Search

Your search keyword '"Miliacin"' showing total 10 results
Start Over Descriptor "Miliacin" Publisher hal ccsd
10 results on '"Miliacin"'

1. Hydrogen isotopic fractionations during syntheses of lipid biomarkers in the seeds of broomcorn millet (Panicum miliaceum L.) under controlled environmental conditions

Author

Patricia Richard, Nicolas Bossard, Valery J. Terwilliger, Claude Le Milbeau, Elisabeth Vergès, Philippe Biron, Jérémy Jacob, Thierry Bariac, Institut des Sciences de la Terre d'Orléans - UMR7327 (ISTO), Bureau de Recherches Géologiques et Minières (BRGM) (BRGM)-Observatoire des Sciences de l'Univers en région Centre (OSUC), Institut national des sciences de l'Univers (INSU - CNRS)-Observatoire de Paris, Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université d'Orléans (UO)-Centre National de la Recherche Scientifique (CNRS)-Institut national des sciences de l'Univers (INSU - CNRS)-Observatoire de Paris, Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université d'Orléans (UO)-Centre National de la Recherche Scientifique (CNRS)-Institut national des sciences de l'Univers (INSU - CNRS)-Université d'Orléans (UO)-Centre National de la Recherche Scientifique (CNRS), Biogéosystèmes Continentaux - UMR7327, Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université d'Orléans (UO)-Centre National de la Recherche Scientifique (CNRS)-Institut national des sciences de l'Univers (INSU - CNRS)-Université d'Orléans (UO)-Centre National de la Recherche Scientifique (CNRS)-Bureau de Recherches Géologiques et Minières (BRGM) (BRGM)-Observatoire des Sciences de l'Univers en région Centre (OSUC), Laboratoire des Sciences du Climat et de l'Environnement [Gif-sur-Yvette] (LSCE), Institut national des sciences de l'Univers (INSU - CNRS)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université de Versailles Saint-Quentin-en-Yvelines (UVSQ), Géochrononologie Traceurs Archéométrie (GEOTRAC), Institut national des sciences de l'Univers (INSU - CNRS)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université de Versailles Saint-Quentin-en-Yvelines (UVSQ)-Institut national des sciences de l'Univers (INSU - CNRS)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université de Versailles Saint-Quentin-en-Yvelines (UVSQ), Institut d'écologie et des sciences de l'environnement de Paris (iEES Paris ), Institut de Recherche pour le Développement (IRD)-Sorbonne Université (SU)-Université Paris-Est Créteil Val-de-Marne - Paris 12 (UPEC UP12)-Centre National de la Recherche Scientifique (CNRS)-Université de Paris (UP)-Institut National de Recherche pour l’Agriculture, l’Alimentation et l’Environnement (INRAE), LE STUDIUM (LE STUDIUM), Bureau de Recherches Géologiques et Minières (BRGM) (BRGM)-Centre national du machinisme agricole, du génie rural, des eaux et forêts (CEMAGREF)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de recherche pour le développement [IRD] : UR-Centre National de la Recherche Scientifique (CNRS)-Institut National de Recherche pour l’Agriculture, l’Alimentation et l’Environnement (INRAE), University of Kansas [Kansas City], Simon Fraser University (SFU.ca), Ministère de la Recherche et de l’Enseignement Supérieur (Action Thématique Prioritaire, 2009-2012)., Le Studium® (Loire Institute for Advanced Studies)., ANR-10-JCJC-0607,PalHydroMil,Reconstructions paléohydrologiques à partir du dD de lipides produits par les végétaux supérieurs. Calibration, validation et application aux variations hydrologiques dans les Alpes pendant l'âge du Bronze(2010), Université de Versailles Saint-Quentin-en-Yvelines (UVSQ)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Institut national des sciences de l'Univers (INSU - CNRS)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS), Université de Versailles Saint-Quentin-en-Yvelines (UVSQ)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Institut national des sciences de l'Univers (INSU - CNRS)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS)-Université de Versailles Saint-Quentin-en-Yvelines (UVSQ)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Institut national des sciences de l'Univers (INSU - CNRS)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS), Institut de Recherche pour le Développement (IRD)-Sorbonne Université (SU)-Université Paris-Est Créteil Val-de-Marne - Paris 12 (UPEC UP12)-Centre National de la Recherche Scientifique (CNRS)-Institut National de Recherche pour l’Agriculture, l’Alimentation et l’Environnement (INRAE), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Institut de recherche pour le développement [IRD] : UR-Centre National de la Recherche Scientifique (CNRS), POTHIER, Nathalie, and Jeunes Chercheuses et Jeunes Chercheurs - Reconstructions paléohydrologiques à partir du dD de lipides produits par les végétaux supérieurs. Calibration, validation et application aux variations hydrologiques dans les Alpes pendant l'âge du Bronze - - PalHydroMil2010 - ANR-10-JCJC-0607 - JCJC - VALID

Subjects
010504 meteorology & atmospheric sciences, Hydrogen, chemistry.chemical_element, Biosynthetic fractionation hydrogen isotopes Panicum miliaceum Biogeochemical chambers compound-specific δ2H, Fractionation, Leaf water, 010502 geochemistry & geophysics, Graminoid, 01 natural sciences, GEOF, [SDU] Sciences of the Universe [physics], Triterpene, Geochemistry and Petrology, Relative humidity, [SDU.ENVI]Sciences of the Universe [physics]/Continental interfaces, environment, 0105 earth and related environmental sciences, chemistry.chemical_classification, Panicum miliaceum, biology, Chemistry, food and beverages, miliacin, biology.organism_classification, [SDU.ENVI] Sciences of the Universe [physics]/Continental interfaces, environment, [SDU]Sciences of the Universe [physics], Environmental chemistry, biomarker, Lipid biomarkers
Abstract

