Unravelling the function of funerary pottery vessels of the 2nd-1st millennia BC in the Dailaman Province (Iran) through typology, petrography, and organic residue analyses.

Pottery vessels often comprise major burial goods at archaeological sites, thus providing valuable information for reconstructing past mortuary practices. However, because of the uncertainty of its function or use, which has been interpreted mostly through typological studies alone, the analytical potential of pottery as a burial good has not been fully exploited. This study applied bio-chemical and geochemical analyses for the first time to funerary pottery vessels of the Iron Age of North Iran to examine their function and use. The study materials are from the necropolis of Ghalekuti, Dailaman, excavated in the 1960s. Direct radiocarbon dating conducted on human and animal bones in the graves and typological analysis of the pottery anchored the chronological position of the pottery materials to the 2nd and 1st millennium BC. A petrographic analysis revealed that pottery vessels can be classified into six fabric types, including those with coarse tempers that are effective for cooking. Pottery pastes with finer inclusions less suited for cooking appeared during the early first millennium BC (Iron Age III). To obtain further insight into the function of the pottery, we conducted organic residue analyses. The results demonstrated that the vessels retained remains of botanical and animal origin. In particular, jars with tubular spouts, characteristic of the Iron Age III period, were likely specialised for botanical products. Interestingly, both carcass and dairy products from ruminant animals (cattle and caprine) were processed in short-neck jars and bowls, including spouted bowls, suggesting their use in a liquid state. Products from ruminants, particularly dairy products, may have played a significant role in the daily and ritual use of pottery vessels during the study period in Northern Iran. These results indicate that a range of pottery vessels used for specific purposes before the burial was offered for graves, helping us better understand the mortuary practices of Iron Age Iran.

Dating the emergence of dairying by the first farmers of Central Europe using 14C analysis of fatty acids preserved in pottery vessels.

Direct, accurate, and precise dating of archaeological pottery vessels is now achievable using a recently developed approach based on the radiocarbon dating of purified molecular components of food residues preserved in the walls of pottery vessels. The method targets fatty acids from animal fat residues, making it uniquely suited for directly dating the inception of new food commodities in prehistoric populations. Here, we report a large-scale application of the method by directly dating the introduction of dairying into Central Europe by the Linearbandkeramik (LBK) cultural group based on dairy fat residues. The radiocarbon dates (n = 27) from the 54th century BC from the western and eastern expansion of the LBK suggest dairy exploitation arrived with the first settlers in the respective regions and were not gradually adopted later. This is particularly significant, as contemporaneous LBK sites showed an uneven distribution of dairy exploitation. Significantly, our findings demonstrate the power of directly dating the introduction of new food commodities, hence removing taphonomic uncertainties when assessing this indirectly based on associated cultural materials or other remains.

Direct 14C dating of equine products preserved in archaeological pottery vessels from Botai and Bestamak, Kazakhstan.

Direct and accurate radiocarbon dating of lipid residues preserved in ceramics is a recently established method that allows direct dating of specific food products and their inception in human subsistence strategies. The method targets individual fatty acids originating from animal fats such as ruminant dairy, ruminant adipose, non-ruminant adipose and aquatic fats. Horse lipid residues found in Central Asian pottery vessels are also directly dateable using this new method. Here we present the identification of equine lipid residues preserved in two pottery assemblages from the Neolithic and Eneolithic in Kazakhstan and their direct 14C dating. The site of Botai, previously radiocarbon-dated to the 4th millennium BC, was used as a reference to evaluate the dates obtained directly on horse lipids. The direct dating of equine products extracted from Botai potsherds are shown to be compatible with previous 14C dates at the site. The site of Bestamak, lacking previous14C measurements, had been relatively dated to the Neolithic based on pottery typologies. The direct dating of equine residues made it possible to anchor the pottery assemblage of Bestamak in the 6th millennium BC confirming their Neolithic attribution. These findings demonstrate the potential for dating horse products through a compound-specific approach, while highlighting challenges in 14C dating individual fatty acids from lipid extracts in which their abundances differ substantially. Supplementary Information: The online version contains supplementary material available at 10.1007/s12520-022-01630-2.

