Robert Berstan

Direct chemical evidence for widespread dairying in prehistoric Britain

Domesticated animals formed an important element of farming practices in prehistoric Britain, a fact revealed through the quantity and variety of animal bone typically found at archaeological sites. However, it is not known whether the ruminant animals were raised purely for their tissues (e.g., meat) or alternatively were exploited principally for their milk. Absorbed organic residues from pottery from 14 British prehistoric sites were investigated for evidence of the processing of dairy products. Our ability to detect dairy fats rests on the observation that the δ13C values of the C18:0 fatty acids in ruminant dairy fats are ≈2.3‰ lower than in ruminant adipose fats. This difference can be ascribed to (i) the inability of the mammary gland to biosynthesize C18:0; (ii) the biohydrogenation of dietary unsaturated fatty acids in the rumen; and (iii) differences (i.e., 8.1‰) in the δ13C values of the plant dietary fatty acids and carbohydrates. The lipids from a total of 958 archaeological pottery vessels were extracted, and the compound-specific δ13C values of preserved fatty acids (C16:0 and C18:0) were determined via gas chromatography-combustion-isotope ratio mass spectrometry. The results provide direct evidence for the exploitation of domesticated ruminant animals for dairy products at all Neolithic, Bronze Age, and Iron Age settlements in Britain. Most significantly, studies of pottery from a range of key early Neolithic sites confirmed that dairying was a widespread activity in this period and therefore probably well developed when farming was introduced into Britain in the fifth millennium B.C.

Direct dating of pottery from its organic residues: new precision using compound-specific carbon isotopes

Techniques for identifying organic residues in pottery have been refined over the years by Professor Evershed and his colleagues. Here they address the problem of radiocarbon dating these residues by accelerator mass spectrometry (AMS) which in turn dates the use of the pot. Fatty acids from carcass and dairy products cooked in the pot were isolated from early Neolithic carinated bowls found at the Sweet Track, Somerset Levels, England, and then dated by AMS. The results were very consistent and gave an excellent match to the dendrochronological date of the trackway. The method has wide potential for the precise dating of pottery use on sites.

Compound-specific stable carbon isotopic detection of pig product processing in British Late Neolithic pottery

By extracting lipids from potsherds and determining the d13C of the most abundant fatty acids, degraded fats from ruminant animals, such as cattle, and non-ruminant animals, such as pigs, can be distinguished. The authors use this phenomenon to investigate Late Neolithic pig exploitation and find that the pig �signature� was more frequently found among residues from Grooved Ware than other prehistoric pottery types.

Radiocarbon dating of single compounds isolated from pottery cooking vessel residues.

We have developed and demonstrated a practical methodology for dating specific compounds (and octadecanoic or stearic acid--C (sub 18:0) --in particular) from the lipid material surviving in archaeological cooking pots. Such compounds may be extracted from about 10 g of cooking potsherd, and, after derivatization, can be purified by gas chromatography. To obtain sufficient material for precise dating repetitive, accumulating, GC separation is necessary. Throughout the 6000-year period studied, and over a variety of site environments within England, dates on C (sub 18:0) show no apparent systematic error, but do have a greater variability than can be explained by the errors due to the separation chemistry and measurement process alone. This variability is as yet unexplained. Dates on C (sub 16:0) show greater variability and a systematic error of approximately 100-150 years too young, and it is possible that this is due to contamination from the burial environment. Further work should clarify this.

Identification of a disinterred grave by molecular and stable isotope analysis

Confirmation of a potential disinterred grave was sought by GC and GC/MS analyses of lipid extracts of whole soils and white particulate matter. Fatty acid profiles and concentrations determined for three of the soils correlated with the deposition of a large amount of exogenous organic matter, most likely adipocere and/or decomposed body fat. Determination of C16:0 and C18:0 fatty acid delta13C values by GC/C/IRMS revealed the input to be isotopically distinct from common British domesticated animals, plotting closely to values determined for adipose fat obtained from of a murder victim. By considering the difference between delta13C values (delta13C18:0-16:0) a potential isotopic proxy for identifying the source of adipocere (human) and adipose tissue was proposed.

Isotope effects associated with the preparation and methylation of fatty acids by boron trifluoride in methanol for compound-specific stable hydrogen isotope analysis via gas chromatography/thermal conversion/isotope ratio mass spectrometry

RATIONALE Compound-specific stable hydrogen isotope analysis of fatty acids is being used increasingly as a means of deriving information from a diverse range of materials of archaeological, geological and environmental interest. Preparative steps required prior to isotope ratio mass spectrometry (IRMS) analysis have the potential to alter determined δD values and hence must be accounted for if accurate δD values for target compounds are to be obtained. METHODS Myristic, palmitic, stearic, arachidic and behenic saturated fatty acids were derivatised to their respective fatty acid methyl esters (FAMEs), using 14% (w/v) boron trifluoride in methanol then analysed by gas chromatography/thermal conversion/IRMS (GC/TC/IRMS). FAMEs generated from fatty acid sodium salts of unknown δD values were then used to test a correction factor determined for this method of derivatisation. RESULTS Derivatisation was found to alter the hydrogen isotopic composition of FAMEs although this effect was reproducible and can be accounted for. The difference between the mean corrected and mean bulk δD values was always less than 6.7 ‰. Extraction of saturated fatty acids and acyl lipids from samples, subsequent hydrolysis, then separation on a solid-phase extraction cartridge, was found to alter the determined δD values by less than one standard deviation. CONCLUSIONS Overall, it has been shown that for natural abundance hydrogen isotope determinations, the isolation and derivatisation of extracted fatty acids alters the determined δD values only by a numerical increment comparable with the experimental error. This supports the use of the described analytical protocol as an effective means of determining fatty acid δD values by GC/TC/IRMS.