International audience; Compound specific hydrogen isotopic analyses have the potential to reveal the biosynthetic pathways of biomarkers and to reconstruct the effects of water stress in a plant, or in an ecosystem. Although C4 graminoids are of great geological interest and are some of the world's leading crops, there are few experimental studies of their biomarker responses to hydrological conditions. Here, we study a C4 graminoid, broomcorn millet, and compare the effects of controlled changes in environmental conditions on the distributions of n-alkane homologues and on the pentacyclic triterpene, miliacin, which is a biomarker for broomcorn millet; both were measured in the seeds of the graminoid. Broomcorn millet plants were propagated in hydroponic solutions with four different δ2H values for each of two growth chambers, differing in relative humidity (58 and 74 %). Analyses of δ2H values of the lipid compounds (miliacin and n-alkanes) in seeds and water extracted from transpiring and non-transpiring organs allowed us to quantify the apparent (lipids vs. source water to plant) and biosynthetic (lipids vs. leaf water) fractionations during miliacin and n-alkane syntheses. Miliacin and n-alkane δ2H values were linearly related to leaf water δ2H values, permitting credible biosynthetic fractionations to be calculated for n-alkanes (average -149.5‰ ± 11) and miliacin (-118‰ ± 5). These biosynthetic fractionations were within the range of published values for compounds with their respective biosynthetic pathways, although a 2H-enrichment of miliacin compared to n-alkanes remains unexplained.Whereas a 16% decrease in relative humidity had no significant impact on the biosynthetic fractionation of miliacin, n-C25 and n-C27 alkanes, it led to a ∼25‰ decrease in biosynthetic fractionation for n-C31 and n-C33 alkanes. This could be the consequence of a contribution of more depleted pools of hydrogen atoms in cytoplasmic water (compared to chloroplastic hydrogen pools) during the n-alkyl lipid elongation process. This finding suggests that the respective influences of source water δ2H values and relative humidity on the δ2H values of organic compounds may be discretely inferred by examining the δ2H values of compounds synthesized from distinct sources of hydrogen in cells. It provides clues to the biosynthetic fractionations in a C4 plant for compounds derived from distinct pathways, but also highlights specific issues related to seed lipids that would require further research.

Published
2021
Full Text
View/download PDF

2. Archaeobotanical investigations at the earliest horse herder site of Botai in Kazakhstan

Author

S. Zakharov, V. F. Zaibert, Martin K. Jones, A. K. Outram, Emma Lightfoot, Jérémy Jacob, Xinyi Liu, Giedre Motuzaite Matuzeviciute, Lithuanian Institute of History, McDonald Institute for Archaeological Research, University of Cambridge [UK] (CAM), Washington University in Saint Louis (WUSTL), Géochrononologie Traceurs Archéométrie (GEOTRAC), Laboratoire des Sciences du Climat et de l'Environnement [Gif-sur-Yvette] (LSCE), Institut national des sciences de l'Univers (INSU - CNRS)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université de Versailles Saint-Quentin-en-Yvelines (UVSQ)-Institut national des sciences de l'Univers (INSU - CNRS)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université de Versailles Saint-Quentin-en-Yvelines (UVSQ), University of Exeter, Al-Farabi Kazakh National University, Department of Archaeology and Anthropology, Université de Versailles Saint-Quentin-en-Yvelines (UVSQ)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Institut national des sciences de l'Univers (INSU - CNRS)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS)-Université de Versailles Saint-Quentin-en-Yvelines (UVSQ)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Institut national des sciences de l'Univers (INSU - CNRS)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS), and Al-Farabi Kazakh National University [Almaty] (KazNU)

Subjects
010506 paleontology, Archeology, [SHS.ARCHEO]Humanities and Social Sciences/Archaeology and Prehistory, Population, 01 natural sciences, GEOF, law.invention, Eurasiansteppe, Miliacin, Paleoethnobotany, Bronze Age, law, [SDU.STU.GC]Sciences of the Universe [physics]/Earth Sciences/Geochemistry, 0601 history and archaeology, Radiocarbon dating, education, 0105 earth and related environmental sciences, education.field_of_study, 060102 archaeology, Eneolithic, Subsistence agriculture, Excavation, Agriculture, 06 humanities and the arts, Chalcolithic, 15. Life on land, Archaeology, Geography, Anthropology, [SDU.STU.ST]Sciences of the Universe [physics]/Earth Sciences/Stratigraphy, Period (geology), Archaeobotany
Abstract

International audience; This paper presents new radiocarbon dates and the results of the first archaeobotanical investigations at Eneolithic Botai site, for the first time aiming to explore the plant food component in the diet of Botai population and if the inhabitants of the Botai were a part of an early crop food exchange network. Our excavation of a hut circle and associated radiocarbon dating placed its occupation within a date range commencing around 3550 and 3030 cal BC and ending between 3080 and 2670 cal BC. A separate feature (likely a stove or kiln), excavated in test trench E, would seem to be younger, around 2000 cal BC. The dating of the site thus also indicates a previously unknown later occupation at Botai, opening further discussions on human subsistence and interaction as well as horse management in northern Eurasia from the Eneolithic to the Bronze Age. The archaeobotanical results, derived from systematic sampling and analysis of macrobotanical remains, plant phytoliths, and molecular biomarker analysis show that the Botai populations were not part of any wider crop network. The relatively small seed count would indicate that plant foods did not constitute a substantial component of economic life. On the other hand, the presence of miliacin could suggest possible millet cultivation or consumption in this region at some point in the past, possibly after the main occupation period of Botai.