Dairying, diseases and the evolution of lactase persistence in Europe.

In European and many African, Middle Eastern and southern Asian populations, lactase persistence (LP) is the most strongly selected monogenic trait to have evolved over the past 10,000 years1. Although the selection of LP and the consumption of prehistoric milk must be linked, considerable uncertainty remains concerning their spatiotemporal configuration and specific interactions2,3. Here we provide detailed distributions of milk exploitation across Europe over the past 9,000 years using around 7,000 pottery fat residues from more than 550 archaeological sites. European milk use was widespread from the Neolithic period onwards but varied spatially and temporally in intensity. Notably, LP selection varying with levels of prehistoric milk exploitation is no better at explaining LP allele frequency trajectories than uniform selection since the Neolithic period. In the UK Biobank4,5 cohort of 500,000 contemporary Europeans, LP genotype was only weakly associated with milk consumption and did not show consistent associations with improved fitness or health indicators. This suggests that other reasons for the beneficial effects of LP should be considered for its rapid frequency increase. We propose that lactase non-persistent individuals consumed milk when it became available but, under conditions of famine and/or increased pathogen exposure, this was disadvantageous, driving LP selection in prehistoric Europe. Comparison of model likelihoods indicates that population fluctuations, settlement density and wild animal exploitation-proxies for these drivers-provide better explanations of LP selection than the extent of milk exploitation. These findings offer new perspectives on prehistoric milk exploitation and LP evolution.

Tree-rings reveal two strong solar proton events in 7176 and 5259 BCE.

The Sun sporadically produces eruptive events leading to intense fluxes of solar energetic particles (SEPs) that dramatically disrupt the near-Earth radiation environment. Such events have been directly studied for the last decades but little is known about the occurrence and magnitude of rare, extreme SEP events. Presently, a few events that produced measurable signals in cosmogenic radionuclides such as 14C, 10Be and 36Cl have been found. Analyzing annual 14C concentrations in tree-rings from Switzerland, Germany, Ireland, Russia, and the USA we discovered two spikes in atmospheric 14C occurring in 7176 and 5259 BCE. The ~2% increases of atmospheric 14C recorded for both events exceed all previously known 14C peaks but after correction for the geomagnetic field, they are comparable to the largest event of this type discovered so far at 775 CE. These strong events serve as accurate time markers for the synchronization with floating tree-ring and ice core records and provide critical information on the previous occurrence of extreme solar events which may threaten modern infrastructure.

Living off the land: Terrestrial-based diet and dairying in the farming communities of the Neolithic Balkans.

The application of biomolecular techniques to archaeological materials from the Balkans is providing valuable new information on the prehistory of the region. This is especially relevant for the study of the neolithisation process in SE Europe, which gradually affected the rest of the continent. Here, to answer questions regarding diet and subsistence practices in early farming societies in the central Balkans, we combine organic residue analyses of archaeological pottery, taxonomic and isotopic study of domestic animal remains and biomolecular analyses of human dental calculus. The results from the analyses of the lipid residues from pottery suggest that milk was processed in ceramic vessels. Dairy products were shown to be part of the subsistence strategies of the earliest Neolithic communities in the region but were of varying importance in different areas of the Balkan. Conversely, milk proteins were not detected within the dental calculus. The molecular and isotopic identification of meat, dairy, plants and beeswax in the pottery lipids also provided insights into the diversity of diet in these early Neolithic communities, mainly based on terrestrial resources. We also present the first compound-specific radiocarbon dates for the region, obtained directly from absorbed organic residues extracted from pottery, identified as dairy lipids.

Chemical evidence of dairying by hunter-gatherers in highland Lesotho in the late first millennium AD.

