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.     

First results on thermally induced porosity in chlorite cooking vessels from Merv (Turkmenistan) and implications for the formation and preservation of archaeological lipid residues

Excavations at the ancient city of Merv in Turkmenistan have yielded a significant assemblage of ceramic and stone vessel fragments from contexts dating to the Sasanian and medieval periods (5th–13th centuries AD). Many of the vessel fragments are encrusted with apparent food residue deposits offering scope for organic residue analysis and the potential to compare the use of these two very different vessel types. To enable meaningful comparison we sought to establish whether the vessel stone (a talc-chlorite schist) can absorb and preserve organic residues indicative of past use. This paper reports the first investigation to address this question using standard methods for archaeological residue analysis coupled with study of the properties of the schist fabric and basic absorption experiments. The results demonstrate that heating during cooking, even at relatively low temperatures, modifies the stone microstructure by increasing its porosity. These pores enhance the absorption capacity of the schist fabric such that chlorite cooking pots can absorb and preserve sufficient organic residue to reflect the original processing of foodstuffs, as has been previously demonstrated for ceramic fabrics. Comparison of pore capacity, archaeological residue yield and experimental absorption indicates the significance of pore-size distribution for the relative retention and preservation of organic residues in these fabrics. The results of this study indicate that a wider range of archaeological material may be suitable for absorbed residue analysis than has previously been recognised. The findings also challenge previous assumptions concerning the relationship between the properties of chlorite vessels and their mode of use in Central Asia and Near East in antiquity.     

Starch residues on museum artefacts: implications for determining tool use

A sample of 11 museum artefacts was examined to assess the preservation of any adhering organic residues, particularly starch granules, and to assess the potential for the identification of cooked starchy foods. The primary aim was to examine starchy deposits, extract starch granules and examine their physical condition to increase our understanding of the taphonomy of starch granules and associated organic residues in archived material and archaeological deposits. The study shows that organic plant residues could be recovered from archived artefacts and makes a significant contribution to understanding the function of this material. Recovered starch granules showed an interesting pattern of varying organic preservation on the surface of stone and wooden artefacts. Some starch granules were found to be well preserved while others in the same sample appeared to have been affected by enzyme degrading micro-organisms. Recovered residues included fully gelatinised starch.     

The decomposition of starch grains in soils: implications for archaeological residue analyses

Recent research involving starch grains recovered from archaeological contexts has highlighted the need for a review of the mechanisms and consequences of starch degradation specifically relevant to archaeology. This paper presents a review of the plant physiological and soil biochemical literature pertinent to the archaeological investigation of starch grains found as residues on artefacts and in archaeological sediments. Preservative and destructive factors affecting starch survival, including enzymes, clays, metals and soil properties, as well as differential degradation of starches of varying sizes and amylose content, were considered. The synthesis and character of chloroplast-formed ‘transitory’ starch grains, and the differentiation of these from ‘storage’ starches formed in tubers and seeds were also addressed. Findings of the review include the higher susceptibility of small starch grains to biotic degradation, and that protective mechanisms are provided to starch by both soil aggregates and artefact surfaces. These findings suggest that current reasoning which equates higher numbers of starch grains on an artefact than in associated sediments with the use of the artefact for processing starchy plants needs to be reconsidered. It is argued that an increased understanding of starch decomposition processes is necessary to accurately reconstruct both archaeological activities involving starchy plants and environmental change investigated through starch analysis.     

Ancient DNA confirms a local origin of domesticated chenopod in eastern North America

Domesticated chenopod was an important starchy seed crop in eastern North America before the rise of maize agriculture. Domesticated chenopod first appeared in North America during the fourth millennium B.P., however its wild progenitor and site of domestication remain unresolved. Archaeological evidence suggests a local domestication in the Eastern Woodlands, while morphological similarities with modern Mexican cultivars indicate a possible introduction from Mesoamerica. To distinguish between these two scenarios, we isolate chloroplast DNA (cpDNA) from modern and archaeological North American chenopods sampled from across their geographic range. Our results demonstrate that the chenopod grown in the Eastern Woodlands was locally-derived, indicating that independent domestication events gave rise to the ancient eastern North American and modern Mexican cultivars. These results strengthen the argument for an entirely native pre-maize crop complex with chenopod as a major component.     

