Bias in carbon concentration and δ13C measurements of organic matter due to cleaning treatments with organic solvents

We acknowledge the financial support from the UnivEarths Labex program of Sorbonne Paris Cite (ANR 11-IDEX-00005-02). CH and AL acknowledge support from the Max Planck Society. EES and RB were funded by the NASA Exobiology grant NNX16AI37G and the Virtual Planetary Laboratory of the NASA Astrobiology Institute and were technically assisted by Andy Schauer.Interpreting the organic carbon content (TOC) and stable carbon isotopic composition (δ13C) of organic matter in the sedimentary rock record depends on our capability to accurately measure them, while excluding sources of contamination. This however becomes increasingly problematic as we analyze samples with ever-lower organic carbon content. Accordingly, organic solvents are sometimes used to remove contaminating traces of modern organic matter from ancient rock samples. However, especially for very low TOC samples, traces of solvents or their impurities remaining in the sample may contribute a significant organic contamination that can impact the bulk measurements of both TOC and δ13C values. This study, including three independent investigations performed in different laboratories, is the first detailed examination of the effect of cleaning treatments on the reliability of TOC and δ13C values in a range of natural rock samples and synthetic materials with low TOC content from below detection limit to 3330 ppm. We investigated the four most common organic solvents used to remove modern organic matter: dichloromethane (DCM), n-hexane, methanol and ethanol, and evaluated the effect of grain size and mineralogy. We find that (i) cleaning treatments with methanol, n-hexane and dichloromethane contaminate rock samples when used directly on sample powder, regardless of the grain size; (ii) this pollution buffers the natural variability and homogenizes the δ13C values of samples around the isotopic composition of the solvent, i.e. between −27 and −29‰; (iii) the extent of contamination depends on the solvent used, DCM being the most contaminating (up to 6000 ppm) and ethanol the only solvent that does not seem to contaminate rock samples above our detection limit; (iv) sample mineralogy also exerts an influence on the extent of contamination, clay minerals being more prone to adsorb contaminants. We conclude that the response of carbon concentrations and the stable carbon isotopic composition of organic matter in geological samples to cleaning treatments is neither negligible nor systematic when investigating samples with low carbon content.PostprintPeer reviewe

Oxygenated carbonization on wood isotopic sigal (δ13C) : aim to dendroclimatic reconstructions on archeological charcoals

Les charbons de bois trouvés en contexte archéologique permettent de reconstituer les couverts forestiers passés et les pratiques sylvicoles associées. Le δ13C de ces charbons a été utilisé pour des reconstructions paléoclimatiques, cependant ses variations peuvent aussi être dues à la carbonisation. Afin de mieux contraindre, à l’échelle du cerne, les variations du δ13C du bois dues à la carbonisation, des carbonisations ont été faites avec des échantillons de chêne cadicufoliés en conditions proches des foyers domestiques. Une diminution du δ13C après la carbonisation a été observée. Cet effet est très variable, notamment en fonction du compartiment du bois considéré (aubier, duramen, bois initial, bois final). Ces mesures de δ13C ont été complétées par celles du taux de carbone montrant qu’il ne varie pas parallèlement au δ13C. De ce fait l’utilisation, prônée par certains travaux, du taux de carbone pour évaluer les variations de d13C suite à la carbonisation n’est pas pertinente. Cependant, les variations cerne à cerne et intracerne du δ13C ne sont pas significativement affectées par la carbonisation, et des reconstructions climatiques à partir du δ13C de bois carbonisés paraissent donc envisageables. Afin de tester cette approche cerne à cerne, plusieurs charbons archéologiques issus du site Néolithique de Chalain, dont les paléoclimats étaient bien documentés, ont été échantillonnés. Cette approche a été couplée à des mesures dendro-anthracologiques (largeurs des cernes, proportion du bois final, rayon de courbure et proportion de vaisseaux avec des thylles) afin de mieux comprendre les variations de δ13C mesurées, et de tenter de les coupler aux pratiques sylvicoles. Les valeurs de δ13C sont en accord avec les paléoclimats déjà inférés et les variations intra-cerne, ou saisonnières, de δ13C révèlent que la période froide était caractérisée par des saisons plus contrastées. Les mesures dendro-anthracologiques ont permis, entre autres, de préciser les variations de δ13C entre les différents compartiments du bois et de proposer une interprétation concernant les variations des pratiques sylvicoles en lien avec le climat. En conclusion, la carbonisation oxygénée provoque un abaissement des valeurs de δ13C du bois mais n’empêche pas les reconstructions paléo-climatiques à partir de leurs variations, notamment saisonnières, mesurées sur des charbons archéologiques.Archeological charcoals are used for reconstructing past woodland vegetation and the related historical forest practices. Charcoals δ13C are used for paleoclimate reconstructions. To better constrain the use of δ13C, we investigated the effect of oxygenated carbonization on ring scale δ13C variations in oak wood. Results showed a significant decrease of δ13C values after carbonization. This effect, however, is highly variable according to the wood compartment considered: heartwood, sapwood, earlywood, or latewood. Carbon content measurements do not exhibit the same variations along oxygenated carbonization as observed with δ13C. Therefore, the use of carbon content for evaluating carbonization effects on δ13C, which is proposed by some authors, is not appropriate. Interannual and seasonal δ13C variations, however, are not significantly affected by oxygenated carbonization. Thus, paleoclimate reconstruction from charcoals δ13C appears possible. To test both ring scale variations, archeological charcoals were sampled from a climatically well documented Neolithic site of Chalain. Several dendro-anthracological parameters (latewood proportion, duraminization, charcoal-pith distance estimation) were characterized for a better understanding of δ13C variations, in order to integrate historical woodland practices and the climatic interpretations. Charcoal tree-rings exhibited width and δ13C significantly different between the two studied periods, in agreement with previously inferred climatic difference. Intra-ring δ13C suggested that the cool and moist climatic period also corresponded to higher seasonal contrast than the dryer climatic period. Dendro-anthracological parameters allow better understanding of δ13C variations between wood compartments and provide information on past woodland exploitations. To conclude, oxygenated carbonizations induce a decrease in wood δ13C values, but do not prevent the paleoclimate interpretations of δ13C variations in archeological charcoals