The recovery of Early Iron Age artefacts and domestic animal remains from hunter-gatherer contexts at Likoaeng, Lesotho, has been argued to indicate contact between highland hunter-gatherers and Early Iron Age agropastoralist communities settled in lowland areas of southeastern Africa during the second half of the first millennium AD. However, disagreement between archaeozoological studies and ancient DNA means that the possibility that those hunter-gatherers kept livestock themselves remains controversial. Here we report analyses of pottery-absorbed organic residues from two hunter-gatherer sites and one agriculturalist site in highland Lesotho to reconstruct prehistoric subsistence practices. Our results demonstrate the exploitation of secondary products from domestic livestock by hunter-gatherers in Lesotho, directly dated to the seventh century AD at Likoaeng and the tenth century AD at the nearby site of Sehonghong. The data provide compelling evidence for the keeping of livestock by hunter-gatherer groups and their probable incorporation as ancillary resources into their subsistence strategies.

Molecular and isotopic evidence for milk, meat, and plants in prehistoric eastern African herder food systems.

The development of pastoralism transformed human diets and societies in grasslands worldwide. The long-term success of cattle herding in Africa has been sustained by dynamic food systems, consumption of a broad range of primary and secondary livestock products, and the evolution of lactase persistence (LP), which allows digestion of lactose into adulthood and enables the milk-based, high-protein, low-calorie diets characteristic of contemporary pastoralists. Despite the presence of multiple alleles associated with LP in ancient and present-day eastern African populations, the contexts for selection for LP and the long-term development of pastoralist foodways in this region remain unclear. Pastoral Neolithic (c 5000 to 1200 BP) faunas indicate that herders relied on cattle, sheep, and goats and some hunting, but direct information on milk consumption, plant use, and broader culinary patterns is rare. Combined chemical and isotopic analysis of ceramic sherds (n = 125) from Pastoral Neolithic archaeological contexts in Kenya and Tanzania, using compound-specific δ13C and Δ13C values of the major fatty acids, provides chemical evidence for milk, meat, and plant processing by ancient herding societies in eastern Africa. These data provide the earliest direct evidence for milk product consumption and reveal a history of reliance on animal products and other nutrients, likely extracted through soups or stews, and plant foods. They document a 5,000-y temporal framework for eastern Africa pastoralist cuisines and cultural contexts for selection for alleles distinctive of LP in eastern Africa.

Accurate compound-specific 14C dating of archaeological pottery vessels.

Pottery is one of the most commonly recovered artefacts from archaeological sites. Despite more than a century of relative dating based on typology and seriation1, accurate dating of pottery using the radiocarbon dating method has proven extremely challenging owing to the limited survival of organic temper and unreliability of visible residues2-4. Here we report a method to directly date archaeological pottery based on accelerator mass spectrometry analysis of 14C in absorbed food residues using palmitic (C16:0) and stearic (C18:0) fatty acids purified by preparative gas chromatography5-8. We present accurate compound-specific radiocarbon determinations of lipids extracted from pottery vessels, which were rigorously evaluated by comparison with dendrochronological dates9,10 and inclusion in site and regional chronologies that contained previously determined radiocarbon dates on other materials11-15. Notably, the compound-specific dates from each of the C16:0 and C18:0 fatty acids in pottery vessels provide an internal quality control of the results6 and are entirely compatible with dates for other commonly dated materials. Accurate radiocarbon dating of pottery vessels can reveal: (1) the period of use of pottery; (2) the antiquity of organic residues, including when specific foodstuffs were exploited; (3) the chronology of sites in the absence of traditionally datable materials; and (4) direct verification of pottery typochronologies. Here we used the method to date the exploitation of dairy and carcass products in Neolithic vessels from Britain, Anatolia, central and western Europe, and Saharan Africa.

Four millennia of dairy surplus and deposition revealed through compound-specific stable isotope analysis and radiocarbon dating of Irish bog butters.