Investigating the presence of ancient absorbed organic residues in groundstone using GC–MS and other analytical techniques: a residue study of several prehistoric milling tools from central California

Analysis of absorbed organic molecules in groundstone could provide a valuable means to study resource use and processing in antiquity. The following study analyzed extracts from the surfaces of several central California milling tools to assess whether organic residues remained from prehistoric resource processing. It also sought to determine which source identification methods are likely to be successful at providing information about the type, or even the specific identify, of resources that were processed. Lipids (primarily fatty acids) were analyzed using GC–MS and the presence of phenolic compounds was assessed with UV-Vis spectroscopy. Milling surfaces were compared to previously broken surfaces from the same tool with the assumption that both surfaces had been exposed to similar post-depositional conditions. Results supported the presence of ancient residues in milling tools. A higher concentration of fatty acids was recovered from milling surfaces than paired broken surfaces. Furthermore, measurable amounts of azelaic acid (an oxidation product of some unsaturated fatty acids) were present in most milling surfaces, but not in broken surfaces. However, results also indicated that environmentally absorbed lipids formed a significant portion of the total lipid content. Thus, it is suggested that future analyses employ a biomarker approach, rather than criteria based on ratios of common fatty acids, to identify sources of organic residues in prehistoric milling tools.     

药物残留物分析技术的考古学应用

有机残留物分析技术是使用有机化学分析手段鉴定有机残留物的性质和来源的主要方法①。与人类活动有关的有机物,其残留的生化成分残存于考古遗址内多种多样的器物和沉积物中。通过一定的分离和鉴定技术,例如色谱分离和质谱鉴定等适当的技术,可以揭示残留物生物分子成分,从而指示与人类活动相关的有机物及其利用情况,对陶器等用具、工具的功能解读、遗址环境重建、古人类行为复原和食谱分析等方面都可以起到一定程度的辅助作用②、③、④、⑤。古代人类的衣食住行都与植物和动物资源相关,特别是古代人类的医疗活动,根据各种动植物资源的药性药理,治疗各种疾病或者养生健体。由于药物多来源于动植物资源,不易保存,能够保存下来的药材实在少之又少,在考古遗址中关于药物利用的实物证据甚为罕见。因此,残留物分析就成为考古学研究中药物发展史分析的重要手段之一。     

Determining Olmec maize use through bulk stable carbon isotope analysis

Bulk stable carbon isotope analysis on absorbed organic residues in ceramics can be an effective method for discerning patterns of maize use when the ceramics come from relatively uniform archaeological contexts. The bulk stable carbon isotope method is faster and less costly than the more commonly used compound-specific stable carbon isotope analysis. Moreover, the bulk stable carbon isotope method can determine the presence of C4 plant carbon in samples in which organic compounds have degraded. Bulk stable carbon isotope analysis was used to discern patterns of maize (Zea mays mays) use among a sample of 24 ceramic sherds from an Early Franco Period feasting deposit (ca. cal 650 B.C.) at the Olmec site of San Andrés, La Venta, Tabasco, Mexico. A comparison of the δ 13C results of different categories of ceramics showed that proportionally more maize was used in luxury beverage service wares than in utilitarian vessels, suggesting that maize-based beverages were prominent in this probable elite feasting episode.     

Paleodietary implications from stable carbon isotope analysis of experimental cooking residues

The regional timing of maize introduction in eastern North America is a long-standing topic of archaeological interest. Most recently, Morton and Schwarcz [2004. Paleodietary implications from stable isotopic analysis of residues on prehistoric Ontario ceramics. Journal of Archaeological Science 31, 503–517] investigated the timing of maize introduction in Ontario through isotope analysis of charred cooking residues adhering to the interior of prehistoric ceramic containers. They interpret their results to suggest maize was incorporated into diets after A.D. 600. We assess their approach and conclusions with stable carbon isotope assays on three sets of experimental cooking residues, evaluating the variable combustion of carbon fractions, contributions of fats and carbohydrates, and the contribution of total carbon. We also undertake multiple resource modeling of two part food mixes with green maize and maize flour. Our results suggest that systematic under representation of maize can result depending on residue composition and that some prior knowledge of C3 plant and animal contents is necessary to interpret stable carbon isotope values on cooking residues. We question the independent use of stable carbon isotope analysis of charred cooking residues as a viable technique for extracting paleodietary information.     

Extracting residues from stone tools for optical analysis: towards an experiment-based protocol

The identification of residues is traditionally based on the distinctive morphologies of the residue fragments by means of light microscopy. Most residue fragments are amorphous, in the sense that they lack distinguishing shapes or easily visible structures under reflected light microscopy. Amorphous residues can only be identified by using transmitted light microscopy, which requires the extraction of residues from the tool’s surface. Residues are usually extracted with a pipette or an ultrasonic bath in combination with distilled water. However, a number of researchers avoid residue extraction because it is unclear whether current extraction techniques are representative for the use-related residue that adheres to a flaked stone tool. In this paper, we aim at resolving these methodological uncertainties by critically evaluating current extraction methodologies. Attention is focused on the variation in residue types, their causes of deposition and their adhesion and on the most successful technique for extracting a range of residue types from the stone tool surface. Based on an experimental reference sample in flint, we argue that a stepwise extraction protocol is most successful in providing representative residue extractions and in preventing damage, destruction or loss of residue.     

