RESUMO
Seeds of domesticated Vicia (vetch) species (family Fabaceae-Faboideae) are produced and consumed worldwide for their nutritional value. Seed accessions belonging to 16 different species of Vicia-both domesticated and wild taxa-were subjected to a chemotaxonomic study using ultraperformance liquid chromatography-mass spectrometry (UPLC-MS) analyzed by chemometrics. A total of 89 metabolites were observed in the examined Vicia accessions. Seventy-eight out of the 89 detected metabolites were annotated. Metabolites quantified belonged to several classes, viz., flavonoids, procyanidins, prodelphinidins, anthocyanins, stilbenes, dihydrochalcones, phenolic acids, coumarins, alkaloids, jasmonates, fatty acids, terpenoids, and cyanogenics, with flavonoids and fatty acids amounting to the major classes. Flavonoids, fatty acids, and anthocyanins showed up as potential chemotaxonomic markers in Vicia species discrimination. Fatty acids were more enriched in Vicia faba specimens, while the abundance of flavonoids was the highest in Vicia parviflora. Anthocyanins allowed for discrimination between Vicia hirsuta and Vicia sepium. To the best of our knowledge, this is the first report on employing UPLC-MS metabolomics to discern the diversity of metabolites at the intrageneric level among Vicia species.
Assuntos
Metaboloma , Espectrometria de Massas em Tandem , Cromatografia Líquida de Alta Pressão , Cromatografia Líquida , Flavonoides/análise , Metabolômica , Sementes/químicaRESUMO
This paper starts from theoretical and methodical considerations about the role of archaeobotanical finds in culinary archaeology, emphasizing the importance of processed cereal preparations as the "missing link" between crop and consumption. These considerations are exemplified by the discussion of abundant new archaeobotanical data from the Late Bronze Age copper mining site of Prigglitz-Gasteil, situated at the easternmost fringe of the Alps. At this site, copper ore mining in opencast mines took place from the 11th until the 9th century BCE (late Urnfield Culture), as well as copper processing (beneficiation, smelting, refining, casting) on artificial terrain terraces. During archaeological excavations from 2010 to 2014, two areas of the site were investigated and sampled for archaeobotanical finds and micro-debris in a high-resolution approach. This paper aims at 1) analysing the food plant spectrum at the mining settlement of Prigglitz-Gasteil basing on charred plant macroremains, 2) investigating producer/consumer aspects of Prigglitz-Gasteil in comparison to the Bronze Age metallurgical sites of Kiechlberg, Klinglberg, and Mauken, and 3) reconstructing the miners' and metallurgists' diets. Our analyses demonstrate that the plant-based diet of the investigated mining communities reflects the general regional and chronological trends rather than particular preferences of the miners or metallurgists. The lack of chaff, combined with a high occurrence of processed food, suggests that the miners at Prigglitz-Gasteil were supplied from outside with ready-to-cook and processed grain, either from adjacent communities or from a larger distance. This consumer character is in accordance with observation from previously analysed metallurgical sites. Interestingly, the components observed in charred cereal products (barley, Hordeum vulgare, and foxtail millet, Setaria italica) contrast with the dominant crop taxa (broomcorn millet, Panicum miliaceum, foxtail millet, and lentil, Lens culinaris). Foraging of fruits and nuts also significantly contributed to the daily diet.
Assuntos
Agricultura/história , Arqueologia , Produtos Agrícolas , Dieta , Áustria , História AntigaRESUMO
Fennel (Foeniculum vulgare Miller) is a popular aromatic plant native to the Mediterranean basin and cultivated worldwide that is valued for the nutritional and health benefits of its fruits. Headspace solid-phase microextraction of 12 fennel accessions of cultivated (F. vulgare subsp. vulgare) and wild forms (F. vulgare subsp. piperitum) of different origins was carried out for assessing their volatile distribution. Fifty-four volatiles were identified, with ethers amounting for the major class at ca. 52-99% attributed to the abundance of (E)-anethole and estragole. Several subsp. vulgare accessions proved to be excellent sources of the chief aroma (E)-anethole (95.9-98.4%), whereas high levels of estragole at ca. 72% were observed in subsp. piperitum from Minia and Khartoum and must be considered in the safety assessment of fennel. Other volatile classes were detected including ketones, esters, aldehydes, alcohols, and hydrocarbons (monoterpenes, sesquiterpenes, and diterpenes). Fenchone exceeded 15% of the total volatiles in some fennel specimens, linked to a conspicuous bitter aftertaste. The members of subsp. piperitum were more enriched in monoterpene hydrocarbons with sabinene found exclusively in these, while subsp. vulgare comprised a higher content of ethers. Principle component analysis determined isoterpinolene as a special component in subsp. piperitum. In all specimens from the same group, estragole was the most distinguished volatile compound according to the findings from orthogonal partial least squares-discriminant analysis. The highest estimated estragole levels were detected in subsp. piperitum from Minia at 89.8 mg/g. This comparative study provides the first comprehensive insight into volatile profiling of 12 fennel fruit varieties.