Bog butters are large white or yellow waxy deposits regularly discovered within the peat bogs of Ireland and Scotland. They represent an extraordinary survival of prehistoric and later agricultural products, comprising the largest deposits of fat found anywhere in nature. Often found in wooden containers or wrapped in animal bladders, they are considered to have been buried intentionally by past farming communities. While previous analysis has determined that Irish bog butters derive from animal fat, their precise characterisation could not be achieved due to diagenetic compositional alterations during burial. Via compound-specific stable isotope analysis, we provide the first conclusive evidence of a dairy fat origin for the Irish bog butter tradition, which differs from bog butter traditions observed elsewhere. Our research also reveals a remarkably long-lived tradition of deposition and possible curation spanning at least 3500 years, from the Early Bronze Age (c. 1700 BC) to the 17th century AD. This is conclusively established via an extensive suite of both bulk and compound-specific radiocarbon dates.

Practical Considerations in High-Precision Compound-Specific Radiocarbon Analyses: Eliminating the Effects of Solvent and Sample Cross-Contamination on Accuracy and Precision.

Preparative capillary gas chromatography (pcGC) is widely used for the isolation of single compounds for radiocarbon determinations. While being effective at isolating compounds, there are still genuine concerns relating to contamination associated with the isolation procedure, such as incomplete removal of solvent used to recover isolated compounds from the traps and cross-contamination, which can lead to erroneous 14C determinations. Herein we describe new approaches to identifying and removing these two sources of contamination. First, we replaced the common "U" trap design, which requires recovery of compounds using organic solvent, with a novel solventless trapping system (STS), consisting of a simple glass tube containing a glass wool plug, allowing condensation of a target compound in the wool and its solventless recovery by pushing the glass wool directly into a foil capsule for graphitization. With the STS trap, an average of 95.7% of the target compound was recovered, and contamination from column bleed was reduced. In addition, comparison of 14C determinations of fatty acid methyl ester (FAME) standards determined offline to those isolated by pcGC in STS traps showed excellent reproducibility and accuracy compared to those isolated using the commercial "U" traps. Second, "coldspots" were identified in the instrument, i.e., the termini of capillaries in the preparative unit, which can be cleaned of compounds condensed from earlier runs using a heat gun. Our new procedure, incorporating these two modifications, was tested on archeological fat hoards, producing 14C dates on isolated C16:0 and C18:0 fatty acids statistically consistent with the bulk dates of the archeological material.

Use of a 700 MHz NMR Microcryoprobe for the Identification and Quantification of Exogenous Carbon in Compounds Purified by Preparative Capillary Gas Chromatography for Radiocarbon Determinations.

Preparative capillary gas chromatography (PCGC) is the central technique used for the purification of volatile or semivolatile organic compounds for radiocarbon analysis using accelerator mass spectrometry (AMS). While thicker film columns offer efficient separations, cyclic poly(dimethylsiloxanes) (PDMS) derived from the column's stationary phase have been highlighted as a potential source of contaminant carbon in "trapped" compounds. The PDMS CH3 groups are of "infinite" radiocarbon age due to the fossil carbon origin of the feedstock used in production. Hence, column bleed, if present at sufficiently high concentrations, would shift the radiocarbon ages of trapped compounds to older ages. Quantification of the column bleed in trapped samples, however, is extremely challenging and up to now has only been achieved through indirect 14C determinations of chromatographic blanks, which are used for post 14C determination "corrections". As part of wider investigations aimed at better understanding the chemical nature of contamination in compound-specific 14C determinations, herein, we report a rigorous approach to column bleed identification and quantification. Using reference fatty acid methyl esters (FAMEs), 1H nuclear magnetic resonance spectroscopy (NMR), employing a 700 MHz instrument equipped with a 1.7 mm microcryoprobe optimized for 1H observation, was able to detect low submicrogram amounts of low molecular weight compounds (<500 Da). Direct quantification of PCGC "trapped" FAMEs was achieved based on the recorded 1H NMR spectra. Gravimetrically prepared calibration mixtures of cyclic PMDSs and FAMEs showed column bleed abundance to be below 0.03% w/w of the "trapped" FAMEs, which would lead to a maximum shift in radiocarbon age of <3 years toward older values. We therefore conclude that column bleed contamination has a negligible effect on the 14C determination of FAMEs prepared using the chromatographic method described. The 1H NMR analysis also revealed the absence of other protonated carbon-containing components that would affect radiocarbon determinations at the precisions achievable by AMS.