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.     

IDENTIFICATION OF AN ADHESIVE USED TO REPAIR A ROMAN JAR

A combination of micro-analytical techniques, including thin layer chromatography (TLC), gas chromatography (GC), and combined gas chromatography/mass spectrometry (GC/MS), was employed to study the lipid composition of an adhesive used to repair an Ecton ware jar, recovered from Roman sediments of the River Nene at West Cotton (Rounds, Northamptonshire, U.K.). GC of the total lipid extract of the adhesive showed a complex pattern which was difficult to interpret. TLC was used to fractionate the extract. The fractions were then trimethylsilylated and submitted to GC and GC/MS. Betulin, lupeol, lupenone, allobetul-2-ene, and several other pentacyclic triterpenoid compounds were shown to be present in the ancient material. The similarities between the lipid compositions of the adhesive and of contemporary birch bark tar and a birch bark total lipid extract led to the conclusion that the adhesive was derived largely from birch bark, thus providing the first firm evidence for the use of birch bark tar in ancient Britain.     

THE PROVENANCE AND PRODUCTION TECHNOLOGY OF BRONZE AGE AND IRON AGE POTTERY FROM TELL MISHRIFEH/QATNA (SYRIA)*

This work deals with the archaeometric study of the Bronze Age and Iron Age pottery from Tell Mishrifeh/Qatna (central‐western Syria), where the complete cycle of ceramic production is well documented. Petrographic, chemical and diffractometric analyses were carried out on both potsherds and a clayey material found in a separation basin within the area of the workshops. Petrographic groups were defined and maximum firing temperatures and redox firing conditions were estimated, providing constraints on identifying the production technology and its evolution with time. The studied potsherds turned out to be locally produced, with only a few cases of possible similarities with those described for other localities along the Orontes Valley, and in a couple of cases with evidence of pottery exchange.     

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.     

CHARACTERIZATION OF NATURAL PRODUCTS ON NATIVE AMERICAN ARCHAEOLOGICAL AND ETHNOGRAPHIC MATERIALS FROM THE GREAT BASIN REGION,U.S.A.: A PRELIMINARY STUDY

Although documentary evidence provided by ethnographers makes reference to the source of adhesives, sealants, dyestuffs and medicines used by the communities of the Great Basin, much of it is sporadic and unspecified. However, observations of amorphous deposits surviving on stone tools, ceramics, basketry and wooden artefacts have prompted an investigation of their identity, procurement and use. The aim initially is to study samples from a number of archaeological and ethnographic contexts from the region. Comparative material includes higher plant and insect resins. The study provides a unique opportunity to document use patterns in plant and animal resources in the Great Basin region.     

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.     

ESTIMATION OF THE AGE OF A PRE‐INDUSTRIAL IRON SITE IN KOREA*

A pre‐industrial iron‐smelting site in Korea, whose period of active use is placed on typological grounds between the eighth and 18th centuries ad , has been dated using accelerator mass spectrometry and thermoluminescence. The ages of two charcoal samples were 77 ± 25 and 81 ± 25 years bp , with the calibrated date for both ranging from ad 1700 to ad 1955, while a clay fragment dated to ad 1650 ± 50. The results from typology and radiocarbon seem insignificant due to the considerable uncertainties involved, but in combination with the thermoluminescence result they place the most probable date of the site at around ad 1700.     

CHARACTERIZATION OF RED‐COLOURED SLIPS (ALMAGRA) ON ISLAMIC CERAMICS IN MUSLIM SPAIN*

Small objects found in Islamic (eleventh‐century) kilns excavated in Zaragoza (Spain) were studied to determine the nature of the red coating of almagra pottery. Ceramics with almagra decoration were completely coated with a glossy deep‐red layer, a slip, applied to the body before firing. Chemical and mineralogical studies were carried out, together with analysis of a surface treatment with organic compounds. The results of this study confirm that almagra ceramics were produced by means of a specific and elaborate process (slip preparation, firing and wax application), demonstrating the introduction of this slip into local production during the Islamic period.     

EVIDENCE FOR THE MIXING OF FATS AND WAXES IN ARCHAEOLOGICAL CERAMICS

Lipid residues from two Late Saxon/early medieval ceramic vessels recovered from excavations at West Cotton, Raunds, Northamptonshire, U.K., have been investigated by high-temperature gas chromatography (GC) and GC/mass spectrometry (GC/MS). The solvent extracts of sherds sampled from different points on each vessel (i.e., base, body and rim) were analysed quantitatively and qualitatively and compounds were identified which were characteristic of beeswax and animal fat. Furthermore, by determining the sites of accumulation of the specific lipid types and their concentrations in different parts of the vessels it can be inferred that the beeswax was added to the vessels prior to the addition of the fat. It was concluded that the two vessels performed different functions in antiquity.     

