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Register a new userNitrogen isotopic fractionation during abiotic synthesis of organic solid particles
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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.
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Using the Green Bank Telescope (GBT), we have obtained accurate measurements of the $^{14}$N/$^{15}$N isotopic ratio in ammonia in two nearby cold, dense molecular clouds, Barnard~1 and NGC 1333. The $^{14}$N/$^{15}$N ratio in Barnard~1, $334 pm 50$ (3$sigma$), is particularly well constrained and falls in between the local interstellar medium/proto-solar value of $sim 450$ and the terrestrial atmospheric value of 272. The NGC 1333 measurement is consistent with the Barnard~1 result, but has a larger uncertainty. We do not see evidence for the very high $^{15}$N enhancements seen in cometary CN. Sensitive observations of a larger, carefully selected sample of prestellar cores with varying temperatures and gas densities can significantly improve our understanding of the nitrogen fractionation in the local interstellar medium and its relation to the isotopic ratios measured in various solar system reservoirs.
Context. The increased sensitivity and high spectral resolution of millimeter telescopes allow the detection of an increasing number of isotopically substituted molecules in the interstellar medium. The 14N/ 15N ratio is difficult to measure directly for carbon containing molecules. Aims. We want to check the underlying hypothesis that the 13C/ 12C ratio of nitriles and isonitriles is equal to the elemental value via a chemical time dependent gas phase chemical model. Methods. We have built a chemical network containing D, 13C and 15N molecular species after a careful check of the possible fractionation reactions at work in the gas phase. Results. Model results obtained for 2 different physical conditions corresponding respectively to a moderately dense cloud in an early evolutionary stage and a dense depleted pre-stellar core tend to show that ammonia and its singly deuterated form are somewhat enriched in 15N, in agreement with observations. The 14N/ 15N ratio in N2H+ is found to be close to the elemental value, in contrast to previous models which obtain a significant enrichment, as we found that the fractionation reaction between 15N and N2H+ has a barrier in the entrance channel. The large values of the N2H+/15NNH+ and N2H+/ N15NH+ ratios derived in L1544 cannot be reproduced in our model. Finally we find that nitriles and isonitriles are in fact significantly depleted in 13C, questioning previous interpretations of observed C15N, HC15N and H15NC abundances from 13C containing isotopologues.
C-fractionation has been studied from a theoretical point of view with different models of time-dependent chemistry, including both isotope-selective photodissociation and low-temperature isotopic exchange reactions. Recent chemical models predict that the latter may lead to a depletion of $^{13}$C in nitrile-bearing species, with $^{12}$C/$^{13}$C ratios two times higher than the elemental abundance ratio of 68 in the local ISM. Since the carbon isotopic ratio is commonly used to evaluate the $^{14}$N/$^{15}$N ratios with the double-isotope method, it is important to study C-fractionation in detail to avoid incorrect assumptions. In this work we implemented a gas-grain chemical model with new isotopic exchange reactions and investigated their introduction in the context of dense and cold molecular gas. In particular, we investigated the $^{12}$C/$^{13}$C ratios of HNC, HCN, and CN using a grid of models, with temperatures and densities ranging from 10 to 50 K and 2$times$10$^{3}$ to 2$times$10$^{7}$ cm$^{-3}$, respectively. We suggest a possible $^{13}$C exchange through the $^{13}$C + C$_{3}$ $rightarrow$ $^{12}$C +$^{13}$CC$_{2}$ reaction, which does not result in dilution, but rather in $^{13}$C enhancement, for molecules formed starting from atomic carbon. This effect is efficient in a range of time between the formation of CO and its freeze-out on grains. Furthermore, we show that the $^{12}$C/$^{13}$C ratios of nitriles are predicted to be a factor 0.8-1.9 different from the local value of 68 for massive star-forming regions. This result also affects the $^{14}$N/$^{15}$N ratio: a value of 330 obtained with the double-isotope method is predicted to be 260-1150, depending on the physical conditions. Finally, we studied the $^{12}$C/$^{13}$C ratios by varying the cosmic-ray ionization rate: the ratios increase with it because of secondary photons and cosmic-ray reactions.
Silicon and Mg in differentiated rocky bodies exhibit heavy isotope enrichments that have been attributed to evaporation of partially or entirely molten planetesimals. We evaluate the mechanisms of planetesimal evaporation in the early solar system and the conditions that controlled attendant isotope fractionations. Energy balance at the surface of a body accreted within ~1 Myr of CAI formation and heated from within by 26Al decay results in internal temperatures exceeding the silicate solidus, producing a transient magma ocean with a thin surface boundary layer of order < 1 meter that would be subject to foundering. Bodies that are massive enough to form magma oceans by radioisotope decay (ge 0.1%) can retain hot rock vapor even in the absence of ambient nebular gas. We find that a steady-state rock vapor forms within minutes to hours and results from a balance between rates of magma evaporation and atmospheric escape. Vapor pressure buildup adjacent to the surfaces of the evaporating magmas would have inevitably led to an approach to equilibrium isotope partitioning between the vapor phase and the silicate melt. Numerical simulations of this near-equilibrium evaporation process for a body with a radius of ~ 700 km yield a steady-state far-field vapor pressure corresponding to 95% saturation. Approaches to equilibrium isotope fractionation between vapor and melt should have been the norm during planet formation due to the formation of steady-state rock vapor atmospheres and/or the presence of protostellar gas. We model the Si and Mg isotopic composition of bulk Earth and show that the best fit is for a carbonaceous chondrite-like source material with about 12% loss of Mg and 15% loss of Si resulting from near-equilibrium evaporation into the solar protostellar disk of hydrogen gas on timescales of 10,000 to 100,000 years.
Aims: The two stable isotopes of nitrogen, 14N and 15N, exhibit a range of abundance ratios both inside and outside the solar system. The elemental ratio in the solar neighborhood is 440. Recent ALMA observations showed HCN/HC15N ratios from 83 to 156 in six T Tauri and Herbig disks and a CN/C15 N ratio of 323 +/- 30 in one T Tauri star. We aim to determine the dominant mechanism responsible for these enhancements of 15N: low-temperature exchange reactions or isotope-selective photodissociation of N2. Methods: Using the thermochemical code DALI, we model the nitrogen isotope chemistry in circumstellar disks with a 2D axisymmetric geometry. Our chemical network is the first to include both fractionation mechanisms for nitrogen. The model produces abundance profiles and isotope ratios for several key N-bearing species. We study how these isotope ratios depend on various disk parameters. Results: The formation of CN and HCN is closely coupled to the vibrational excitation of H2 in the UV-irradiated surface layers of the disk. Isotope fractionation is completely dominated by isotope-selective photodissociation of N2. The column density ratio of HCN over HC15N in the disks inner 100 au does not depend strongly on the disk mass, the flaring angle or the stellar spectrum, but it is sensitive to the grain size distribution. For larger grains, self-shielding of N2 becomes more important relative to dust extinction, leading to stronger isotope fractionation. Between disk radii of ~50 and 200 au, the models predict HCN/HC15N and CN/C15N abundance ratios consistent with observations of disks and comets. The HCN/HC15N and CN/C15N column density ratios in the models are a factor of 2-3 higher than those inferred from the ALMA observations.
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