In the nascent solar system, primitive organic matter was a major contributor of volatile elements to planetary bodies, and could have played a key role in the development of the biosphere. However, ...the origin of primitive organics is poorly understood. Most scenarios advocate cold synthesis in the interstellar medium or in the outer solar system. Here, we report the synthesis of solid organics under ionizing conditions in a plasma setup from gas mixtures (H ₂(O)−CO−N ₂−noble gases) reminiscent of the protosolar nebula composition. Ionization of the gas phase was achieved at temperatures up to 1,000 K. Synthesized solid compounds share chemical and structural features with chondritic organics, and noble gases trapped during the experiments reproduce the elemental and isotopic fractionations observed in primitive organics. These results strongly suggest that both the formation of chondritic refractory organics and the trapping of noble gases took place simultaneously in the ionized areas of the protoplanetary disk, via photon- and/or electron-driven reactions and processing. Thus, synthesis of primitive organics might not have required a cold environment and could have occurred anywhere the disk is ionized, including in its warm regions. This scenario also supports N ₂ photodissociation as the cause of the large nitrogen isotopic range in the solar system.
Significance Refractory organics are the main hosts of carbon, nitrogen, and other biogenic elements in primitive solar system material. We have synthesized refractory organics by ionizing a gas mixture reminiscent of the composition of the protosolar nebula, at temperatures up to 1,000 K in a plasma. Synthesized compounds share chemical and structural features with chondritic organics, and trapped noble gases reproduce well the elemental and isotopic characteristics of meteoritic noble gases. Our study suggests that organosynthesis took place in the solar system, including in its warm regions, and was ubiquitous anywhere the nebular gas was subject to ionization.
The Paris chondrite provides an excellent opportunity to study CM chondrules and refractory inclusions in a more pristine state than currently possible from other CMs, and to investigate the earliest ...stages of aqueous alteration captured within a single CM bulk composition. It was found in the effects of a former colonial mining engineer and may have been an observed fall. The texture, mineralogy, petrography, magnetic properties and chemical and isotopic compositions are consistent with classification as a CM2 chondrite. There are ∼45vol.% high-temperature components mainly Type I chondrules (with olivine mostly Fa0–2, mean Fa0.9) with granular textures because of low mesostasis abundances. Type II chondrules contain olivine Fa7 to Fa76. These are dominantly of Type IIA, but there are IIAB and IIB chondrules, II(A)B chondrules with minor highly ferroan olivine, and IIA(C) with augite as the only pyroxene. The refractory inclusions in Paris are amoeboid olivine aggregates (AOAs) and fine-grained spinel-rich Ca–Al-rich inclusions (CAIs). The CAI phases formed in the sequence hibonite, perovskite, grossite, spinel, gehlenite, anorthite, diopside/fassaite and forsterite. The most refractory phases are embedded in spinel, which also occurs as massive nodules. Refractory metal nuggets are found in many CAI and refractory platinum group element abundances (PGE) decrease following the observed condensation sequences of their host phases. Mn–Cr isotope measurements of mineral separates from Paris define a regression line with a slope of 53Mn/55Mn=(5.76±0.76)×106. If we interpret Cr isotopic systematics as dating Paris components, particularly the chondrules, the age is 4566.44±0.66Myr, which is close to the age of CAI and puts new constraints on the early evolution of the solar system. Eleven individual Paris samples define an O isotope mixing line that passes through CM2 and CO3 falls and indicates that Paris is a very fresh sample, with variation explained by local differences in the extent of alteration. The anhydrous precursor to the CM2s was CO3-like, but the two groups differed in that the CMs accreted a higherproportion of water. Paris has little matrix (∼47%, plus 8% fine grained rims) and is less altered than other CM chondrites. Chondrule silicates (except mesostasis), CAI phases, submicron forsterite and amorphous silicate in the matrix are all well preserved in the freshest domains, and there is abundant metal preserved (metal alteration stage 1 of Palmer and Lauretta (2011)). Metal and sulfide compositions and textures correspond to the least heated or equilibrated CM chondrites, Category A of Kimura et al. (2011). The composition of tochilinite–cronstedtite intergrowths gives a PCP index of ∼2.9. Cronstedtite is more abundant in the more altered zones whereas in normal highly altered CM chondrites, with petrologic subtype 2.6–2.0 based on the S/SiO2 and ∑FeO/SiO2 ratios in PCP or tochilinite–cronstedtite intergrowths (Rubin et al., 2007), cronstedtite is destroyed by alteration. The matrix in fresh zones has CI chondritic volatile element abundances, but interactions between matrix and chondrules occurred during alteration, modifying the volatile element abundances in the altered zones. Paris has higher trapped Ne contents, more primitive organic compounds, and more primitive organic material than other CMs. There are gradational contacts between domains of different degree of alteration, on the scale of ∼1cm, but also highly altered clasts, suggesting mainly a water-limited style of alteration, with no significant metamorphic reheating.