Published
2019
Full Text
View/download PDF

3. Molecular, isotopic and radiocarbon evidence for broomcorn millet cropping in Northeast France since the Bronze Age

Author

Blandine Courel, Estelle Motsch, Clément Féliu, Damien Ertlen, Irka Hajdas, Philippe Schaeffer, Stefano M. Bernasconi, Emile Moser, Dominique Schwartz, Pierre Adam, Quentin Ebert, Institut de Chimie de Strasbourg, Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), Institut national de recherches archéologiques préventives (Inrap), Archéologie et histoire ancienne : Méditerranée - Europe (ARCHIMEDE), Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Ministère de la Culture et de la Communication (MCC)-Centre National de la Recherche Scientifique (CNRS), Geologisches Institut [ETH Zürich], Eidgenössische Technische Hochschule - Swiss Federal Institute of Technology [Zürich] (ETH Zürich), Laboratory of Ion Beam Physics, Laboratoire Image, Ville, Environnement (LIVE), Université de Strasbourg (UNISTRA)-Centre National de la Recherche Scientifique (CNRS), and Université de Strasbourg (UNISTRA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
010506 paleontology, [SHS.ARCHEO]Humanities and Social Sciences/Archaeology and Prehistory, 010502 geochemistry & geophysics, 01 natural sciences, Panicum miliaceum, Archaeometry, law.invention, Miliacin, Geochemistry and Petrology, Bronze Age, law, [CHIM.ANAL]Chemical Sciences/Analytical chemistry, Silo, Radiocarbon dating, 0105 earth and related environmental sciences, biology, Ecology, biology.organism_classification, Archaeology, Soil lipids, Digging, Soil water, Period (geology), Pedological traps, Compound-specific radiocarbon analysis, Cropping, [CHIM.RADIO]Chemical Sciences/Radiochemistry, Geology
Abstract

Molecular and isotopic investigation of lipids from soils filling several structures from an archaeological site located at Obernai (Alsace, NE France) has revealed the presence of miliacin, a triterpenoid marker from Panicum miliaceum (broomcorn millet), indicating that this cereal was cultivated at the site. The concentration profiles of miliacin within silos and its detection in other archaeological structures (e.g., Gaulish pit) suggest that miliacin did not originate from cereals stored in the silos but rather came from remains of millet from cultivated soils which filled the silos after they were abandoned. Furthermore, the 14C age of miliacin isolated from a silo of the Second Iron Age was shown to be considerably older (Bronze Age) than the structure itself, revealing that the soil filling the silo therefore archived the molecular signature from past millet cropping, predating the digging of the silo. Thus, radiocarbon dating of the isolated miliacin allowed the timing of millet cropping to be determined, showing that it was established during the Bronze Age and the Roman Gaul period at Obernai. This is the first evidence of millet cultivation in Alsace dating back to the Bronze Age, bringing new perspectives on agricultural practices and past dietary practice in Eastern France. The combination of molecular studies and radiocarbon dating of individual lipids highlights the potential of hollow structures like silos and pits to act as “pedological traps”, recording information on past vegetation cover or agricultural practices from the surface horizons of surrounding soils that filled these structures after abandonment.

Published
2017
Full Text
View/download PDF

4. (D/H) Isotopic Fractionation by Anisotropic NAD 2D-NMR Spectroscopy: Exploiting the Analytical Wealth of Oriented Solvents to Investigate Molecules of Interest

Author

Lesot, Philippe, Berdagué, Philippe, Jacob, Jérémy, Institut de Chimie Moléculaire et des Matériaux d'Orsay (ICMMO), Université Paris-Sud - Paris 11 (UP11)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), Institut des Sciences de la Terre d'Orléans - UMR7327 (ISTO), Bureau de Recherches Géologiques et Minières (BRGM) (BRGM)-Observatoire des Sciences de l'Univers en région Centre (OSUC), Institut national des sciences de l'Univers (INSU - CNRS)-Observatoire de Paris, Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université d'Orléans (UO)-Centre National de la Recherche Scientifique (CNRS)-Institut national des sciences de l'Univers (INSU - CNRS)-Observatoire de Paris, Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université d'Orléans (UO)-Centre National de la Recherche Scientifique (CNRS)-Institut national des sciences de l'Univers (INSU - CNRS)-Université d'Orléans (UO)-Centre National de la Recherche Scientifique (CNRS), ANR-10-JCJC-0607,PalHydroMil,Reconstructions paléohydrologiques à partir du dD de lipides produits par les végétaux supérieurs. Calibration, validation et application aux variations hydrologiques dans les Alpes pendant l'âge du Bronze(2010), Centre National de la Recherche Scientifique (CNRS)-Université d'Orléans (UO)-Institut national des sciences de l'Univers (INSU - CNRS)-Observatoire des Sciences de l'Univers en région Centre (OSUC), Institut national des sciences de l'Univers (INSU - CNRS)-Centre National de la Recherche Scientifique (CNRS)-Université d'Orléans (UO)-Observatoire de Paris, Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Institut national des sciences de l'Univers (INSU - CNRS)-Centre National de la Recherche Scientifique (CNRS)-Université d'Orléans (UO)-Observatoire de Paris, and Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Bureau de Recherches Géologiques et Minières (BRGM) (BRGM)