RESUMO
Broomcorn millet (Panicum miliaceum L.) is not one of the founder crops domesticated in Southwest Asia in the early Holocene, but was domesticated in northeast China by 6000 BC. In Europe, millet was reported in Early Neolithic contexts formed by 6000 BC, but recent radiocarbon dating of a dozen 'early' grains cast doubt on these claims. Archaeobotanical evidence reveals that millet was common in Europe from the 2nd millennium BC, when major societal and economic transformations took place in the Bronze Age. We conducted an extensive programme of AMS-dating of charred broomcorn millet grains from 75 prehistoric sites in Europe. Our Bayesian model reveals that millet cultivation began in Europe at the earliest during the sixteenth century BC, and spread rapidly during the fifteenth/fourteenth centuries BC. Broomcorn millet succeeds in exceptionally wide range of growing conditions and completes its lifecycle in less than three summer months. Offering an additional harvest and thus surplus food/fodder, it likely was a transformative innovation in European prehistoric agriculture previously based mainly on (winter) cropping of wheat and barley. We provide a new, high-resolution chronological framework for this key agricultural development that likely contributed to far-reaching changes in lifestyle in late 2nd millennium BC Europe.
Assuntos
Agricultura/história , Produtos Agrícolas/história , Panicum/crescimento & desenvolvimento , Arqueologia , Produtos Agrícolas/crescimento & desenvolvimento , Domesticação , Europa (Continente) , História Antiga , Datação RadiométricaRESUMO
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.
Assuntos
Arqueologia/métodos , Cerveja/história , Grão Comestível , Proteínas de Plantas/ultraestrutura , Cerveja/análise , Grão Comestível/química , Grão Comestível/ultraestrutura , Egito , Europa (Continente) , História Antiga , Humanos , Microscopia Eletrônica de Varredura , Plântula/química , Plântula/ultraestruturaRESUMO
The Iceman site is unique in the bryology of the Quaternary. Only 21 bryophytes (mosses and liverworts) grow now in the immediate vicinity of the 5,300 year old Iceman discovery site at 3,210m above sea level in the Ötztal Alps, Italy. By contrast 75 or more species including at least ten liverworts were recovered as subfossils frozen in, on and around the Iceman from before, at and after his time. About two thirds of the species grow in the nival zone (above 3,000m above sea level) now while about one third do not. A large part of this third can be explained by the Iceman having both deliberately and inadvertently carried bryophytes during his last, fatal journey. Multivariate analyses (PCA, RDA) provide a variety of explanations for the arrivals of the bryophytes in the rocky hollow where the mummy was discovered. This is well into the nival zone of perennial snow and ice with a very sparse, non-woody flora and very low vegetation cover. Apart from the crucial anthropochory (extra-local plants), both hydrochory (local species) and zoochory (by wild game such as ibex of both local and extra-local species) have been important. Anemochory of mainly local species was of lesser importance and of extra-local species probably of little or no importance. The mosses Neckera complanata and several other ecologically similar species as well as a species of Sphagnum (bogmoss) strongly support the claim that the Iceman, took northwards up Schnalstal, South Tyrol, as the route of the last journey. A different species of bogmoss, taken from his colon is another indication the Iceman's presence at low altitude south of Schnalstal during his last hours when he was first high up, low down and finally at over 3,000m.