CHEMICAL COMPOSITION OF A BOG BODY ADIPOCERE

Chemical analyses were carried out on adipocere obtained from a bog body recovered from a peat bog at Meenybradden, County Donegal, Ireland. Chromatographic (thin-layer chromatography and gas chromatography) and mass spectrometric analyses, combined with microanalytical chemical transformations, have yielded detailed compositional information. An absence of intact triacylglycerols, diacylglycerols and monoacylglycerols indicates that hydrolysis is complete. Consequently the adipocere is composed mainly of fatty carboxylic acids. The high proportion of palmitic and stearic acids, together with depleted oleic acid content, indicates that extensive reduction and, possibly, β-oxidation have occurred during burial in the peat bog. Hydration of the double-bond in oleic acid has also occurred, as is shown by the formation of 10-hydroxystearic acid. The monoenoic fatty carboxylic acids that are present, composed mainly of C₁₈ and C₁₆ compounds, comprise a mixture of positional isomers. The results are compared and contrasted with those obtained from previous studies of the lipid composition of other adipoceres and cadavers of archaeological interest.     

CYPRIOT BLACK-ON-RED WARE: TOWARDS A CHARACTERIZATION

Chemical analysis of Early Iron Age sherds from Cyprus and the Levant using atomic absorption spectrometry shows that Black-on-Red ware was manufactured only in Cyprus. Two types of fabric are isolated, calcareous and non-calcareous, and their technological significance discussed. The presence of trade links between the Cypriot sites of Kition and Amathus and sites in the Levant is suggested.     

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 ANCIENT LACQUER FILM USING TWO-STAGE PYROLYSIS-GAS CHROMATOGRAPHY/MASS SPECTROMETRY*

Oriental lacquer has been used as a surface coating for wood, porcelain and metal, and three different types are known: Japanese (or Chinese) lacquer (urushiol-based), Vietnamese lacquer (laccol-based) and Burmese lacquer (thitsiol-based). Identification of these types in ancient coatings is very important in conservation and restoration studies. A two-stage pyrolysis-gas chromatography/mass spectrometry method is effective for the analysis of lacquer films. This is shown here using an ancient lacquer film sample from medieval material excavated at Tobarikyu (Japan), The sample was identified, by comparison with linseed oil and authentic lacquer films, as an urushiol-based Rhus vernicifera (Japanese) lacquer which includes an added oil component.     

The Preservation and Identification of Piñon Resins by GC‐MS in Pottery from the Western Great Basin

Gas chromatography — mass spectrometry analysis of a sherd from the Nevada Test Site revealed a high quantity of terpenes, including sesquiterpenoids and diterpenoids, demonstrating that piñon resins were prepared in the pot in prehistoric times. The presence of these biomarkers allowed for a very specific identification of the products prepared in the pot, a level of detail not often achieved in lipid residue analysis. That the terpenes are relatively unoxidized demonstrates that they are quite stable over long periods of time. The study also shows that sherds on the surface of archaeological sites can preserve lipids and terpenes and are amenable to organic residue analysis.     

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.     

Trude Dothan (1922–2016): In Memoriam

Abstract

This paper sheds new light on the most common type of pottery associated with advanced phases of Early Bronze I (EB I) in the southern Jordan valley: the distinctive family or group known as Um Hammad Ware, or Proto-Urban D (PUD) Ware. To date, this kind of pottery was thought to be concentrated mostly around the site of Tell Um Hammad. This study presents new evidence suggesting that this ware was dispersed over a region considerably wider than previously understood, and that the centre of its manufacture was probably in the region of western Wadi Far'ah. This paper also explores the possibility that the origins of this family are to be found in the pottery traditions of the Golan region during the Chalcolithic period.     

A Study Of The Firing Technique Of Pottery From Kaman‐Kalehöyük,Turkey, by Synchrotron Radiation‐Induced Fluorescence X‐Ray Absorption Near‐Edge Structure (Xanes) Analysis*

Fe K‐XANES spectra of a series of pottery sherds excavated from the archaeological site of Kaman‐Kalehöyük, Turkey, were measured to reveal the firing technique of the pottery. The analysis disclosed relationships among the chemical form of the iron, the firing conditions and the colour of the pottery. The pottery referred to as ‘Grey Ware’ found at this site was classified into two groups according to the chemical form of the iron. Also, it was revealed that the Iron Age pottery referred to as ‘Cream Ware’ was produced first under reducing conditions, and then fired under oxidizing conditions.     

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.