Effets de la carbonisation oxygénée sur le signal isotopique (δ13C) du bois : vers une dendroclimatologie isotopique sur charbons archéologiques

Archeological charcoals are used for reconstructing past woodland vegetation and the related historical forest practices. Charcoals δ13C are used for paleoclimate reconstructions. To better constrain the use of δ13C, we investigated the effect of oxygenated carbonization on ring scale δ13C variations in oak wood. Results showed a significant decrease of δ13C values after carbonization. This effect, however, is highly variable according to the wood compartment considered: heartwood, sapwood, earlywood, or latewood. Carbon content measurements do not exhibit the same variations along oxygenated carbonization as observed with δ13C. Therefore, the use of carbon content for evaluating carbonization effects on δ13C, which is proposed by some authors, is not appropriate. Interannual and seasonal δ13C variations, however, are not significantly affected by oxygenated carbonization. Thus, paleoclimate reconstruction from charcoals δ13C appears possible. To test both ring scale variations, archeological charcoals were sampled from a climatically well documented Neolithic site of Chalain. Several dendro-anthracological parameters (latewood proportion, duraminization, charcoal-pith distance estimation) were characterized for a better understanding of δ13C variations, in order to integrate historical woodland practices and the climatic interpretations. Charcoal tree-rings exhibited width and δ13C significantly different between the two studied periods, in agreement with previously inferred climatic difference. Intra-ring δ13C suggested that the cool and moist climatic period also corresponded to higher seasonal contrast than the dryer climatic period. Dendro-anthracological parameters allow better understanding of δ13C variations between wood compartments and provide information on past woodland exploitations. To conclude, oxygenated carbonizations induce a decrease in wood δ13C values, but do not prevent the paleoclimate interpretations of δ13C variations in archeological charcoals.Les charbons de bois trouvés en contexte archéologique permettent de reconstituer les couverts forestiers passés et les pratiques sylvicoles associées. Le δ13C de ces charbons a été utilisé pour des reconstructions paléoclimatiques, cependant ses variations peuvent aussi être dues à la carbonisation. Afin de mieux contraindre, à l’échelle du cerne, les variations du δ13C du bois dues à la carbonisation, des carbonisations ont été faites avec des échantillons de chêne cadicufoliés en conditions proches des foyers domestiques. Une diminution du δ13C après la carbonisation a été observée. Cet effet est très variable, notamment en fonction du compartiment du bois considéré (aubier, duramen, bois initial, bois final). Ces mesures de δ13C ont été complétées par celles du taux de carbone montrant qu’il ne varie pas parallèlement au δ13C. De ce fait l’utilisation, prônée par certains travaux, du taux de carbone pour évaluer les variations de d13C suite à la carbonisation n’est pas pertinente. Cependant, les variations cerne à cerne et intracerne du δ13C ne sont pas significativement affectées par la carbonisation, et des reconstructions climatiques à partir du δ13C de bois carbonisés paraissent donc envisageables. Afin de tester cette approche cerne à cerne, plusieurs charbons archéologiques issus du site Néolithique de Chalain, dont les paléoclimats étaient bien documentés, ont été échantillonnés. Cette approche a été couplée à des mesures dendro-anthracologiques (largeurs des cernes, proportion du bois final, rayon de courbure et proportion de vaisseaux avec des thylles) afin de mieux comprendre les variations de δ13C mesurées, et de tenter de les coupler aux pratiques sylvicoles. Les valeurs de δ13C sont en accord avec les paléoclimats déjà inférés et les variations intra-cerne, ou saisonnières, de δ13C révèlent que la période froide était caractérisée par des saisons plus contrastées. Les mesures dendro-anthracologiques ont permis, entre autres, de préciser les variations de δ13C entre les différents compartiments du bois et de proposer une interprétation concernant les variations des pratiques sylvicoles en lien avec le climat. En conclusion, la carbonisation oxygénée provoque un abaissement des valeurs de δ13C du bois mais n’empêche pas les reconstructions paléo-climatiques à partir de leurs variations, notamment saisonnières, mesurées sur des charbons archéologiques

