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A novel route for identifying starch diagenetic products in the archaeological record

ABSTRACT: This work introduces a novel analytical chemistry method potentially applicable to the study of archaeological starch residues. The investigation involved the laboratory synthesis of model Maillard reaction mixtures and their analysis through Fourier-Transform Ion Cyclotron Resonance Mass Spectrometry (FTICR-MS). Thus, starch from sixteen plant species were matured while reacting it with the amino acid glycine. The FTICR-MS analysis revealed > 5,300 molecular compounds, with numerous unique heteroatom rich compound classes, ranging from 20 (Zea mays) to 50 (Sorghum bicolor). These classes were investigated as repositories of chemical structure retaining source and process-specific character, linked back to botanical provenance. We discussed the Maillard reaction products thus generated, a possible pathway for the preservation of degraded starch, while also assessing diagenetic recalcitrance and adsorption potential to mineral surfaces. In some cases, hydrothermal experimentation on starches without glycine reveals that the chemical complexity of the starch itself is sufficient to produce some Maillard reaction products. The article concludes that FTICR-MS offers a new analytical window to characterize starchy residue and its diagenetic products, and is able to recognize taxonomic signals with the potential to persist in fossil contexts.

SUBMITTER: Oldenburg T

PROVIDER: S-EPMC8601532 | biostudies-literature |

REPOSITORIES: biostudies-literature

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Project description:The detection of direct archaeological remains of alcoholic beverages and their production is still a challenge to archaeological science, as most of the markers known up to now are either not durable or diagnostic enough to be used as secure proof. The current study addresses this question by experimental work reproducing the malting processes and subsequent charring of the resulting products under laboratory conditions in order to simulate their preservation (by charring) in archaeological contexts and to explore the preservation of microstructural alterations of the cereal grains. The experimentally germinated and charred grains showed clearly degraded (thinned) aleurone cell walls. The histological alterations of the cereal grains were observed and quantified using reflected light and scanning electron microscopy and supported using morphometric and statistical analyses. In order to verify the experimental observations of histological alterations, amorphous charred objects (ACO) containing cereal remains originating from five archaeological sites dating to the 4th millennium BCE were considered: two sites were archaeologically recognisable brewing installations from Predynastic Egypt, while the three broadly contemporary central European lakeshore settlements lack specific contexts for their cereal-based food remains. The aleurone cell wall thinning known from food technological research and observed in our own experimental material was indeed also recorded in the archaeological finds. The Egyptian materials derive from beer production with certainty, supported by ample contextual and artefactual data. The Neolithic lakeshore settlement finds currently represent the oldest traces of malting in central Europe, while a bowl-shaped bread-like object from Hornstaad-Hörnle possibly even points towards early beer production in central Europe. One major further implication of our study is that the cell wall breakdown in the grain's aleurone layer can be used as a general marker for malting processes with relevance to a wide range of charred archaeological finds of cereal products.

Project description:Reindeer herding probably developed during the Late Iron Age onwards and is still an important part of the subsistence and culture of many peoples in northern Eurasia. However, despite the importance of this husbandry in the history of these Arctic people, the period and place of the origin as well as the spread of domestic reindeer is still highly debated. Besides the existence of different breeding methods in these territories, identifying domesticated individuals in the archaeological record is complicated because reindeers are considered to still be in the early phases of the domestication process. Indeed, the traditional morphological markers used in zooarchaeology to decipher the domestication syndrome are hardly perceptible in these early stages. In this work, we propose solutions for identifying domestic reindeer bones using 3D geometric morphometrics on isolated elements from the long bones of the forelimb (i.e. humerus, radio-ulna and metacarpal). These bones are important to understand both the feeding behaviour and the mobility of reindeer, and the potential effect of load-carrying or draught in the case of domestic reindeer. We analysed 123 modern specimens from Fennoscandia, including the two interbreeding subspecies currently present in these territories: mountain reindeer (Rangifer tarandus tarandus) and forest reindeer (R.t. fennicus); and where the sex and the lifestyle were known (i.e. free-ranging, racing or draught and captive individuals). A good level of discrimination between the size and shape variables of the bones of the forelimb was found among both subspecies and sexes. Moreover, individuals bred in captivity had smaller bone elements and a thinner and more slender morphology than free-ranging individuals. This demonstrates that the long bones of the forelimb can provide information on changes in feeding and locomotor behaviour prompted by the domestication process, like control and/or reduction of mobility and food of individual reindeer by humans. This also demonstrates that analysis in 3D geometric morphometrics is useful in detecting reindeer incipient domestication markers. Our results can be used by archaeologists to trace the early stages of domestication from fossil reindeer remains, and aid in reconstructing the socio-economic changes of past Arctic populations over time.

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A novel route for identifying starch diagenetic products in the archaeological record

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