Assuntos
Briófitas , Fenômenos Ecológicos e Ambientais , Hepatófitas , Gelo , Arqueologia , HumanosRESUMO
Cereals, in addition to being a major ingredient in daily meals, also play a role in the preparation of foodstuffs for ritual purposes. This paper deals with finds that may correspond to such ritual preparations retrieved from the hillfort site of Stillfried an der March. The site, spreading across an area of ca. 23 ha, held a very important position among settlements of Late Urnfield period (particularly during the 10th- 9th c. BCE), acting as a central place where large scale storage of grain as well as textile and metal production took place under the control of local elites. Three incomplete ring-shaped charred organic objects, found together with 14 rings and ring fragments made of clay were discovered in a secondary filled silo pit, excavated among a total of about 100 pits of this kind at the site. The overall good state of preservation of the organic ring fragments suggests that they were deposited intact on the bottom of the pit and covered well so that no re-deposition or damage occurred. This could be indicate their intentional placement in this position. Light and scanning electron microscopy revealed that the charred organic rings are cereal products containing hulled barley and a wheat species. Indications that the objects were shaped from a wet cereal mixture and had been subsequently dried without baking are discussed, as well as the possible significance of the find assemblage. The annular objects are put in context with the contemporary cereal spectrum as well as other cereal preparations from Stillfried, outlining their different chaînes opératoires for handling cereal food.
Assuntos
Arqueologia , Pão , Grão Comestível , Áustria , Biodiversidade , TriticumRESUMO
Fabaceae is well-known for its seed nutritious and bioactive composition as exemplified by Lupinus and Lens. Developing efficient analytical approaches for profiling their bioactive matrix is a prerequisite to provide proof for their health benefits or nutritive traits. Eight Lupinus and Lens seed accessions were subjected to liquid chromatography-mass spectrometry (UPLC-MS)-based metabolomic study, which identified 66 metabolites, viz. flavonoids, alkaloids, saponins, phenolics, fatty acids and sphingolipids. Chemometric tools were explored to assess heterogeneity across the two genera leading to elucidation of the species-most enriched and differential metabolites. The two dark-colored lentil cultivars are identified as the richest source of functional foods with presumed therapeutic benefits; however, Lupinus hispanicus was proved to be the most nutritive accession. To our knowledge, this study provides the first UPLC-MS-based comparative metabolite profiling of Lupinus and Lens seeds. This platform was also able to discern metabolites diversity at the intraspecific level among Lupinus species and Lens cultivars.
Assuntos
Cromatografia Líquida/métodos , Lens (Planta)/química , Lupinus/anatomia & histologia , Metaboloma , Sementes/química , Espectrometria de Massas em Tandem/métodos , Alcaloides/análise , Áustria , Ácidos Graxos/análise , Flavonoides/análise , Alimento Funcional/análise , Análise Multivariada , Fenóis/análise , Extratos Vegetais/análise , Saponinas/análise , Esfingolipídeos/análiseRESUMO
Lens culinaris and several Lupinus species are two legumes regarded as potential protein resources aside from their richness in phytochemicals. Consequently, characterization of their metabolite composition seems warranted to be considered as a sustainable commercial functional food. This study presents a discriminatory holistic approach for metabolite profiling in accessions of four lentil cultivars and four Lupinus species via gas chromatography/mass spectrometry. A total of 107 metabolites were identified, encompassing organic and amino acids, sugars, and sterols, along with antinutrients, viz., alkaloids and sugar phosphates. Among the examined specimens, four nutritionally valuable accessions ought to be prioritized for future breeding to include Lupinus hispanicus, enriched in organic ( ca. 11.7%) and amino acids ( ca. 5%), and Lupinus angustifolius, rich in sucrose ( ca. 40%), along with two dark-colored lentil cultivars 'verte du Puy' and 'Black Beluga' enriched in peptides. Antinutrient chemicals were observed in Lupinus polyphyllus, owing to its high alkaloid content. Several species-specific markers were also revealed using multivariate data analyses.
