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.     

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.     

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.     

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.     

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.     

ORGANIC RESIDUE ANALYSIS IN ARCHAEOLOGY: THE ARCHAEOLOGICAL BIOMARKER REVOLUTION*

Organic residue analysis utilizes analytical organic chemical techniques to identify the nature and origins of organic remains that cannot be characterized using traditional techniques of archaeological investigation (because they are either amorphous or invisible). The field is founded upon the principle that the biomolecular, or biochemical, components of organic materials associated with human activity survive in a wide variety of locations and deposits at archaeological sites. The archaeological information contained in organic residues is represented by the biomolecular components of the natural products that contribute to the formation of a given residue. By applying appropriate separation (chromatographic) and identification (mass spectrometric) techniques, the preserved, and altered, biomolecular components of such residues can be revealed. Once identified, the Archaeological Biomarker Concept can be applied, wherein the structure and even isotopic composition(s) of a given biomolecule or suite of biomolecules (the ‘chemical fingerprint’) can be related to the compositions of organisms exploited by humans in the past. As the organic residue field emerges from its pre‐paradigmatic phase, and the organic residue revolution gathers pace, the way is open for challenging many long‐held archaeological hypotheses and offering new perspectives on the study of human activity in the past.     

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.     

UNDER THE HAMMER: RESIDUES RESULTING FROM PRODUCTION AND MICROWEAR ON EXPERIMENTAL STONE TOOLS*

This paper presents the results of an experimental programme investigating the effects of production processes on stone tools and their interference with use‐related features. In the first part of the experimental programme, a series of flint flakes was retouched with different kinds of hammers in order to assess the extent and nature of percussion residues. After careful environmental scanning electron microscope (ESEM) observation and energy‐dispersive X‐ray (EDX) analysis, the retouched flakes were thoroughly cleaned and the underlying flint deformation was recorded. The second part of the experimental programme involved selecting several uncleaned retouched pieces for use in short woodworking, hide‐processing and butchery experiments. These pieces were observed and analysed before, during and after use. Some of the percussion features proved to be surprisingly resistant to use, and in some cases turned out to be strikingly similar in appearance to use‐generated features.     

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.     

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.