Subjects
hydrogen isotopes, [SDV.EE.ECO]Life Sciences [q-bio]/Ecology, environment/Ecosystems, [CHIM.ORGA]Chemical Sciences/Organic chemistry, [SDU.STU.GC]Sciences of the Universe [physics]/Earth Sciences/Geochemistry, [SHS.ENVIR]Humanities and Social Sciences/Environmental studies, [SDE.MCG]Environmental Sciences/Global Changes, paleoclimate, miliacin, [SDU.ENVI]Sciences of the Universe [physics]/Continental interfaces, environment, GEOF, deuterium, RMN
Abstract

International audience; The deuterium/hydrogen (D/H)i ratio measurement by quantitative 2H-{1H} NMR spectroscopy is a method of choice in numerous analytical fields such as the study of biosynthetic pathway or kinetic isotopic effects associated with enzyme-catalyzed reaction, the determination of botanical or geographical origin of biocompounds, and last by not least, the authentication of molecules in the frame of the fight against counterfeigthing [1,2]. As the solvent used in the « SNIF-NMR » protocol is both isotropic (liquid) and achiral, the efficiency of the current protocol is basically limited for two reasons : i) the small 2H chemical shift dispersion of deuterium nuclei (expressed i Hz); ii) the impossibility of spectrally discriminating enantiotopic sites (methylene prostereogenic sites) in prochiral molecules or enantiomers of chiral molecules, hence precluding the quantification of isotopic fractionation on methylene prostereogenic sites or mirror-image isomers [3].To overcome these drawbacks, the natural abundance deuterium bidimensional NMR (NAD 2D-NMR) using chiral oriented phases is a powerful way to separate deuterium signals of monodeutero-isotopomers on the basis of the quadrupolar interaction, not longer averaged to zero as in isotropic NMR. The distribution of quadrupolar doublets on the 2D maps significantly facilitates the analysis of overcrowded NAD 1D-NMR spectra obtained in liquid state, thus providing a real original and robust approach to classical tool [2-5]. To illustrate the analytical potential of the method, various illustrative examples of (pro)chiral molecules of interest are presented. Among them, the case of miliacin of a triterpenic chiral molecular biomarker found in sedimentary archives is examined [6,7]. Among perspectives, this approach has the potential to permit predicting isotopic natural fractionations during pentacyclic triterpene diagenesis.References:[1] G. J. Martin, M.L. Martin, Tet. Lett., 22, 3525, (1981).[2] P. Lesot, Encyclopedia of Magnetic Resonance (eMagRes), 2 (3), 315, (2013).[3] P. Lesot, C. Aroulanda, H. Zimmermann, Z. Luz Chem. Soc. Rev., 44, 230, (2015). [4] P. Lesot, Z. Serhan, I. Billault, Anal. Bioanal. Chem., 399, 1187, (2011).[5] Z. Serhan, I. Billault, A. Borgogno, A. Ferrarini, P. Lesot, Chem. Eur. J., 18, 117, (2012). [6] P. Berdagué, P. Lesot, J. Jacob, V.-J. Terwilliger, C. Le Milbeau, Geochim. Cosmochim. Acta, 173, 337, (2016).[7] http://www.cnrs.fr/inc/communication/direct_labos/lesot2.htm http://www.insu.cnrs.fr/environnement/actualites

Published
2016

5. Contribution of NAD 2D-NMR in liquid crystals to the determination of hydrogen isotope profile of methyl groups in miliacin

Author

Philippe Lesot, Jérémy Jacob, Valery J. Terwilliger, P. Berdagué, Claude Le Milbeau, Université Paris-Saclay, Institut de Chimie Moléculaire et des Matériaux d'Orsay (ICMMO), Institut de Chimie du CNRS (INC)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS), Centre National de la Recherche Scientifique (CNRS), Université d'Orléans (UO), Institut des Sciences de la Terre d'Orléans - UMR7327 (ISTO), Centre National de la Recherche Scientifique (CNRS)-Université d'Orléans (UO)-Institut national des sciences de l'Univers (INSU - CNRS)-Observatoire des Sciences de l'Univers en région Centre (OSUC), Institut national des sciences de l'Univers (INSU - CNRS)-Observatoire de Paris, Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université d'Orléans (UO)-Centre National de la Recherche Scientifique (CNRS)-Institut national des sciences de l'Univers (INSU - CNRS)-Observatoire de Paris, Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université d'Orléans (UO)-Centre National de la Recherche Scientifique (CNRS)-Bureau de Recherches Géologiques et Minières (BRGM) (BRGM), University of Kansas [Kansas City], and ANR-10-JCJC-0607,PalHydroMil,Reconstructions paléohydrologiques à partir du dD de lipides produits par les végétaux supérieurs. Calibration, validation et application aux variations hydrologiques dans les Alpes pendant l'âge du Bronze(2010)

Subjects
Deuterium NMR, Amyrin, 010504 meteorology & atmospheric sciences, Stereochemistry, Isotope profile, 010502 geochemistry & geophysics, Biosynthesis, 01 natural sciences, Diagenesis, chemistry.chemical_compound, Miliacin, Geochemistry and Petrology, Computational chemistry, Molecule, [SDU.ENVI]Sciences of the Universe [physics]/Continental interfaces, environment, 0105 earth and related environmental sciences, Isotope, chemistry, Deuterium, Liquid crystal, 13. Climate action, [SDU]Sciences of the Universe [physics], Yield (chemistry), Natural abundance, Site-specific, Pentacyclic triterpene, Two-dimensional nuclear magnetic resonance spectroscopy
Abstract