Reconstructing the original biogeochemistry of organic fossils requires quantifying the extent of the chemical transformations that they underwent during burial-induced maturation processes. Here, we ...performed laboratory experiments on chemically different organic materials in order to simulate the thermal maturation processes that occur during diagenesis. Starting organic materials were microorganisms and organic aerosols. Scanning transmission X-ray microscopy (STXM) was used to collect X-ray absorption near edge spectroscopy (XANES) data of the organic residues. Results indicate that even after having been submitted to 250 °C and 250 bars for 100 days, the molecular signatures of microorganisms and aerosols remain different in terms of nitrogen-to-carbon atomic ratio and carbon and nitrogen speciation. These observations suggest that burial-induced thermal degradation processes may not completely obliterate the chemical and molecular signatures of organic molecules. In other words, the present study suggests that organic molecular heterogeneities can withstand diagenesis and be recognized in the fossil record.
The main carrier of primordial heavy noble gases in chondrites is thought to be an organic phase, known as phase Q, whose precise characterization has resisted decades of investigation. The Q noble ...gas component shows elemental and isotopic fractionation relative to the Solar, in favor of heavy elements and isotopes. These noble gas characteristics were experimentally simulated using a plasma device called the “Nebulotron”. In this study, we synthesized thirteen solid organic samples by electron-dissociation of CO, in which a noble gas mixture was added. The analysis of their heavy noble gas (Ar, Kr and Xe) contents and isotopic compositions reveals enrichment in the heavy noble gas isotopes and elements relative to the light ones. The isotope fractionation is mass-dependent and is consistent with a mn- type law, where n≥1. Based on a plasma model, we propose that the ambipolar diffusion of ions in the ionized CO gas medium is at the origin of the noble gas isotopic fractionation. In addition, the elemental fractionation of experimental and chondritic samples can be accounted for by the Saha law of plasma equilibrium, which does not depend on the respective noble gas masses but rather on their ionization potentials. Our results suggest that the Q noble gases were trapped into growing organic particles starting from solar gases that were fractionated in an ionized medium by ambipolar diffusion and Saha processes. This would imply that both the formation of chondritic organic matter and the trapping of noble gases took place simultaneously in the ionized areas of the protoplanetary disk.
The formation of organic compounds is generally assumed to result from abiotic processes in the Solar System, with the exception of biogenic organics on Earth. Nitrogen-bearing organics are of ...particular interest, notably for prebiotic perspectives but also for overall comprehension of organic formation in the young Solar System and in planetary atmospheres. We have investigated abiotic synthesis of organics upon plasma discharge, with special attention to N isotope fractionation. Organic aerosols were synthesized from N2–CH4 and N2–CO gaseous mixtures using low-pressure plasma discharge experiments, aimed at simulating chemistry occurring in Titan's atmosphere and in the protosolar nebula, respectively. The nitrogen content, the N speciation and the N isotopic composition were analyzed in the resulting organic aerosols. Nitrogen is efficiently incorporated into the synthesized solids, independently of the oxidation degree, of the N2 content of the starting gas mixture, and of the nitrogen speciation in the aerosols. The aerosols are depleted in 15N by 15–25‰ relative to the initial N2 gas, whatever the experimental setup is. Such an isotopic fractionation is attributed to mass-dependent kinetic effect(s).
Nitrogen isotope fractionation upon electric discharge cannot account for the large N isotope variations observed among Solar System objects and reservoirs. Extreme N isotope signatures in the Solar System are more likely the result of self-shielding during N2 photodissociation, exotic effect during photodissociation of N2 and/or low temperature ion-molecule isotope exchange. Kinetic N isotope fractionation may play a significant role in the Titan's atmosphere. On the Titan's night side, 15N-depletion resulting from electron driven reactions may counterbalance photo-induced 15N enrichments occurring on the day's side. We also suggest that the low δ15N values of Archaean organic matter (Beaumont and Robert, 1999) are partly the result of abiotic synthesis of organics that occurred at that time, and that the subsequent development of the biosphere resulted in shifts of δ15N towards higher values.
•Nitrogen-rich aerosols synthesis in low pressure plasma discharge experiments.•N2–CH4 and N2–CO initial gas mixtures as Titan's atmosphere and solar nebula proxies.•Synthesized organics are depleted in 15N down to −25‰.•Kinetic isotopic fractionation is likely responsible for this 15N-depletion.•Implications for nitrogen isotopic balance in Titan's atmosphere and early Earth.
