Evolution of the macromolecular structure of sporopollenin during thermal degradation

AbstractReconstructing the original biogeochemistry of organic microfossils requires quantifying the extent of the chemical transformations they experienced during burial and maturation processes. In the present study, fossilization experiments have been performed using modern sporopollenin chosen as an analogue for the resistant biocompounds possibly constituting the wall of many organic microfossils. Sporopollenin powder has been processed thermally under argon atmosphere at different temperatures (up to 1000 °C) for varying durations (up to 900 min). Solid residues of each experiment have been characterized using infrared, Raman and synchrotron-based XANES spectroscopies. Results indicate that significant defunctionalisation and aromatization affect the molecular structure of sporopollenin with increasing temperature. Two distinct stages of evolution with temperature are observed: in a first stage, sporopollenin experiences dehydrogenation and deoxygenation simultaneously (below 500 °C); in a second stage (above 500 °C) an increasing concentration in aromatic groups and a lateral growth of aromatic layers are observed. With increasing heating duration (up to 900 min) at a constant temperature (360 °C), oxygen is progressively lost and conjugated carbon–carbon chains or domains grow progressively, following a log-linear kinetic behavior. Based on the comparison with natural spores fossilized within metasediments which experienced intense metamorphism, we show that the present experimental simulations may not perfectly mimic natural diagenesis and metamorphism. Yet, performing such laboratory experiments provides key insights on the processes transforming biogenic molecules into molecular fossils

Cyanobacterial calcification in modern microbialites at the submicrometer scale

International audienceThe search for microfossils in the geological record has been a long-term challenge. Part of the problem comes from the difficulty of identifying such microfossils unambiguously, since they can be morphologically confused with abiotic biomorphs. One route to improve our ability to correctly identify microfossils involves studying fossilization processes affecting bacteria in modern settings. We studied the initial stages of fossilization of cyanobacterial cells in modern microbialites from Lake Alchichica (Mexico), a Mg-rich hyperalkaline crater lake (pH 8.9) hosting currently growing stromatolites composed of aragonite [CaCO3] and hydromagnesite [Mg5(CO3)4(OH)2 * 4(H2O)]. Most of the biomass associated with the microbialites is composed of cyanobacteria. Scanning electron microscopy analyses coupled with confocal laser scanning microscopy observations were conducted to co-localize cyanobacterial cells and associated minerals. These observations showed that cyanobacterial cells affiliated with the order Pleurocapsales become specifically encrusted within aragonite with an apparent preservation of cell morphology. Encrustation gradients from non-encrusted to totally encrusted cells spanning distances of a few hundred micrometers were observed. Cells exhibiting increased levels of encrustation along this gradient were studied down to the nm scale using a combination of focused ion beam (FIB) milling, transmission electron microscopy (TEM) and scanning transmission x-ray microscopy (STXM) at the C, O and N K-edges. Two different types of aragonite crystals were observed: one type was composed of needle-shaped nano-crystals growing outward from the cell body with a crystallographic orientation perpendicular to the cell wall, and another type was composed of larger crystals that progressively filled the cell interior. Exopolymeric substances (EPS), initially co-localized with the cells, decreased in concentration and dispersed away from the cells while crystal growth occurred. As encrustation developed, EPS progressively disappeared, but remaining EPS showed the same spectroscopic signature. In the most advanced stages of fossilization, only the textural organization of the two types of aragonite recorded the initial cell morphology and spatial distribution

Experimental investigation of the stability of Fe-rich carbonates in the lower mantle

International audienceThe fate of carbonates in the Earth's mantle plays a key role in the geodynamical carbon cycle. Although iron is a major component of the Earth's lower mantle, the stability of Fe-bearing carbonates has rarely been studied. Here we present experimental results on the stability of Fe-rich carbonates at pressures ranging from 40 to 105 GPa and temperatures of 1450-3600 K, corresponding to depths within the Earth's lower mantle of about 1000-2400 km. Samples of iron oxides and iron-magnesium oxides were loaded into CO2 gas and laser heated in a diamond-anvil cell. The nature of crystalline run products was determined in situ by X-ray diffraction, and the recovered samples were studied by analytical transmission electron microscopy and scanning transmission X-ray microscopy. We show that Fe-(II) is systematically involved in redox reactions with CO2 yielding to Fe-(III)-bearing phases and diamonds. We also report a new Fe-(III)-bearing high-pressure phase resulting from the transformation of FeCO3 at pressures exceeding 40 GPa. The presence of both diamonds and an oxidized C-bearing phase suggests that oxidized and reduced forms of carbon might coexist in the deep mantle. Finally, the observed reactions potentially provide a new mechanism for diamond formation at great depth