International audience; The hydrogen isotopic composition (δD or (D/H) value) of molecular biomarkers preserved in sedimentary archives is increasingly used to provide clues about the evolution of past climatic conditions. The rationale is that intact biomarkers retain isotopic information related to the climatic conditions that prevailed at the time of their synthesis. Some of these biomarkers may be degraded during diagenesis, however. The extent to which these degradations alter the original δD value of the source biomarker is presently debated and the capacity to resolve the debate by determinations of compound-specific δD values alone is limited. The “bulk” or “global” δD value of any molecule is in fact a composite of δD values at each site within this molecule ((δDi or (D/H)i with i= number of hydrogen/deuterium atoms in the considered molecule). Determination of this site-specific δDi value in biomarkers could not only yield outstanding paleoenvironmental information but also help forecast the impacts of diagenesis and define essential steps in biosynthetic pathways.This task is analytically challenging. Here, we examined the capabilities of natural abundance deuterium 2D-NMR (NAD 2D-NMR) using homopolypeptide liquid crystals as an NMR solvent to: i) analyze the NAD spectra of biomakers; ii) determine the site-specific distribution of hydrogen in the nine methyl groups (δDMei with i= 23 to 31) of miliacin, a pentacyclic triterpene of the amyrin family and key biomarker for broomcorn millet in sedimentary archives. Relative (D/H)Mei values were established by anisotropic NAD 2D-NMR. Then absolute δDMei values were obtained by determining δDMei value of the methoxy group of miliacin using two independent approaches: isotropic NAD NMR (SNIF-NMRTM) and GC-irMS. The resulting isotope profile for miliacin shows, for the first time, large variations in δDMei values that can directly be explained by biosynthetic processes. This approach has also the potential to permit predicting fractionations during pentacyclic triterpene diagenesis.

Published
2016
Full Text
View/download PDF

6. Miliacin in palaeosols from an Early Iron Age in Ukraine reveal in situ cultivation of broomcorn millet

Author

Jérémy Jacob, Giedre Motuzaite-Matuzeviciute, Sergey Telizhenko, Martin K. Jones, McDonald Institute for Archaeological Research, University of Cambridge [UK] (CAM), History Faculty/Department of Archaeology, Vilnius University [Vilnius], Institut des Sciences de la Terre d'Orléans - UMR7327 (ISTO), Centre National de la Recherche Scientifique (CNRS)-Université d'Orléans (UO)-Institut national des sciences de l'Univers (INSU - CNRS)-Observatoire des Sciences de l'Univers en région Centre (OSUC), Institut national des sciences de l'Univers (INSU - CNRS)-Observatoire de Paris, Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université d'Orléans (UO)-Centre National de la Recherche Scientifique (CNRS)-Institut national des sciences de l'Univers (INSU - CNRS)-Observatoire de Paris, Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université d'Orléans (UO)-Centre National de la Recherche Scientifique (CNRS)-Bureau de Recherches Géologiques et Minières (BRGM) (BRGM), Institute of Archaeology in Crimea, National Academy of Science of Ukraine, Department of Archaeology, and Gates Trust and Arts and Humanities Research Council, the PaléoChamps project (AIR Archéométrie, CNRS)

Subjects
010506 paleontology, Archeology, Biogeochemical cycle, Floodplain, Broomcorn millet cultivation, [SDE.MCG]Environmental Sciences/Global Changes, Population, Sarmatian period, 01 natural sciences, law.invention, Miliacin, law, 0601 history and archaeology, Radiocarbon dating, education, [SDU.ENVI]Sciences of the Universe [physics]/Continental interfaces, environment, 0105 earth and related environmental sciences, geography, education.field_of_study, geography.geographical_feature_category, Panicum miliaceum, 060102 archaeology, biology, 06 humanities and the arts, 15. Life on land, biology.organism_classification, Archaeology, Paleosol, Iron Age, Anthropology, Period (geology), Scythian period, Ukraine, Geology
Abstract

International audience; During the archaeobotanical investigation of Scythian-Sarmatian period (Early Iron Age), pits with crop processing waste, discovered in the floodplain of Donets River, eastern Ukraine, and charred remains of cereal grains, dominated by broomcorn millet, were recorded. The grains from the pits were radiocarbon dated to the fifth to first century BC. Those pits are distant from any known contemporaneous settlement. The apparent disconnection of these pits from any local settlement suggests that (1) millet was brought from other locations by mobile groups, or (2) millet was cultivated locally by populations whose settlements have left no discernible archaeological trace. The analysis of molecular biomarkers preserved in palaeosols that are stratigraphically connected to the pits revealed high levels of miliacin, a molecule that can be preserved in ancient soils and sediments, and that is consistent with broomcorn millet (Panicum miliaceum). High levels in miliacin in soils stratigraphically connected to the pits are interpreted as the result of a large biomass of P. miliaceum produced at time of soil formation. Our biogeochemical results applied to a palaeosol thus attest to the in situ cultivation of crops dominated by the broomcorn millet during the early Iron Age in the floodplain of Donets River. Biochemical examination of soils and palaeosols can thus provide useful information on past dynamics of land-use by ancient population, especially when settlements or macrobotanical remains are absent.

