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Register a new userIsotopic fractionation of carbon, deuterium and nitrogen : a full chemical study
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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.
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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.
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.
Although ammonia is an abundant molecule commonly observed towards the dense interstellar medium, it has not yet been established whether its main formation route is from gas-phase ion-molecule reactions or grain-surface hydrogen additions on adsorbed nitrogen atoms. Deuterium fractionation can be used as a tool to constrain formation mechanisms. High abundances of deuterated molecules are routinely observed in the dense interstellar medium, with the ratio between deuterated molecules and the main isotopologue enhanced by several orders of magnitude with respect to the elemental D/H ratio. In the case of ammonia, the detection of its triply deuterated isotopologue hints at high abundances of the deuterated intermediate nitrogen radicals, ND, NHD and ND$_2$. So far however, only ND has been detected in the interstellar medium. In this paper, to constrain the formation of ammonia, we aim at determining the NHD/NH$_2$ and ND$_2$/NHD abundance ratios, and compare them with the predictions of both pure gas-phase and grain-surface chemical models. We searched for the fundamental rotational transitions of NHD and ND$_2$ towards the class 0 protostar IRAS16293-2422, towards which NH, NH$_2$ and ND had been previously detected. Both NHD and ND$_2$ are detected in absorption towards the source. The relative abundance ratios NH$_2$ : NHD : ND$_2$ are close to 8 : 4 : 1. These ratios can be reproduced by our gas-phase chemical model within a factor of two-three. Statistical ratios as expected from grain-surface chemistry are also consistent with our data. Further investigations of the ortho-to-para ratio in ND$_2$ , both theoretical and observational, could bring new constraints to better understand nitrogen hydride chemistry.
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.
We upgraded the chemical network from the UMIST Database for Astrochemistry 2006 to include isotopes such as ^{13}C and ^{18}O. This includes all corresponding isotopologues, their chemical reactions and the properly scaled reaction rate coefficients. We study the fractionation behavior of astrochemically relevant species over a wide range of model parameters, relevant for modelling of photo-dissociation regions (PDRs). We separately analyze the fractionation of the local abundances, fractionation of the total column densities, and fractionation visible in the emission line ratios. We find that strong C^+ fractionation is possible in cool C^+ gas. Optical thickness as well as excitation effects produce intensity ratios between 40 and 400. The fractionation of CO in PDRs is significantly different from the diffuse interstellar medium. PDR model results never show a fractionation ratio of the CO column density larger than the elemental ratio. Isotope-selective photo-dissociation is always dominated by the isotope-selective chemistry in dense PDR gas. The fractionation of C, CH, CH^+, and HCO^+ is studied in detail, showing that the fractionation of C, CH and CH^+ is dominated by the fractionation of their parental species. The light hydrides chemically derive from C^+, and, consequently, their fractionation state is coupled to that of C^+. The fractionation of C is a mixed case depending on whether formation from CO or HCO^+ dominates. Ratios of the emission lines of [C II], [C I], ^{13}CO, and H^{13}CO^+ provide individual diagnostics to the fractionation status of C^+, C, and CO.
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