Isotopic Anomalies in Primitive Solar System Matter: Spin-state Dependent Fractionation of Nitrogen and Deuterium in Interstellar Clouds

Organic material found in meteorites and interplanetary dust particles is enriched in D and 15N. This is consistent with the idea that the functional groups carrying these isotopic anomalies, nitriles and amines, were formed by ion-molecule chemistry in the protosolar nebula. Theoretical models of interstellar fractionation at low temperatures predict large enrichments in both D and 15N and can account for the largest isotopic enrichments measured in carbonaceous meteorites. However, more recent measurements have shown that, in some primitive samples, a large 15N enrichment does not correlate with one in D, and that some D-enriched primitive material displays little, if any, 15N enrichment. By considering the spin-state dependence in ion-molecule reactions involving the ortho and para forms of H2, we show that ammonia and related molecules can exhibit such a wide range of fractionation for both 15N and D in dense cloud cores. We also show that while the nitriles, HCN and HNC, contain the greatest 15N enrichment, this is not expected to correlate with extreme D enrichment. These calculations therefore support the view that Solar System 15N and D isotopic anomalies have an interstellar heritage. We also compare our results to existing astronomical observations and briefly discuss future tests of this model.Comment: Submitted to ApJ

Combined model for 15N\rm ^{15}N, 13C\rm ^{13}C, and spin-state chemistry in molecular clouds

We present a new gas-grain chemical model for the combined isotopic fractionation of carbon and nitrogen in molecular clouds, in which the isotope chemistry of carbon and nitrogen is coupled with a time-dependent description of spin-state chemistry. We updated the rate coefficients of some isotopic exchange reactions considered in the literature, and present here a set of new exchange reactions involving molecules substituted in $\rm ^{13}C$ and $\rm ^{15}N$ simultaneously. We apply the model to a series of zero-dimensional simulations representing a set of physical conditions across a prototypical prestellar core, exploring the deviations of the isotopic abundance ratios in the various molecules from the elemental isotopic ratios as a function of physical conditions and time. We find that the $\rm ^{12}C/^{13}C$ ratio can deviate from the elemental ratio by up to a factor of several depending on the molecule, and that there are highly time-dependent variations in the ratios. The $\rm HCN/H^{13}CN$ ratio, for example, can obtain values of less than 10 depending on the simulation time. The $\rm ^{14}N/^{15}N$ ratios tend to remain close to the assumed elemental ratio within $\sim$ ten per cent, with no clear trends as a function of the physical conditions. Abundance ratios between $\rm ^{13}C$-containing molecules and $\rm ^{13}C$+$\rm ^{15}N$-containing molecules show somewhat increased levels of fractionation due to the newly included exchange reactions, though still remaining within a few tens of per cent of the elemental $\rm ^{14}N/^{15}N$ ratio. Our results imply the existence of gradients in isotopic abundance ratios across prestellar cores, suggesting that detailed simulations are required to interpret observations of isotopically substituted molecules correctly, especially given that the various isotopic forms of a given molecule do not necessarily trace the same gas layers.Comment: Accepted to A\&A; abstract abridged to meet arXiv requirement

On the accretion process in a high-mass star forming region - A multitransitional THz Herschel-HIFI study of ammonia toward G34.26+0.15

[Abridged] Our aim is to explore the gas dynamics and the accretion process in the early phase of high-mass star formation. The inward motion of molecular gas in the massive star forming region G34.26+0.15 is investigated by using high-resolution profiles of seven transitions of ammonia at THz frequencies observed with Herschel-HIFI. The shapes and intensities of these lines are interpreted in terms of radiative transfer models of a spherical, collapsing molecular envelope. An accelerated Lambda Iteration (ALI) method is used to compute the models. The seven ammonia lines show mixed absorption and emission with inverse P-Cygni-type profiles that suggest infall onto the central source. A trend toward absorption at increasingly higher velocities for higher excitation transitions is clearly seen in the line profiles. The $J = 3\leftarrow2$ lines show only very weak emission, so these absorption profiles can be used directly to analyze the inward motion of the gas. This is the first time a multitransitional study of spectrally resolved rotational ammonia lines has been used for this purpose. Broad emission is, in addition, mixed with the absorption in the $1_0-0_0$ ortho-NH$_3$ line, possibly tracing a molecular outflow from the star forming region. The best-fitting ALI model reproduces the continuum fluxes and line profiles, but slightly underpredicts the emission and absorption depth in the ground-state ortho line $1_0-0_0$. The derived ortho-to-para ratio is approximately 0.5 throughout the infalling cloud core similar to recent findings for translucent clouds in sight lines toward W31C and W49N. We find evidence of two gas components moving inwards toward the central region with constant velocities: 2.7 and 5.3 km$\,$s$^{-1}$, relative to the source systemic velocity. The inferred mass accretion rates derived are sufficient to overcome the expected radiation pressure from G34.26+0.15.Comment: 20 pages, 18 figures, accepted by A&A 3 October 201