Published
2016
Full Text
View/download PDF

7. Miliacin from broomcorn millet – a fossil molecule of multiple interests for archaeologists and paleoenvironmentalists

Author

Jacob, Jérémy, Simonneau, Anaëlle, Bossard, Nicolas, Le Milbeau, Claude, Lavrieux, Marlène, Motuzaite-Matuzeviciute, Giedre, Terwilliger, Valery T., Lesot, Philippe, Poissonnier, Bertrand, Billaud, Yves, Institut des Sciences de la Terre d'Orléans - UMR7327 (ISTO), Centre National de la Recherche Scientifique (CNRS)-Université d'Orléans (UO)-Institut national des sciences de l'Univers (INSU - CNRS)-Observatoire des Sciences de l'Univers en région Centre (OSUC), Institut national des sciences de l'Univers (INSU - CNRS)-Centre National de la Recherche Scientifique (CNRS)-Université d'Orléans (UO)-Observatoire de Paris, Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Institut national des sciences de l'Univers (INSU - CNRS)-Centre National de la Recherche Scientifique (CNRS)-Université d'Orléans (UO)-Observatoire de Paris, Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Bureau de Recherches Géologiques et Minières (BRGM) (BRGM), Swiss Federal Institute of Aquatic Science & Technology (EAWA), History Faculty/Department of Archaeology, Vilnius University [Vilnius], McDonald Institute for Archaeological Research, University of Cambridge [UK] (CAM), Institut de Chimie Moléculaire et des Matériaux d'Orsay (ICMMO), Université Paris-Sud - Paris 11 (UP11)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), Institut national de recherches archéologiques préventives (Inrap), Département des Recherches Archéologiques Subaquatiques et Sous-Marines [Marseille] (DRASSM), Ministère de la Culture (MC), ANR-10-JCJC-0607,PalHydroMil,Reconstructions paléohydrologiques à partir du dD de lipides produits par les végétaux supérieurs. Calibration, validation et application aux variations hydrologiques dans les Alpes pendant l'âge du Bronze(2010), Bureau de Recherches Géologiques et Minières (BRGM) (BRGM)-Observatoire des Sciences de l'Univers en région Centre (OSUC), Institut national des sciences de l'Univers (INSU - CNRS)-Observatoire de Paris, Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université d'Orléans (UO)-Centre National de la Recherche Scientifique (CNRS)-Institut national des sciences de l'Univers (INSU - CNRS)-Observatoire de Paris, and Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université d'Orléans (UO)-Centre National de la Recherche Scientifique (CNRS)-Institut national des sciences de l'Univers (INSU - CNRS)-Université d'Orléans (UO)-Centre National de la Recherche Scientifique (CNRS)

Subjects
archaeobotanic, Millet, [SHS.ARCHEO]Humanities and Social Sciences/Archaeology and Prehistory, [CHIM.ORGA]Chemical Sciences/Organic chemistry, [SDE.MCG]Environmental Sciences/Global Changes, miliacin, organic geochemistry, archaeology, caucasus, GEOF, [SDE.ES]Environmental Sciences/Environmental and Society, [SDV.EE.ECO]Life Sciences [q-bio]/Ecology, environment/Ecosystems, [SDU.STU.GC]Sciences of the Universe [physics]/Earth Sciences/Geochemistry, [SHS.ENVIR]Humanities and Social Sciences/Environmental studies, [SDU.ENVI]Sciences of the Universe [physics]/Continental interfaces, environment
Abstract

International audience; Miliacin (olean-18-en-3β-ol methyl ether) is a fossil molecule that was recently detected in Lake le Bourget (LlB, French Alps) sediments. Comparison of potential plant producers with plants thriving around the lake at time of sedimentation concluded that Panicum miliaceum cultivated in the catchment was its most probable source. Since this discovery, it became possible to track the former presence of P. miliaceum over its area of extension and diffusion by detecting miliacin in sediments. This first allowed us reconstructing the history of millet cultivation around LlB, characterized by a beginning around 1700 B.C. and a maximum at 800 B.C. before a drastic drop at the Bronze Age/Iron Age transition. Examination of miliacin in sediments from Lake Lledro (Italy) and Paladru (France) revealed distinct dates of its first occurrence, attesting to a complex pattern of diffusion through the Alps. A twin high resolution record of miliacin in LlB Bronze Age sediments evidences periods of low and high concentrations that could result from varying levels of consumption potentially related to climate changes. While trying tospotpaleo-millet fields cultivated during the Bronze Age around LlB, we have analyzed soils in its surroundings. Miliacin is present but not abundant in soils and there is no logical pattern in its spatial distribution. Insufficient miliacin concentrations prevented any 14 C measurement that would have ascertained a molecular legacy of soils from Bronze Age millet cultivation. Reversely, we found miliacin in paleosoils from Ukraine that attested to the in situ cultivation of millet by Iron Age nomad populations. Miliacin is not solely produced by P. miliaceum. Previous studies indicate it can be found in a large spectrum of organisms (gramineae but also, surprisingly, molds), of which Setaria italica, the Italian millet. We analyzed seeds of several strains of P. miliaceum, several Panicum sp. and other gramineae such as S. italica. We found miliacin very abundant in any cultivar of P. miliaceum, present in all Panicum sp., in somePennisetum sp. but absent fromthree varieties of S. italica. In addition, we were unable to recover miliacin from Chaetomiumolivaceum, a mold, although operating under the

Published
2015

8. Contribution de la RMN 2D DAN anisotrope à la détermination du profil isotopique (D/H) i dans des biomarqueurs: étude de la miliacine