Assuntos
Lens (Planta)/química , Lupinus/química , Extratos Vegetais/química , Alcaloides/química , Cromatografia Gasosa-Espectrometria de Massas/métodos , Lupinus/metabolismo , Valor Nutritivo , Sementes/química , Sementes/metabolismoRESUMO
The site of Parkhaus Opéra is located on the north-eastern shore of Lake Zürich (Switzerland) and was documented during a rescue excavation in 2010 and 2011 by the Office for Urbanism, City of Zürich. Two charred bread-like objects were found in late Neolithic Layer 13 of the pile-dwelling, and are investigated using a novel set of analyses for cereal-based foodstuffs. Tissue remains of barley and wheat were identified, as well as a schizocarp of celery (cf. Apium graveolens), providing the first evidence for the use of bread condiments in the Neolithic. Cereal particle sizes were recorded and used to draw conclusions regarding milling and sieving of the raw material. Gas bubbles in the charred objects were measured in order to evaluate possible leavening of the dough. The outcomes of this research significantly advance the understanding of the production traits of cereal-based food during the Neolithic. The analytical techniques proposed by this study open up new possibilities for systematic and consistent investigations of cereal-based archaeological foodstuffs.
Assuntos
Arqueologia , Pão/análise , Grão Comestível/química , Grão Comestível/metabolismo , Triticum/química , Triticum/metabolismo , Indústria de Processamento de Alimentos , Humanos , SuíçaRESUMO
Trigonella foenum-graecum is a plant of considerable value for its nutritive composition as well as medicinal effects. This study aims to examine Trigonella seeds using a metabolome-based ultra-performance liquid chromatography-mass spectrometry (UPLC-MS) in parallel to gas chromatography-mass spectrometry (GC-MS) coupled with multivariate data analyses. The metabolomic differences of seeds derived from three Trigonella species, i.e., T. caerulea, T. corniculata, and T. foenum-graecum, were assessed. Under specified conditions, we were able to identify 93 metabolites including 5 peptides, 2 phenolic acids, 22 C/O-flavonoid conjugates, 26 saponins, and 9 fatty acids using UPLC-MS. Several novel dipeptides, saponins, and flavonoids were found in Trigonella herein for the first time. Samples were classified via unsupervised principal component analysis (PCA) followed by supervised orthogonal projection to latent structures-discriminant analysis (OPLS-DA). A distinct separation among the investigated Trigonella species was revealed, with T. foenum-graecum samples found most enriched in apigenin-C-glycosides, viz. vicenins 1/3 and 2, compared to the other two species. In contrast to UPLC-MS, GC-MS was less efficient to classify specimens, with differences among specimens mostly attributed to fatty acyl esters. GC-MS analysis of Trigonella seed extracts led to the identification of 91 metabolites belonging mostly to fatty acyl esters, free fatty acids followed by organic acids, sugars, and amino acids. This study presents the first report on primary and secondary metabolite compositional differences among Trigonella seeds via a metabolomics approach and reveals that, among the species examined, the official T. foenum-graecum presents a better source of Trigonella secondary bioactive metabolites.
Assuntos
Metaboloma , Metabolômica/métodos , Extratos Vegetais/metabolismo , Sementes/metabolismo , Trigonella/metabolismo , Cromatografia Gasosa-Espectrometria de Massas , Análise Multivariada , Análise de Componente PrincipalRESUMO
Nigella sativa, commonly known as black cumin seed, is a popular herbal supplement that contains numerous phytochemicals including terpenoids, saponins, flavonoids, alkaloids. Only a few of the ca. 15 species in the genus Nigella have been characterized in terms of phytochemical or pharmacological properties. Here, large scale metabolic profiling including UPLC-PDA-MS and GC-MS with further multivariate analysis was utilized to classify 6 Nigella species. Under optimized conditions, we were able to annotate 52 metabolites including 8 saponins, 10 flavonoids, 6 phenolics, 10 alkaloids, and 18 fatty acids. Major peaks in UPLC-MS spectra contributing to the discrimination among species were assigned as kaempferol glycosidic conjugates, with kaempferol-3-O-[glucopyranosyl-(1â2)-galactopyranosyl-(1â2)-glucopyranoside, identified as potential taxonomic marker for N. sativa. Compared with GC-MS, UPLC-MS was found much more efficient in Nigella sample classification based on genetic and geographical origin. Nevertheless, both GC-MS and UPLC-MS support the remote position of Nigella nigellastrum in relation to the other taxa.