Mixed results of seven methods for organic residue analysis applied to one vessel with the residue of a known foodstuff

Several methods of archaeological organic residue analysis were applied to a single unglazed and unseasoned ceramic vessel that had absorbed residues of heated camel milk. Sections of the wall of this vessel were sent to eleven archaeological laboratories. Seven reported their results before the identity of the residue was revealed, during the 70th Annual Meeting of the Society for American Archaeology. Methods included stable carbon and nitrogen isotope ratio analysis, protein analysis and lipid analysis. These laboratory techniques provide a biochemical analysis of the residue in a ceramic matrix, the archaeological interpretation of which can be rather difficult. The exact source of the residue was not identified by any laboratory, but it is evident that residue analysis can provide valuable information, especially when combined with additional archaeological and historical data. We therefore support a close cooperation of those working in this field to develop it to its full potential.     

Experiments with Lithic Tools: Understanding Starch Residues from Crop Harvesting

Stone knives were used widely in Neolithic East Asia, presumably in the harvesting of grain crops, but their function has not been clearly understood due to the lack of study of residues from these tools. To address this issue, starch grain analysis was employed to study the residues on the surface of ancient stone knives and large amounts of starches were recovered. The sources of these starches, however, were not well understood, because harvesting of crops involves the cutting of stems rather than direct contact with starchy seeds. To determine whether harvesting could deposit these types of residues, we designed a simulation experiment using stone flakes to harvest ears of wheat, rice and foxtail millet, then analysed the residues on both the flakes and in the plant tissues. A large number of starch grains were found in the stems, including both typical morphotypes from seeds and newly described types that occur only in stems, which can be used as indicators of harvesting. Our study demonstrates that starch grains from residues on the surfaces of archaeological stone knives can indicate not only that the tools were used to harvest ears, but also the type of crops harvested.     

PINE RESINS AND POTTERY SEALING: ANALYSIS OF ABSORBED AND VISIBLE POTTERY RESIDUES FROM CENTRAL NEW YORK STATE*

Analysis was performed on absorbed and visible residues from 21 New York State prehistoric pottery sherds dating from 2905 ± 35 bp (Intcal04) (1256–998 cal bc ) to 425 ± 40 bp (Intcal04) (1417–1626 cal ad ). The use of pine resin was detected in 10 of 12 absorbed residue samples and 11 of 17 sherds subjected to visible residue analysis. It seems likely that the pots were resin‐sealed to make them more impermeable, constituting the first chemical evidence of extensive resin‐sealing in North America. A comparison of the results of absorbed and visible residues from eight of the sherds indicates that the two kinds of residue provide complementary evidence of vessel use.     

Potential misidentification of in situ archaeological tool-residues: starch and conidia

Microscopic identification of organic residues in situ on the surface of archaeological artefacts is an established procedure. Where soil components morphologically similar to use-residue types exist within the soil, however, there remains the possibility that these components may be misidentified as authentic residues. The present study investigates common soil components known as conidia, fungal spores which may be mistaken for starch grains. Conidia may exhibit the rotating extinction cross under cross-polarised light commonly diagnostic of starch, and may be morphologically indistinguishable from small starch grains, particularly at the limits of microscope resolution. Conidia were observed on stone and ceramic archaeological artefacts from Honduras, Palau and New Caledonia, as well as experimental artefacts from Papua New Guinea. The findings act as a caution that in situ analysis of residues, and especially of those less than 5 μm in size, may be subject to misidentification.     

Clues to Stone Tool Function Re-examined: Comparing Starch Grain Frequencies on Used and Unused Obsidian Artefacts

The identification of plant residues observed on prehistoric stone artefacts has often been used to inform on tool function without adequate consideration of potential contamination due to post-depositional processes. The paper redresses this balance by proposing a methodology which combines use-wear and residue analyses with systematic testing of depositional context to distinguish residues formed during tool use from accidental contamination. A case study involving obsidian artefacts from an open site in Papua New Guinea is used to illustrate the new approach. Starch grains, a class of residue which has had little attention outside Australia, were chosen as the focus of study because of their abundance at this site. The frequency of starch grains extracted from residues on stone artefacts was compared with those in sediments adhering to and adjacent to the artefact. A use-wear study conducted as a blind test provided an independent measure of whether the artefacts had been used. The frequency of starch grains was shown to be significantly correlated with used artefacts and not correlated with unused artefacts or the sediments. The case study demonstrates the importance of testing for contamination and also illustrates the benefit of studying starch grains as a class of plant residue.     