Effets de la carbonisation oxygénée sur le signal isotopique (d13C) du bois: vers une dendroclimatologie isotopique sur charbons archéologiques

Archeological charcoals are used for reconstructing past woodland vegetation and the related historical forest practices. Charcoals d13C are used for paleoclimate reconstructions. To better constrain the use of d13C, we investigated the effect of oxygenated carbonization on ring scale d13C variations in oak wood. Results showed a significant decrease of d13C values after carbonization. This effect, however, is highly variable according to the wood compartment considered: heartwood, sapwood, earlywood, or latewood. Carbon content measurements do not exhibit the same variations along oxygenated carbonization as observed with d13C. Therefore, the use of carbon content for evaluating carbonization effects on d13C, which is proposed by some authors, is not appropriate. Interannual and seasonal d13C variations, however, are not significantly affected by oxygenated carbonization. Thus, paleoclimate reconstruction from charcoals d13C appears possible.To test both ring scale variations, archeological charcoals were sampled from a climatically well documented Neolithic site of Chalain. Several dendro-anthracological parameters (latewood proportion, duraminization, charcoal-pith distance estimation) were characterized for a better understanding of d13C variations, in order to integrate historical woodland practices and the climatic interpretations. Charcoal tree-rings exhibited width and d13C significantly different between the two studied periods, in agreement with previously inferred climatic difference. Intra-ring d13C suggested that the cool and moist climatic period also corresponded to higher seasonal contrast than the dryer climatic period. Dendro-anthracological parameters allow better understanding of d13C variations between wood compartments and provide information on past woodland exploitationsTo conclude, oxygenated carbonizations induce a decrease in wood d13C values, but do not prevent the paleoclimate interpretations of d13C variations in archeological charcoals.Les charbons de bois trouvés en contexte archéologique permettent de reconstituer les couverts forestiers passés et les pratiques sylvicoles associées. Le d13C de ces charbons a été utilisé pour des reconstructions paléoclimatiques, cependant ses variations peuvent aussi être dues à la carbonisation. Afin de mieux contraindre, à l’échelle du cerne, les variations du d13C du bois dues à la carbonisation, des carbonisations ont été faites avec des échantillons de chêne cadicufoliés en conditions proches des foyers domestiques. Une diminution du d13C après la carbonisation a été observée. Cet effet est très variable, notemment en fonction du compartiment du bois considéré (aubier, duramen, bois initial, bois final). Ces mesures de d13C ont été complétées par celles du taux de carbone montrant qu’il ne varie pas parralèllement au d13C. De ce fait l’utilisation, pronée par certains travaux, du taux de carbone pour évaluer les variations de d13C suite à la carbonisation n’est pas pertinente. Cependant, les variations cerne à cerne et intracerne du d13C ne sont pas significativement affectées par la carbonisation, et des reconstructions climatiques à partir du d13C de bois carbonisés paraissent donc envisageables.Afin de tester cette approche cerne à cerne, plusieurs charbons archéologiques issus du site Néolithique de Chalain, dont les paléoclimats étaient bien documentés, ont été échantillonnés. Cette approche a été couplée à des mesures dendro-anthracologiques (largeurs des cernes, proportion du bois final, rayon de courbure et proportion de vaisseaux avec des thylles) afin de mieux comprendre les variations de d13C mesurées, et de tenter de les coupler aux pratiques sylvicoles. Les valeurs de d13C sont en accord avec les paléoclimats déjà inférés et les variations intra-cerne, ou saisonières, de d13C révèlent que la période froide était caractérisée par des saisons plus contrastées. Les mesures dendro-anthracologiques ont permis, entre autres, de préciser les variations de d13C entre les différents compartiments du bois et de proposer une interprétation concernant les variations des pratiques sylvicoles en lien avec le climat.En conclusion, la carbonisation oxygénée provoque un abaissement des valeurs de d13C du bois mais n’empêche pas les reconstructions paléo-climatiques à partir de leurs variations, notamment saisonnières, mesurées sur des charbons archéologiques

