUCTING ASPECTS OF TRADE AND EXCHANGE IN BITUMEN‐COATED CERAMIC VESSELS BETWEEN IRAN AND SRI LANKA FROM THE THIRD TO THE NINTH CENTURIES AD*

In contrast with artefactual studies of long‐distance trade and exchange in South Asia during the Prehistoric and Early Historic periods ( Ardika et al. 1993 ; Gogte 1997 ; Krishnan and Coningham 1997 ; Tomber 2000 ; Gupta et al. 2001 ; Ford et al. 2005 ), few scientifically orientated analyses have focused on artefacts from the region's Historic period. During excavations at the ancient city of Anuradhapura, Sri Lanka, a number of buff ware ceramics with a putative organic coating on the interior were recovered ( Coningham 2006 ). Dated stylistically to between the third and ninth centuries ad , analysis of the coatings using gas chromatography–mass spectrometry (GC–MS) and stable isotope analysis (carbon and deuterium) confirmed that the coatings are bitumen—an organic product associated with petroleum deposits. There are no known bitumen sources in Sri Lanka, and biomarker distributions and isotopic signatures suggest that the majority of the samples appear to have come from a single bitumen source near Susa in Iran. The relationship between the bitumen coatings and the vessels is discussed, and it is suggested that the coatings were used to seal permeable ceramic containers to allow them to transport liquid commodities. This study enhances our knowledge of networks of trade and exchange between Sri Lanka and western Asia during Historic times.     

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.     

TECHNOLOGICAL STUDY OF PTOLEMAIC – EARLY ROMAN FAIENCE FROM MEMPHIS,EGYPT*

Fourteen fragments of faience vessels from the Ptolemaic/Roman period found at the Egyptian site of Memphis, near Cairo, were analysed by SEM. The fragments included high‐relief polychrome vessels, which are first produced in numbers in this period. Analysis allowed the composition and microstructure of the vessels to be assessed and conclusions drawn as to the raw materials of manufacture. Combining this information with archaeological evidence from excavation of the kilns and associated finds, it was possible to reconstruct the production technology of the vessels.