Exploring microbial life in the multi-extreme environment of Dallol, Ethiopia

Early Earth and ExoEarths: origin and evolution of life (2017. Varsovia)The Danakil depression at the Afar region in Ethiopia is one of the most unique and extreme environments on Earth. At the confluence of three tectonic plates in the East African rift (Triple Afar Junction), the Afar Depression is the only place on Earth where the transition from continental to oceanic crust (rift-to drift process) can be observed on land. Several types of extreme environments co-exist in this area, including highly acidic hydrothermal springs linked to the local volcanic activity at the Dallol dome, as well as desert evaporites and hypersaline lakes that resulted from the intense evaporation of an ancient enclosed sea. Although there have been more than 50 years since the area was first explored, information about its chemistry and geology is limited, and its biology remains completely unknown. In January 2016 and in January 2017, after several years of preparation, we organized two interdisciplinary expeditions to the Dallol area in order to explore the presence of life and mineral-microbe interactions under these geochemical extremes. To do so, and in combination with geochemical and mineralogical studies, we are applying molecular analyses based on 16S rRNA gene sequences, metagenomic and cultural approaches. Here, we will present preliminary results on the presence of life and microbial diversity identified in several sites of this multi-extreme environment.Centre National de la Recherche Scientifique, Université Paris-Sud, FranciaLaboratoire de microbiologie des environnements extrêmes, Centre National de la Recherche Scientifique, Université de Bretagne Occidentale, FranciaDepartamento de Ecología, Universidad Autónoma de Madrid, EspañaUnidad de Baleares, Instituto Geológico y Minero de España, EspañaInstituto Andaluz de Ciencias de la Tierra, Consejo Superior de Investigaciones Científicas, EspañaInstituto Andaluz de Ciencias de la Tierra, Universidad de Granada, EspañaLaboratoire de Minéralogie, Physique des Matériaux et Cosmochimie , Centre National de la Recherche Scientifique, Université Pierre et Marie Curie, FranciaPeer reviewe

Early precipitated micropyrite in microbialites: A time capsule of microbial sulfur cycling

Microbialites are organosedimentary rocks that have occurred throughout the Earth’s history. The relationships between diverse microbial metabolic activities and isotopic signatures in biominerals forming within these microbialites are key to understanding modern biogeochemical cycles, but also for accurate interpretation of the geologic record. Here, we performed detailed mineralogical investigations coupled with NanoSIMS (Nanoscale Secondary Ion Mass Spectrometry) analyses of pyrite S isotopes in mineralising microbial mats from two different environments, a hypersaline lagoon (Cayo Coco, Cuba) and a volcanic alkaline crater lake (Atexcac, Mexico). Both microbialite samples contain two distinct pyrite morphologies: framboids and euhedral micropyrites, which display distinct ranges of δ34S values1. Considering the sulfate-sulfur isotopic compositions associated with both environments, micropyrites display a remarkably narrow range of Δpyr (i.e. Δpyr ≡ δ34SSO4 − δ34Spyr) between 56 and 62‰. These measured Δpyr values agree with sulfate-sulfide equilibrium fractionation, as observed in natural settings characterised by low microbial sulfate reduction respiration rates. Moreover, the distribution of S isotope compositions recorded in the studied micropyrites suggests that sulfide oxidation also occurred at the microbialite scale. These results highlight the potential of micropyrites to capture signatures of microbial sulfur cycling and show that S isotope composition in pyrites record primarily the local micro-environments induced by the microbialite

Ultracarbonaceous Antarctic micrometeorites recovered from snow at the Dome C - CONCORDIA station.

第6回極域科学シンポジウム[OA] 南極隕石11月17日（火）　国立国語研究所 2階 講

Silica in Protoplanetary Disks

Mid-infrared spectra of a few T Tauri stars (TTS) taken with the Infrared Spectrograph (IRS) on board the Spitzer Space Telescope show prominent narrow emission features indicating silica (crystalline silicon dioxide). Silica is not a major constituent of the interstellar medium; therefore, any silica present in the circumstellar protoplanetary disks of TTS must be largely the result of processing of primitive dust material in the disks surrouding these stars. We model the silica emission features in our spectra using the opacities of various polymorphs of silica and their amorphous versions computed from earth-based laboratory measurements. This modeling indicates that the two polymorphs of silica, tridymite and cristobalite, which form at successively higher temperatures and low pressures, are the dominant forms of silica in the TTS of our sample. These high temperature, low pressure polymorphs of silica present in protoplanetary disks are consistent with a grain composed mostly of tridymite named Ada found in the cometary dust samples collected from the STARDUST mission to Comet 81P/Wild 2. The silica in these protoplanetary disks may arise from incongruent melting of enstatite or from incongruent melting of amorphous pyroxene, the latter being analogous to the former. The high temperatures of 1200K-1300K and rapid cooling required to crystallize tridymite or cristobalite set constraints on the mechanisms that could have formed the silica in these protoplanetary disks, suggestive of processing of these grains during the transient heating events hypothesized to create chondrules.Comment: 47 pages, 9 figures, to appear in the 1 January, 2009 issue of the Astrophysical Journa

Study of Interactions Between Microbes and Minerals by Scanning Transmission X-Ray Microscopy (STXM)

Scanning Transmission X-ray Microscopy (STXM) and Transmission Electron Microscopy (TEM) were combined to characterize various samples of geomicrobiological interest down to the nanometer scale. An approach based on energy-filtered imaging was used to examine microbe-mineral interactions and the resulting biominerals, as well as biosignatures in simplified laboratory samples. This approach was then applied to natural samples, including natural biofilms entombed in calcium carbonate precipitates and bioweathered silicates and facilitated location of bacterial cells and provided unique insights about their biogeochemical interactions with minerals at the 30-40 nm scale