The persistence of caffeine in experimentally produced black drink residues

Black drink is a native North American caffeinated tea produced from the leaves of Ilex vomitoria. The beverage was an important part of prehistoric Southeastern culture, as it was the only native source of caffeine in North America. The leaves of I. vomitoria were, therefore, a potentially valuable trade resource during the period. As such, the ability to identify archaeological black drink residues is useful to Southeastern archaeologists. In order to determine the plausibility of detecting I. vomitoria in residues, black drink was repeatedly produced in experimental unglazed pottery. The resulting potsherds were buried in several environmental contexts, recovered, and underwent absorbed pottery residue analysis. After two months of burial in three different soil types, plus a control stored in the freezer, caffeine was well-preserved in all sherds, suggesting that caffeine is a potentially useful biomarker for the detection of black drink.     

Swept under the rug: the problem of unacknowledged ambiguity in lithic residue identification

Microscopic analysis of organic residues on stone tools is used to interpret prehistoric stone tool functions. The morphology of some residues can be difficult to interpret, yet this ambiguity is rarely acknowledged in the literature. Our research seeks to understand the nature of this ambiguity by objectively identifying ambiguous residues in our reference collection. We trained four archaeologists in residue analysis using one part of our reference collection, then tested their ability to identify sixty-eight residues in another part of the same collection. Forty-eight of the residues in the test (70%) were correctly identified by three or all four subjects. We considered the remaining twenty residues, which were correctly identified by two or fewer of the subjects, to be ambiguous. These are most often in the hide-scraping, bone-scraping, and hardwood-scraping (macerated) categories, and tend to have an atypical morphology which falls in the range of variability of another residue category. Some of these residues also have optical properties which make them more difficult to image than others. We explore the potential for scanning electron microscopy (SEM) to improve residue identification in a second test. This test shows a modest improvement in identification success rates of ambiguous residues when SEM images are included. We conclude that while images from different types of microscopes can improve reliability of identification, some residues will always be ambiguous. Rather than being ignored, these ambiguities should be brought to light, closely examined, and published as such.     

HONEY AND DRIPPING: NEOLITHIC FOOD RESIDUES FROM RUNNYMEDE BRIDGE

Summary. This paper illustrates the prospects for a fuller understanding of ancient foodstuffs by applying a range of analytical techniques to charred food residues on pottery. The relevant techniques of organic chemistry are briefly described. First results on Neolithic material from Runnymede stand amongst few for prehistoric Europe. They demonstrate the potential importance of such analyses both in redressing imbalances present at the site level and in opening wider issues, such as the functions attached to particular pot forms. The identification of beeswax in a British Neolithic context prompts an enquiry into the nature of early bee management and the suggestion that 'forest beekeeping'may have been widespread in temperate Neolithic Europe.     

Identifying biomolecular origins of solid organic residues preserved in Iron Age Pottery using DTMS and MVA

The chemical characterisation of solid organic residues found in ceramic vessels, can provide archaeologists with valuable information about ancient diets. Although several selective analytical techniques have been applied to the analysis of specific classes of compounds, such as extractable lipids, waxes, terpenoids and protein fragments, a non-selective analytical technique is required to characterise and categorise complete solid organic residues. In this study, Direct Temperature-resolved Mass Spectrometry (DTMS) is used for the characterisation of 34 solid residues situated on vessels recovered from an indigenous settlement from the Roman period at Uitgeest – Groot Dorregeest (The Netherlands). Sample preparation is limited to grinding very small samples (5–10 μg) and suspending them in water. DTMS analysis of aliquots (1–2 μL) of this suspension gave information about a broad range of organic compounds, such as lipids, polynuclear aromatic hydrocarbons, markers for residual proteins and polysaccharides, and for newly formed complex condensed polymers. Multivariate analysis of the DTMS spectra identified five different chemotypes: groups of residues with comparable chemical characteristics. The biomolecular origin of each of these chemotypes is identified by comparison with experimentally charred reference materials. The chemotypes A₁ and A₂ consist of charred residues identified as starch-rich foods (mixed with animal or plant products), chemotype C consists of protein-rich charred animal products without starch, chemotype B contains smoke condensates from wood fires, and chemotype D consists of special protein-rich and lipid-free foods or non-food products.     

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.