Similar levels of deuteration in the pre-stellar core L1544 and the protostellar core HH211

In the centre of pre-stellar cores, deuterium fractionation is enhanced due to the low temperatures and high densities. Therefore, the chemistry of deuterated molecules can be used to study the earliest stages of star formation. We analyse the deuterium fractionation of simple molecules, comparing the level of deuteration in the envelopes of the pre-stellar core L1544 in Taurus and the protostellar core HH211 in Perseus. We used single-dish observations of CCH, HCN, HNC, HCO$^+$, and their $^{13}$C-, $^{18}$O- and D-bearing isotopologues, detected with the Onsala 20m telescope. We derived the column densities and the deuterium fractions of the molecules. Additionally, we used radiative transfer simulations and results from chemical modelling to reproduce the observed molecular lines. We used new collisional rate coefficients for HNC, HN$^{13}$C, DNC, and DCN that consider the hyperfine structure of these molecules. We find high levels of deuteration for CCH (10%) in both sources, consistent with other carbon chains, and moderate levels for HCN (5-7%) and HNC (8%). The deuterium fraction of HCO$^+$ is enhanced towards HH211, most likely caused by isotope-selective photodissociation of C$^{18}$O. Similar levels of deuteration show that the process is likely equally efficient towards both cores, suggesting that the protostellar envelope still retains the chemical composition of the original pre-stellar core. The fact that the two cores are embedded in different molecular clouds also suggests that environmental conditions do not have a significant effect on the deuteration within dense cores. Radiative transfer modelling shows that it is necessary to include the outer layers of the cores to consider the effects of extended structures. Besides HCO$^+$ observations, HCN observations towards L1544 also require the presence of an outer diffuse layer where the molecules are relatively abundant.Comment: 27 pages, 17 figures, accepted for publication in A&

On the nature of the enigmatic object IRAS 19312+1950: A rare phase of massive star formation?

IRAS 19312+1950 is a peculiar object that has eluded firm characterization since its discovery, with combined maser properties similar to an evolved star and a young stellar object (YSO). To help determine its true nature, we obtained infrared spectra of IRAS 19312+1950 in the range 5-550 $\mu$m using the Herschel and Spitzer space observatories. The Herschel PACS maps exhibit a compact, slightly asymmetric continuum source at 170 $\mu$m, indicative of a large, dusty circumstellar envelope. The far-IR CO emission line spectrum reveals two gas temperature components: $\approx0.22M_{\odot}$ of material at $280\pm18$ K, and $\approx1.6M_{\odot}$ of material at $157\pm3$ K. The OI 63 $\mu$m line is detected on-source but no significant emission from atomic ions was found. The HIFI observations display shocked, high-velocity gas with outflow speeds up to 90 km s$^{-1}$ along the line of sight. From Spitzer spectroscopy, we identify ice absorption bands due to H$_2$O at 5.8 $\mu$m and CO$_2$ at 15 $\mu$m. The spectral energy distribution is consistent with a massive, luminous ($\sim2\times10^4L_{\odot}$) central source surrounded by a dense, warm circumstellar disk and envelope of total mass $\sim500$-$700M_{\odot}$, with large bipolar outflow cavities. The combination of distinctive far-IR spectral features suggest that IRAS 19312+1950 should be classified as an accreting high-mass YSO rather than an evolved star. In light of this reclassification, IRAS 19312+1950 becomes only the 5th high-mass protostar known to exhibit SiO maser activity, and demonstrates that 18 cm OH maser line ratios may not be reliable observational discriminators between evolved stars and YSOs.Comment: 16 pages. Accepted for publication in Ap