L’azote et les gaz rares présents dans les astéroïdes, les comètes et les atmosphères planétaires sont piégés dans de la matière organique et ont des compositions chimiques qui sont différentes de ...celle du Soleil, représentatif du gaz primordial à partir duquel les différents objets du système solaire se sont formés il y a 4,5 milliards d’années. Au cours de cette thèse, des synthèses de matière carbonée à partir d’un mélange de gaz ont été réalisées dans un plasma appelé le Nébulotron, afin de mieux comprendre les processus à l’origine des compositions de l’azote et des gaz rares présents dans les météorites. Les caractéristiques de la matière organique ainsi que la composition des gaz rares piégés dans les météorites sont relativement bien reproduites dans les expériences, mais pas celle de l’azote. Ces résultats expérimentaux permettent de proposer des mécanismes clé à l’origine des compositions des éléments volatils présents dans les objets du système solaire.
Nitrogen and noble gases present in asteroids, comets or planetary atmospheres are trapped in organic matter and bear a composition that is different from the composition of the Sun, which is representative of the primordial gas from which the different objects in the solar system were formed 4.5 billion years ago. During this thesis, experimental syntheses of organic matter from gas mixtures in a plasma setup called the Nebulotron were performed in order to better understand the processes responsible for this chemical difference between the meteorites and the Sun for nitrogen and noble gases. The characteristics of the organic matter and the signature of the noble gases trapped in meteorites are relatively well reproduced in the experiments, whereas the composition of nitrogen is not. These experimental results give hints about the key mechanisms that are responsible for the variations of the volatile elements composition in the solar system objects.
The longest distance between subaerial shield volcanoes in the Hawaiian Islands is between the islands of Kaua'i and O'ahu, where a field of submarine volcanic cones formed astride the axis of the ...Hawaiian chain during a period of low magma productivity. The submarine volcanoes lie 25-30 km west of Ka'ena Ridge that extends 80 km from western O'ahu. These volcanoes were sampled by three Jason2 dives. The cones are flat topped, <400 m high and 0.4-2 km in diameter at water depths between 2700 and 4300 m, and consist predominantly of pillowed flows. Ar-Ar and K-Ar ages of 11 tholeiitic lavas are between 4.9 and 3.6 Ma. These ages overlap with shield volcanism on Kaua'i (5.1-4.0 Ma) and Wai'anae shield basalts (3.9-3.1 Ma) on O'ahu. Young alkalic lavas (circa 0.37 Ma) sampled southwest of Ka'ena Ridge are a form of offshore secondary volcanism. Half of the volcanic cones contain high-SiO sub(2) basalts (51.0-53.5 wt % SiO sub(2)). The trends of isotopic compositions of West Ka'ena tholeiitic lavas diverge from the main Ko'olau-Kea shield binary mixing trend in isotope diagrams and extend to lower super(208)Pb/ super(204)Pb and super(206)Pb/ super(204)Pb than any Hawaiian tholeiitic lava. West Ka'ena tholeiitic lavas have geochemical and isotopic characteristics similar to volcanoes of the Loa trend. Hence, our results show that the Loa-type volcanism has persisted for at least 4.9 Myr, beginning prior to the development of the dual, subparallel chain of volcanoes. Several West Ka'ena samples are similar to higher SiO sub(2), Loa trend lavas of Ko'olau Makapu'u stage, Lana'i, and Kaho'olawe; these lavas may have been derived from a pyroxenite source in the mantle. The high Ni contents of olivines in West Ka'ena lavas also indicate contribution from pyroxenite-derived melting. Average compositions of Hawaiian shield volcanoes show a clear relation between super(206)Pb/ super(204)Pb and SiO sub(2) within Loa trend volcanoes, which supports a prominent but variable influence of pyroxenite in the Hawaiian plume source. In addition, both Pb isotopes and volcano volume show a steady increase with time starting from a minimum west of Ka'ena Ridge. The entrained mafic component in the Hawaiian plume is probably not controlling the increasing magma productivity in the Hawaiian Islands.