Author

Berdagué, Philippe, Jacob, Jérémy, Terwilliger, Valerie, Lemilbeau, Claude, Lesot, Philippe, Institut de Chimie Moléculaire et des Matériaux d'Orsay (ICMMO), Université Paris-Sud - Paris 11 (UP11)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), Institut des Sciences de la Terre d'Orléans - UMR7327 (ISTO), Bureau de Recherches Géologiques et Minières (BRGM) (BRGM)-Observatoire des Sciences de l'Univers en région Centre (OSUC), Institut national des sciences de l'Univers (INSU - CNRS)-Observatoire de Paris, Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université d'Orléans (UO)-Centre National de la Recherche Scientifique (CNRS)-Institut national des sciences de l'Univers (INSU - CNRS)-Observatoire de Paris, Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université d'Orléans (UO)-Centre National de la Recherche Scientifique (CNRS)-Institut national des sciences de l'Univers (INSU - CNRS)-Université d'Orléans (UO)-Centre National de la Recherche Scientifique (CNRS), ANR-10-JCJC-0607,PalHydroMil,Reconstructions paléohydrologiques à partir du dD de lipides produits par les végétaux supérieurs. Calibration, validation et application aux variations hydrologiques dans les Alpes pendant l'âge du Bronze(2010), Centre National de la Recherche Scientifique (CNRS)-Université d'Orléans (UO)-Institut national des sciences de l'Univers (INSU - CNRS)-Observatoire des Sciences de l'Univers en région Centre (OSUC), Institut national des sciences de l'Univers (INSU - CNRS)-Centre National de la Recherche Scientifique (CNRS)-Université d'Orléans (UO)-Observatoire de Paris, Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Institut national des sciences de l'Univers (INSU - CNRS)-Centre National de la Recherche Scientifique (CNRS)-Université d'Orléans (UO)-Observatoire de Paris, and Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Bureau de Recherches Géologiques et Minières (BRGM) (BRGM)

Subjects
paléoclimats, abondance naturelle, [CHIM.ORGA]Chemical Sciences/Organic chemistry, [SDU.STU.CL]Sciences of the Universe [physics]/Earth Sciences/Climatology, [SDU.STU.GC]Sciences of the Universe [physics]/Earth Sciences/Geochemistry, [SHS.ENVIR]Humanities and Social Sciences/Environmental studies, deutérium, miliacin, GEOF, biomarqueur, RMN
Abstract

International audience; Références :[1] Ph Lesot, C. Aroulanda, H. Zimmermann, Z. Luz, Chem. Soc. Rev., 44, 2330, (2015).[2] Ph. Lesot, Encyclopedia of Magnetic Resonance (eMagRes), 2(3), 315, (2013).[3] Z. Serhan, I. Billault, A. Borgogno, A. Ferrarini, Ph. Lesot, Chem. Eur. J., 18, 117, (2012).[4] N. Bossard, J. Jacob, C. LeMilbeau, J. Sauze, V.J. Terwilliger, B. Poissonnier, E. Vergès Org. Geochem., 63, 48, (2013).[5] Ph. Berdagué, Ph. Lesot, J. Jacob, V.J. Terwilliger, C. LeMilbeau, Geochemica Cosmo-chimica Acta, soumise, (2015).

Published
2015

9. Pertinence et calibration d'un nouveau marqueur paléohydrologique : le rapport isotopique de l'hydrogène mesuré sur la miliacine

Author

Bossard, Nicolas, Institut des Sciences de la Terre d'Orléans - UMR7327 (ISTO), Centre National de la Recherche Scientifique (CNRS)-Université d'Orléans (UO)-Institut national des sciences de l'Univers (INSU - CNRS)-Observatoire des Sciences de l'Univers en région Centre (OSUC), Institut national des sciences de l'Univers (INSU - CNRS)-Observatoire de Paris, Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université d'Orléans (UO)-Centre National de la Recherche Scientifique (CNRS)-Institut national des sciences de l'Univers (INSU - CNRS)-Observatoire de Paris, Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université d'Orléans (UO)-Centre National de la Recherche Scientifique (CNRS)-Bureau de Recherches Géologiques et Minières (BRGM) (BRGM), Université d'Orléans, and Elisabeth Lallier-Vergès

Subjects
Isotopes de l’hydrogène, Miliacin, Paleohydrology, Broomcorn millet, [SDU.STU]Sciences of the Universe [physics]/Earth Sciences, Miliacine, Paléohydrologie, Hydrogen isotopes
Abstract