The use of chromium reduction in the analysis of organic carbon and inorganic sulfur isotope compositions in Archean rocks

International audienceOne of the most serious issues with deciphering the evolution of organisms and their biogeochemical environments from the ancient rock record is the difficulty in obtaining well-preserved samples. Although not much can be done to avoid diagenetic and metamorphic alteration when they have occurred, alteration due to weathering can be avoided by working on drill core samples. This implies however that the amount of sample is limited, which may in turn restrain the number of possible chemical and isotopic analyses that can be performed. In order to save sample we show here that the chemical protocol used for the sulfur sulfide extraction (for later sulfur isotope analyses) is also suitable to decarbonate samples (for later organic carbon isotope analyses). In the case of carbonated rocks, both sulfur sulfide extraction and decarbonation require high amounts of sample so that coupling them may save a significant amount of sample and time. In addition it allows both organic carbon (TOC and δ 13 C) and sulfur isotope composition measurements to be performed on the exact same powder , which is essential when trying to understand couplings between S and C cycles in heterogeneous samples. We thus tested the efficiency of the acidic chromium solution, commonly used to extract sulfur from sulfide, for sample decarbonation on various Archean rocks. Our results show that no significant carbon isotope fraction-ation is caused by this new decarbonation protocol, even for the samples with low organic carbon content. The chromium solution seems to be perfectly adapted for the analysis of organic matter in the ancient rock record, at least when the rock samples have experienced low greenschist facies metamorphism. Further tests will be needed to verify if this protocol can also be used for less mature organic matter

Tree-ring δ¹³C of archeological charcoals as indicator of past climatic seasonality. A case study from the Neolithic settlements of Lake Chalain (Jura, France)

International audienceCharcoal fragments from the Neolithic settlements of Lake Chalain (Jura Mountains, France) 17 were characterized by dendro-anthracology (charcoal-pith distance, tree-ring width, 18 earlywood/latewood proportion) and ring-scale isotope geochemistry (13 C) to assess the 19 relevance of this combined approach for paleoclimate reconstructions. Two differing climatic 20 periods were investigated: (i) a climatic deterioration period characterized by cool and moist 21 conditions and (ii) a climatic improvement period characterized by slightly less precipitation 22 and warmer temperature. Latewood proportion in charcoal tree-rings was similar for the two 23 studied climatic periods. However, the charcoal tree-rings exhibited width and 13 C-content 24 significantly different between the two studied periods, in agreement with previously inferred 25 climatic difference. Monitoring ring-to-ring 13 C variation within each charcoal fragment 26 revealed no noticeable climatic trend, for none of the studied periods. However, calculation of 27 the difference in 13 C-content between earlywood and latewood of a given tree-ring suggested 28 2 that the cool and moist climatic period also corresponded to higher seasonal contrast than 29 the dryer climatic period. Although this exploratory study needs further confirmation, it opens 30 promising developments for paleoclimatic reconstructions based on the stable carbon 31 isotope composition of archaeological charcoals: the potential for recording subtle 32 paleoclimatic variations and seasonal contrasts

Effects of oxygenated carbonization on the isotope signal in tree rings. Implication for ancient charcoals

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Effects of oxygenated carbonization on the isotope signal in tree rings. Implication for ancient charcoals

International audienc

Effects of oxygenated carbonization on the isotope signal in tree rings. Implication for ancient charcoals

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