RESUMEN
The domestication of cattle, sheep and goats had already taken place in the Near East by the eighth millennium bc. Although there would have been considerable economic and nutritional gains from using these animals for their milk and other products from living animals-that is, traction and wool-the first clear evidence for these appears much later, from the late fifth and fourth millennia bc. Hence, the timing and region in which milking was first practised remain unknown. Organic residues preserved in archaeological pottery have provided direct evidence for the use of milk in the fourth millennium in Britain, and in the sixth millennium in eastern Europe, based on the delta(13)C values of the major fatty acids of milk fat. Here we apply this approach to more than 2,200 pottery vessels from sites in the Near East and southeastern Europe dating from the fifth to the seventh millennia bc. We show that milk was in use by the seventh millennium; this is the earliest direct evidence to date. Milking was particularly important in northwestern Anatolia, pointing to regional differences linked with conditions more favourable to cattle compared to other regions, where sheep and goats were relatively common and milk use less important. The latter is supported by correlations between the fat type and animal bone evidence.
Asunto(s)
Bovinos/fisiología , Industria Lechera/historia , Leche/historia , Leche/estadística & datos numéricos , Animales , Cerámica/análisis , Europa (Continente) , Europa Oriental , Ácidos Grasos/análisis , Cabras , Historia Antigua , Humanos , Carne , Leche/química , OvinosRESUMEN
The chemical analyses of "bog butters" recovered from peat bogs of Scotland were performed with the aim of determining their origins. Detailed compositional information was obtained from "bog butter" lipids using high temperature gas chromatography (HTGC) and GC-mass spectrometry (GC-MS). The results indicate the degree to which "bog butters" have undergone diagenetic alterations during burial to form an adipocere like substance, consisting predominantly of hexadecanoic (palmitic) and octadecanoic (stearic) acids. GC-combustion-isotope ratio MS (GC-C-IRMS) was used to determine delta13C values for the dominant fatty acids present, revealing for the first time that "bog butters" were derived from both ruminant dairy fats and adipose fats. The results are compared and contrasted with modern reference fats and adipoceres produced in vitro.
RESUMEN
This study investigates the effects of hydrolysis on the delta13C values of individual amino acids (IAAs) derived from polypeptide standards, and modern and ancient bone collagen. All IAAs were derivatised to their trifluoroacetyl/isopropyl (TFA/IP) esters for delta13C determination using gas chromatography/combustion/isotope ratio mass spectrometry (GC/C/IRMS). Firstly, authentic single poly amino acid standards (SPAAs; n = 5) were hydrolysed for 4, 10, 24 and 48 h. As expected, IAA yields increased as a function of hydrolysis time. Significantly, it was only after 24 h of hydrolysis that IAA delta13C values were statistically identical to bulk SPAA values for all five standards. The accuracy of IAA delta13C values was thus shown to be a function of yield; however, poly phenylalanine demonstrated accurate IAA delta13C values with yields of only 1.4 and 4.3%, after 24 and 48 h of hydrolysis time, respectively. Authentic mixed poly amino acid standards (MPAAs; n = 5) comprising two different amino acids were then hydrolysed for 24 h. Percentage recoveries ranged from 36-95%. Estimates of bulk MPAA delta13C values calculated from measured IAA delta13C values agreed within experimental error with measured bulk MPAA values for three out of the five standards. Finally, the experimental procedure was applied to modern rat (MBCs; n = 20) and ancient ovi-caprine and bovine (ABCs; n = 27) bone collagen samples where the delta13C values of 12 out of its 18 constituent amino acids were determined. Estimated bulk MBC and ABC delta13C values were calculated from constituent amino acid delta13C values using mass balance. With the exclusion of three ABC samples, calculated bulk bone collagen delta13C values (delta13C(BCcal)) were shown to correlate extremely well with measured bone collagen values (delta13C(BCmes)) for both modern and ancient samples, where R2 = 0.91 and 0.84, respectively. Significantly, the variation between calculated and measured bone collagen values (Delta13C(BCcal-BCmes)) exhibited similar ranges for both MBC (from -2.6 to +1.2 per thousand ) and ABC (from -2.7 to +2.2 per thousand ) samples, providing evidence for the preservation of intact collagen in the ancient samples. These results demonstrate that the experimental procedures employed in the acid hydrolytic cleavage of peptides or proteins to their constituent amino acids does not involve significant isotopic fractionation.
Asunto(s)
Aminoácidos/análisis , Aminoácidos/química , Péptidos/química , Proteínas/química , Animales , Huesos , Isótopos de Carbono , Bovinos , Cromatografía de Gases , Colágeno/química , Cromatografía de Gases y Espectrometría de Masas , Hidrólisis , Ratas , Factores de TiempoRESUMEN
Animal fats are preserved at archaeological sites in association with unglazed pottery, human and animal remains, and other deposits or hoards. High-temperature gas chromatography (HT-GC) and combined HT-GC/mass spectrometry (HT-GC/MS) has confirmed the presence of animal fats in lipid extracts of artifacts. Degradation products and pathways have been discerned through the analyses of archaeological finds and the products of laboratory and field-based decay experiments. The origins of preserved fats have been determined through detailed compositional analysis of their component fatty acids by GC, by GC/MS of dimethyl disulfide derivatives of monoenoic components, and by GC-combustion-isotope ratio-MS (GC-C-IRMS), to derive diagenetically robust delta(13)C values. Regiospecific analysis of intact triacylglycerols by high-performance liquid chromatography/MS (HPLC/MS), with atmospheric pressure chemical ionization, provides a further criterion for establishing the origin of fats. Preparative GC has been employed to isolate individual fatty acids from archaeological pottery in sufficient amounts for (14)C dating.