This work aims at developing a new proxy of past hydrological conditions based on the hydrogen isotopic composition (δD) of a sedimentary biomarker that is specific for broomcorn millet (Panicum miliaceum), miliacin. Analysing the spatio-temporal relevancy of this proxy reveals that miliacin δD values of plants cultivated in the field, although dispersed, follow a Gaussian law. Soil miliacin δD values are the same as those found for plants grown the year before. Interannual variations in plant miliacin δD values roughly parallel those of precipitation δD values, slight differences being attributed to differences in relative humidity. The comparison of miliacin δD values in sediments deposited in two distinct settings at the same time in Lake le Bourget attests that this proxy homogeneously integrates climatic conditions over the whole catchment. Cultivation of millet plants in climatic chambers allowed demonstrating that, although source water δD is the principal controlling miliacin δD values, this later is closely correlated to leaf water δD. Slight differences in net biosynthetic fractionation between n-alcanes and miliacin under two relative humidity levels imply that the combined analysis of sedimentary biomarkers produced through distinct biosynthetic pathways could help discriminating between source water δD and relative humidity in paleoenvironmental studies.; Ce travail a pour objectif de développer un nouvel indicateur quantitatif des conditions hydrologiques passées fondé sur la composition isotopique en hydrogène (δD) d’un biomarqueur sédimentaire spécifique du millet commun (Panicum miliaceum), la miliacine. L’étude de la pertinence spatio-temporelle de cet indicateur révèle que le δD miliacine de plants de millet dans un champ, bien que dispersé, suit une loi gaussienne. Le δD miliacine du sol correspond au δD miliacine des plantes cultivées l’année précédente. L’évolution interannuelle du δD miliacine est globallement parallèle à celle du δD des eaux météoriques, les différences pouvant être attribuées à des différences d’humidité. La comparaison des valeurs de δD miliacine dans des sédiments du même âge prélevés sur deux archives distinctes dans le Lac du Bourget témoigne que l’archivage de cet indicateur est intègre de manière homogène les conditions climatiques ayant régné dans le bassin versant. La culture de millet en chambre climatique démontre que, si le δD de l’eau de source est le principal facteur controlant le δD miliacine, ce dernier est très étroitement corrélé au δD de l’eau de la feuille. De légères différences de fractionnement biosynthétique net entre n-alcanes et miliacine sous deux conditions d’humidité laissent supposer que l’analyse combinée de biomarqueurs sédimentaires issus de voies synthétiques distinctes permettrait d’accéder à la fois aux variables paléoenvironnementales clé que sont le δD de l’eau de source et l’humidité.

Published
2013

10. Distribution of miliacin (olean-18-en-3β-ol methyl ether) and related compounds in broomcorn millet (Panicum miliaceum) and other reputed sources: Implications for the use of sedimentary miliacin as a tracer of millet

Author

Valery J. Terwilliger, Joana Sauze, Nicolas Bossard, Elisabeth Vergès, Claude Le Milbeau, Bertrand Poissonnier, Jérémy Jacob, Institut des Sciences de la Terre d'Orléans - UMR7327 (ISTO), Centre National de la Recherche Scientifique (CNRS)-Université d'Orléans (UO)-Institut national des sciences de l'Univers (INSU - CNRS)-Observatoire des Sciences de l'Univers en région Centre (OSUC), Institut national des sciences de l'Univers (INSU - CNRS)-Observatoire de Paris, Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université d'Orléans (UO)-Centre National de la Recherche Scientifique (CNRS)-Institut national des sciences de l'Univers (INSU - CNRS)-Observatoire de Paris, Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université d'Orléans (UO)-Centre National de la Recherche Scientifique (CNRS)-Bureau de Recherches Géologiques et Minières (BRGM) (BRGM), Department of Geography, University of Kansas [Lawrence] (KU), Institut national de recherches archéologiques préventives (Inrap), PaléoChamps project (AIR Archéométrie, CNRS/INSU) and NSF project # BCS0551668, and ANR-10-JCJC-0607,PalHydroMil,Reconstructions paléohydrologiques à partir du dD de lipides produits par les végétaux supérieurs. Calibration, validation et application aux variations hydrologiques dans les Alpes pendant l'âge du Bronze(2010)

Subjects
Setaria, Millet, [SDE.MCG]Environmental Sciences/Global Changes, Ether, 010502 geochemistry & geophysics, 01 natural sciences, Panicum miliaceum, 03 medical and health sciences, chemistry.chemical_compound, Miliacin, Geochemistry and Petrology, Botany, [SDU.ENVI]Sciences of the Universe [physics]/Continental interfaces, environment, 030304 developmental biology, 0105 earth and related environmental sciences, 0303 health sciences, biology, Agriculture, 15. Life on land, biology.organism_classification, Agronomy, chemistry, Pentacyclic triterpenes, Foxtail, Chaetomium olivaceum, Sedimentary rock, Pennisetum, Panicum
Abstract

International audience; Using sedimentary miliacin (olean-18-en-3β-ol methyl ether) as a molecular tracer of the history of Panicum miliaceum (broomcorn millet) cultivation depends upon broomcorn millet being sedimentary miliacin's dominant source. It also requires knowledge of the variability in miliacin concentration in broomcorn millet. Finally, it is affected by the presence of other pentacyclic triterpene methyl ethers (PTMEs) that may exist in conjunction with miliacin in other sources but not in broomcorn millet. Miliacin biosynthesis has been proposed for other Panicum species, Setaria italica (Italian or foxtail millet), Pennisetum sp., and Chaetomium olivaceum (an olive green mold). We found miliacin concentration in seeds of different varieties of P. miliaceum to be similarly high (with trace amounts of β- and α-amyrin methyl ethers). It was absent from hulls and roots, and nominally present in leaves and stems. The transfer of miliacin from plant to sediments is therefore mostly from seeds. it was abundant (often with larger amounts of β- and α-amyrin methyl ethers) in all other Panicum species studied, but only in some species of the genus Pennisetum and was absent from Setaria italica. Neither C. olivaceum nor its growth medium (rice) showed any trace of miliacin. Our results, with miliacin absent from S. italica and C. olivaceum, its high miliacin in seed of P. miliaceum relative to other PTMEs and to other grasses and, considering the high biomass that cultivated broomcorn millet has relative to other potential plant sources, support the use of sedimentary records of miliacin in some contexts to track past millet agricultural dynamics.

Published
2013
Full Text
View/download PDF

Catalog

Books, media, physical & digital resources
See catalog results