The longest distance between subaerial shield volcanoes in the Hawaiian Islands is between the islands of Kaua‘i and O‘ahu, where a field of submarine volcanic cones formed astride the axis of the ...Hawaiian chain during a period of low magma productivity. The submarine volcanoes lie ∼25–30 km west of Ka‘ena Ridge that extends ∼80 km from western O‘ahu. These volcanoes were sampled by three Jason2 dives. The cones are flat topped, <400 m high and 0.4–2 km in diameter at water depths between ∼2700 and 4300 m, and consist predominantly of pillowed flows. Ar‐Ar and K‐Ar ages of 11 tholeiitic lavas are between 4.9 and 3.6 Ma. These ages overlap with shield volcanism on Kaua‘i (5.1–4.0 Ma) and Wai‘anae shield basalts (3.9–3.1 Ma) on O‘ahu. Young alkalic lavas (circa 0.37 Ma) sampled southwest of Ka‘ena Ridge are a form of offshore secondary volcanism. Half of the volcanic cones contain high‐SiO2 basalts (51.0–53.5 wt % SiO2). The trends of isotopic compositions of West Ka‘ena tholeiitic lavas diverge from the main Ko‘olau‐Kea shield binary mixing trend in isotope diagrams and extend to lower 208Pb/204Pb and 206Pb/204Pb than any Hawaiian tholeiitic lava. West Ka‘ena tholeiitic lavas have geochemical and isotopic characteristics similar to volcanoes of the Loa trend. Hence, our results show that the Loa‐type volcanism has persisted for at least 4.9 Myr, beginning prior to the development of the dual, subparallel chain of volcanoes. Several West Ka‘ena samples are similar to higher SiO2, Loa trend lavas of Ko‘olau Makapu‘u stage, Lāna‘i, and Kaho‘olawe; these lavas may have been derived from a pyroxenite source in the mantle. The high Ni contents of olivines in West Ka‘ena lavas also indicate contribution from pyroxenite‐derived melting. Average compositions of Hawaiian shield volcanoes show a clear relation between 206Pb/204Pb and SiO2 within Loa trend volcanoes, which supports a prominent but variable influence of pyroxenite in the Hawaiian plume source. In addition, both Pb isotopes and volcano volume show a steady increase with time starting from a minimum west of Ka‘ena Ridge. The entrained mafic component in the Hawaiian plume is probably not controlling the increasing magma productivity in the Hawaiian Islands.
The formation of organic compounds is generally assumed to result from abiotic processes in the Solar System, with the exception of biogenic organics on Earth. Nitrogen-bearing organics are of ...particular interest, notably for prebiotic perspectives but also for overall comprehension of organic formation in the young solar system and in planetary atmospheres. We have investigated abiotic synthesis of organics upon plasma discharge, with special attention to N isotope fractionation. Organic aerosols were synthesized from N2-CH4 and N2-CO gaseous mixtures using low-pressure plasma discharge experiments, aimed at simulating chemistry occurring in Titan s atmosphere and in the protosolar nebula, respectively. Nitrogen is efficiently incorporated into the synthesized solids, independently of the oxidation degree, of the N2 content of the starting gas mixture, and of the nitrogen speciation in the aerosols. The aerosols are depleted in 15N by 15-25 permil relative to the initial N2 gas, whatever the experimental setup is. Such an isotopic fractionation is attributed to mass-dependent kinetic effect(s). Nitrogen isotope fractionation upon electric discharge cannot account for the large N isotope variations observed among solar system objects and reservoirs. Extreme N isotope signatures in the solar system are more likely the result of self-shielding during N2 photodissociation, exotic effect during photodissociation of N2 and/or low temperature ion-molecule isotope exchange. Kinetic N isotope fractionation may play a significant role in the Titan s atmosphere. We also suggest that the low delta15N values of Archaean organic matter are partly the result of abiotic synthesis of organics that occurred at that time.
The aim of this in vivo study was to radiographically evaluate the proximal contour of composite resin restorations performed using different matrix systems.
Patients with premolars needing class II ...type resin composite restorations involving the marginal ridge were selected. Thirty premolars were selected and randomly divided into three groups (n = 10 each) to receive restorations using different matrix systems: group 1: metal matrix coupled to a carrier matrix and wood wedge (G1-MMW); group 2: sectioned and precontoured metal matrix and elastic wedge (G2-SME); and group 3: a polyester strip and reflective wedge (G3-PMR). After the restorative procedure, bitewing radiographs were performed and analyzed by three calibrated professionals. The quality of the proximal contact and marginal adaptation of the proximal surfaces was classified as either correct or incorrect (undercontour/overcontour).
The Pearson Chi-square statistical test (α = 5%) revealed a statistically difference between frequencies of correct and incorrect restorations (α(2) = 6.787, p < 0.05). The group G2 SME produced a higher frequency of correct proximal contours (90%), while G1-MMW and G3-PMR had a ratio of 40% correct and 60% incorrect contours respectively.
None of the matrix systems was able to prevent the formation of incorrect proximal contours; however, the sectioned and precontoured metal matrix/elastic wedge configuration provided better results as compared to the other groups.
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