Observational tests of interstellar methanol formation

Context. It has been established that the classical gas-phase production of interstellar methanol (CH3OH) cannot explain observed abundances. Instead it is now generally thought that the main formation path has to be by successive hydrogenation of solid CO on interstellar grain surfaces. Aims: While theoretical models and laboratory experiments show that methanol is efficiently formed from CO on cold grains, our aim is to test this scenario by astronomical observations of gas associated with young stellar objects (YSOs). Methods: We have observed the rotational transition quartets J = 2K - 1K of 12CH3OH and 13CH3OH at 96.7 and 94.4 GHz, respectively, towards a sample of massive YSOs in different stages of evolution. In addition, the J = 1-0 transitions of 12C18O and 13C18O were observed towards some of these sources. We use the 12C/13C ratio to discriminate between gas-phase and grain surface origin: If methanol is formed from CO on grains, the ratios should be similar in CH3OH and CO. If not, the ratio should be higher in CH3OH due to 13C fractionation in cold CO gas. We also estimate the abundance ratios between the nuclear spin types of methanol (E and A). If methanol is formed on grains, this ratio is likely to have been thermalized at the low physical temperature of the grain, and therefore show a relative over-abundance of A-methanol. Results: We show that the 12C/13C isotopic ratio is very similar in gas-phase CH3OH and C18O, on the spatial scale of about 40", towards four YSOs. For two of our sources we find an overabundance of A-methanol as compared to E-methanol, corresponding to nuclear spin temperatures of 10 and 16 K. For the remaining five sources, the methanol E/A ratio is less than unity. Conclusions: While the 12C/13C ratio test is consistent with methanol formation from hydrogenation of CO on grain surfaces, the result of the E/A ratio test is inconclusive

A spectral line survey of Orion KL in the bands 486-492 and 541-577 GHz with the Odin satellite I. The observational data

Spectral line surveys are useful since they allow identification of new molecules and new lines in uniformly calibrated data sets. Nonetheless, large portions of the sub-millimetre spectral regime remain unexplored due to severe absorptions by H2O and O2 in the terrestrial atmosphere. The purpose of the measurements presented here is to cover wavelength regions at and around 0.55 mm -- regions largely unobservable from the ground. Using the Odin astronomy/aeronomy satellite, we performed the first spectral survey of the Orion KL molecular cloud core in the bands 486--492 and 541--576 GHz with rather uniform sensitivity (22--25 mK baseline noise). Odin's 1.1 m size telescope, equipped with four cryo-cooled tuneable mixers connected to broad band spectrometers, was used in a satellite position-switching mode. Two mixers simultaneously observed different 1.1 GHz bands using frequency steps of 0.5 GHz (25 hours each). An on-source integration time of 20 hours was achieved for most bands. The entire campaign consumed ~1100 orbits, each containing one hour of serviceable astro-observation. We identified 280 spectral lines from 38 known interstellar molecules (including isotopologues) having intensities in the range 80 to 0.05 K. An additional 64 weak lines remain unidentified. Apart from the ground state rotational 1(1,0)--1(0,1) transitions of ortho-H2O, H218O and H217O, the high energy 6(2,4)--7(1,7) line of para-H2O and the HDO(2,0,2--1,1,1) line have been observed, as well as the 1,0--0,1 lines from NH3 and its rare isotopologue 15NH3. We suggest assignments for some unidentified features, notably the new interstellar molecules ND and SH-. Severe blends have been detected in the line wings of the H218O, H217O and 13CO lines changing the true linewidths of the outflow emission.Comment: 21 pages, 10 figures, 7 tables, accepeted for publication in Astronomy and Astrophysics 30 August 200

