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.     

The Preservation and Interpretation of δ34S Values in Charred Archaeobotanical Remains

The measurement of sulphur isotope (δ³⁴S) values in charred plant remains has the potential to inform understanding of the spatial configuration and ecology of crop production. We investigated the effects of charring, manuring, oxidation and anaerobic soil conditions on modern cereal grain/pulse seed δ³⁴S values, and assessed the effect of chemical pre‐treatment on charred modern and archaeobotanical grain/seed δ³⁴S values. We used these results to interpret δ³⁴S values in archaeobotanical material from Neolithic Çatalhöyük. Our results suggest that δ³⁴S values can be reliably preserved in charred grain/seeds but are subject to influence by anaerobic soil conditions, the effect depending on the timing of flooding in relation to S assimilation.     

Probing dietary change of the Kwädąy Dän Ts'ìnchį individual,an ancient glacier body from British Columbia: II. Deconvoluting whole skin and bone collagen δC values via carbon isotope analysis of individual amino acids

The remains of the Kwäd?y Dän Ts'ìnch? individual, a frozen male human, were recovered from a retreating glacier within the Tatshenshini-Alsek Park in British Columbia in August 1999. In order to provide information on both the geographical origin of this individual and low long he spent in the remote interior region prior to his death, molecular analysis and compound-specific carbon isotope analyses were performed on individual amino acids purified from his skin and bone. Gas chromatographic quantification of constituent amino acids of both tissues revealed a molecular distribution characteristic of collagen, dominated by glycine and to a lesser extent proline, hydroxyproline and alanine. Chiral gas chromatography indicated that protein preservation in both tissues was exceptional. Carbon isotope analysis of a faunal assemblage from an earlier prehistoric site from southern British Columbia provided reference dietary amino acid δ¹³C values for terrestrial (deer and domestic dog) and marine species (salmon and sealion), showing clear separation in all amino acids, particularly glycine which was extremely ¹³C-enriched in the marine animals. The distinction between terrestrial and marine organisms was increased by exploring Δ¹³C_{Glycine-Phenylalanine} values (6.6 ± 0.6‰ and 15.0 ± 2.1‰, respectively), which were higher in the latter by approximately 8‰, mirroring the increased δ¹⁵N_{Bulk collagen} values observed for the marine animals (R² = 0.78; p < 0.001). The Kwäd?y Dän Ts'ìnch? individual's bone had a similarly elevated Δ¹³C_{Glycine-Phenylalanine} value of 15.6 ± 1.0‰, indicating his extreme reliance on marine dietary resources throughout early life. The skin amino acid δ¹³C values were consistently lower than those observed for bone, with a concurrently lower Δ¹³C_{Glycine-Phenylalanine} value of 12.7 ± 0.9‰. The shift between the carbon isotope composition of bone (long-term diet) and skin amino acids (short-term diet) confirmed a sudden divergence away from marine food sources in the last months of life, consistent with his discovery 80 km inland.     

Organic geochemical analysis of archaeological medicine pots from Northern Ghana. The multi-functionality of pottery

Sherds from pots found layered under a granite boulder in the Tong Hills of the Upper East Region of Northern Ghana seem, based on their deposition context to have been used for the preparation of medicines. Organic geochemical and isotopic analyses of these sherds and a modern day analogue reveal an n-alkanoic acid composition that is consistent with their being used in the preparation of plant derived substances. Isotopic analyses of the modern medicine pot indicate a contribution of n-alkanoic acids derived from plants that use C₄ carbon fixation, most likely maize, sorghum and/or millet suggesting that this pot was used for cooking C₄ based plant substances, perhaps, based on current analogy, staple porridge type food. The modern medicine pot could thus have had a prior use. The absence of C₄ plant residues in the archaeological sherds suggests that either staple foodstuffs differed radically to today, or, more likely, were not prepared in vessels that were to be used for medicinal purposes.     

Pigments and Plasters Discovered in the House of Diana (Cosa,Grosseto, Italy): An Integrated Study Between Art History,Archaeology and Scientific Analyses*

The pigments and the plasters of the Roman frescoes discovered at the House of Diana (Cosa, Grosseto, Italy) were analysed using non‐destructive and destructive mineralogical and chemical techniques. The characterization of both pigments and plasters was performed through optical microscopy, scanning electron microscopy and electron microprobe analysis. The pigments were identified by Raman spectroscopy and submitted to stable isotope analysis. The results were integrated with the archaeological data in order to determine and reconstruct the provenance, trade patterns and the employment of the raw materials used for the elaboration of the frescoes.     

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.     

Probing dietary change of the Kwädąy Dän Ts'ìnchį individual,an ancient glacier body from British Columbia: I. Complementary use of marine lipid biomarker and carbon isotope signatures as novel indicators of a marine diet

The remains of the preserved ice body from the Kwäd?y Dän Ts'ìnch? discovery were recovered from a retreating glacier in the Tatshenshini-Alsek Park, British Columbia in August 1999. Despite the remote location 80 km inland, bone collagen stable isotope analysis indicated that the individual spent much of his life in a region rich in marine foods (δ¹³C −13.7‰ and δ¹⁵N +17.9‰). Since finds of such bodies are exceptionally rare we undertook detailed lipid analyses in order to assess their preservation and determine whether they might provide new insights into the individual’s dietary life history. Molecular fingerprinting and compound-specific carbon isotope analysis were performed on individual lipids extracted from his bone (turnover approximately ≥1 year) and skin (turnover approximately several weeks). A considerable abundance was observed of C_12:0, C_14:0, C_16:0, C_16:1, C_18:0 and C_18:1 fatty acids (FAs), cholesterol and hydroxy FAs (the latter being decay products). Most unusual was the presence of long-chain hydroxy FAs (LCHFAs), 10- and 12-hydroxyeicosanoic acid and 10- and 12-hydroxydocosanoic acid, in the bone. The latter components are most likely the products of microbially mediated hydration of the double-bonds of C_20:1 and C_22:1 FAs, the latter almost certainly originating from the consumption of a largely marine-based diet. A suite of three isoprenoidal lipids, phytanic acid, pristanic acid and 4,8,12-trimethyltetradecanoic (TMTD) acid, was also detected supporting the notion of a significant marine component of the diet for a substantial part of his life. In contrast, the skin lipid composition was dominated by C_{16:0 FA}, with lower abundances being observed of the marine LCHFAs and isoprenoidal compounds, suggesting reduced reliance on coastal marine foods in the last period of life. This interpretation is supported by the enhanced marine dietary signal observed in the bone than skin FA δ¹³C values.