Ground-state ammonia and water in absorption towards Sgr B2

Context. Observations of transitions to the ground-state of a molecule are essential to obtain a complete picture of its excitation and chemistry in the interstellar medium, especially in diffuse and/or cold environments. For the important interstellar molecules H₂O and NH₃, these ground-state transitions are heavily absorbed by the terrestrial atmosphere, hence not observable from the ground. Aims: We attempt to understand the chemistry of nitrogen, oxygen, and their important molecular forms, NH₃ and H₂O in the interstellar medium of the Galaxy. Methods: We have used the Odin* submillimetre-wave satellite telescope to observe the ground state transitions of ortho-ammonia and ortho-water, including their ¹⁵N, ¹⁸O, and ¹⁷O isotopologues, towards Sgr B2. The extensive simultaneous velocity coverage of the observations, >500 km s^-1, ensures that we can probe the conditions of both the warm, dense gas of the molecular cloud Sgr B2 near the Galactic centre, and the more diffuse gas in the Galactic disk clouds along the line-of-sight. Results: We present ground-state NH₃ absorption in seven distinct velocity features along the line-of-sight towards Sgr B2. We find a nearly linear correlation between the column densities of NH₃ and CS, and a square-root relation to N₂H⁺. The ammonia abundance in these diffuse Galactic disk clouds is estimated to be about 0.5–1 × 10^-8, similar to that observed for diffuse clouds in the outer Galaxy. On the basis of the detection of H_218O absorption in the 3 kpc arm, and the absence of such a feature in the H_217O spectrum, we conclude that the water abundance is around 10-7, compared to ~10-8 for NH3. The Sgr B2 molecular cloud itself is seen in absorption in NH₃, 15NH₃, H₂O, H_218O, and H_217O, with emission superimposed on the absorption in the main isotopologues. The non-LTE excitation of NH3 in the environment of Sgr B2 can be explained without invoking an unusually hot (500 K) molecular layer. A hot layer is similarly not required to explain the line profiles of the 11,0≥ts10,1 transition from H2O and its isotopologues. The relatively weak 15NH3 absorption in the Sgr B2 molecular cloud indicates a high [ 14N/15N] isotopic ratio >600. The abundance ratio of H_218O and H_217O is found to be relatively low, 2.5–3. These results together indicate that the dominant nucleosynthesis process in the Galactic centre is CNO hydrogen burning. Odin is a Swedish-led satellite project funded jointly by the Swedish National Space Board (SNSB), the Canadian Space Agency (CSA), the National Technology Agency of Finland (Tekes), and the centre National d'Études Spatiales (CNES, France). The Swedish Space Corporation (SSC) was the industrial prime contractor and is also responsible for the satellite operation

Upper limits to interstellar NH^+ and para-NH_2^− abundances. Herschel-HIFI observations towards Sgr B2 (M) and G10.6−0.4 (W31C)

The understanding of interstellar nitrogen chemistry has improved significantly with recent results from the Herschel Space Observatory. To set even better constraints, we report here on deep searches for the NH^+ ground state rotational transition J = 1.5−0.5 of the ^2Π_(1/2) lower spin ladder, with fine-structure transitions at 1013 and 1019 GHz, and the para-NH_2^− 1_(1,1)−0_(0,0) rotational transition at 934 GHz towards Sgr B2 (M) and G10.6−0.4 (W31C) using the Herschel Heterodyne Instrument for the Far-Infrared (HIFI). No clear detections of NH^+ are made and the derived upper limits relative to the total number of hydrogen nuclei are ≲2 × 10^(-12) and ≲7 × 10^(-13) in the Sgr B2 (M) molecular envelope and in the G10.6−0.4 molecular cloud, respectively. The searches are, however, complicated by the fact that the 1 013 GHz transition lies only −2.5 km s^(-1) from a CH_2NH line, which is seen in absorption in Sgr B2 (M), and that the hyperfine structure components in the 1019 GHz transition are spread over 134 km s^(-1). Searches for the so far undetected NH_2^− anion turned out to be unfruitful towards G10.6−0.4, while the para-NH_2^− 1_(1,1)−0_(0,0) transition was tentatively detected towards Sgr B2 (M) at a velocity of 19 km s^(-1). Assuming that the absorption occurs at the nominal source velocity of +64 km s^(-1), the rest frequency would be 933.996 GHz, offset by 141 MHz from our estimated value. Using this feature as an upper limit, we found N(p-NH_2^−) ≲4 × 10^(11) cm^(-2), which implies an abundance of ≲8 × 10^(-13) in the Sgr B2 (M) molecular envelope. The upper limits for both species in the diffuse line-of-sight gas are less than 0.1 to 2% of the values found for NH, NH_2, and NH_3 towards both sources, and the abundance limits are ≲2−4 × 10^(-11). An updated pseudo time-dependent chemical model with constant physical conditions, including both gas-phase and surface chemistry, predicts an NH^+ abundance a few times lower than our present upper limits in diffuse gas and under typical Sgr B2 (M) envelope conditions. The NH_2^− abundance is predicted to be several orders of magnitudes lower than our observed limits, hence not supporting our tentative detection. Thus, while NH_2^− may be very difficult to detect in interstellar space, it could, on the other hand, be possible to detect NH^+ in regions where the ionisation rates of H_2 and N are greatly enhanced