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We report the first detection of triply-deuterated methanol, with 12 observed transitions, towards the low-mass protostar IRAS 16293-2422, as well as multifrequency observations of 13CH3OH, used to derive the column density of the main isotopomer CH3OH. The derived fractionation ratio [CD3OH]/[CH3OH] averaged on a 10 beam is 1.4%. Together with previous CH2DOH and CHD2OH observations, the present CD3OH observations are consistent with a formation of methanol on grain surfaces, if the atomic D/H ratio is 0.1 to 0.3 in the accreting gas. Such a high atomic ratio can be reached in the frame of gas-phase chemical models including all deuterated isotopomers of H3+.
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Deuterated molecules have been detected and studied toward Orion BN/KL in the past decades, mostly with single-dish telescopes. However, high angular resolution data are critical not only for interpreting the spatial distribution of the deuteration ratio but also for understanding this complex region in terms of cloud evolution involving star-forming activities and stellar feedbacks. We present here the first high angular resolution (1.8 arcsec times 0.8 arcsec) images of deuterated methanol CH2DOH in Orion BN/KL observed with the IRAM Plateau de Bure Interferometer from 1999 to 2007 in the 1 to 3 mm range. Six CH2DOH lines were detected around 105.8, 223.5, and 225.9 GHz. In addition, three E-type methanol lines around 101-102 GHz were detected and were used to derive the corresponding CH3OH rotational temperatures and column densities toward different regions across Orion BN/KL. The strongest CH2DOH and CH3OH emissions come from the Hot Core southwest region with an LSR velocity of about 8 km/s. We derive [CH2DOH]/[CH3OH] abundance ratios of 0.8-1.3times10^-3 toward three CH2DOH emission peaks. A new transition of CH3OD was detected at 226.2 GHz for the first time in the interstellar medium. Its distribution is similar to that of CH2DOH. Besides, we find that the [CH2DOH]/[CH3OD] abundance ratios are lower than unity in the central part of BN/KL. Furthermore, the HDO 3(1,2)-2(2,1) line at 225.9 GHz was detected and its emission distribution shows a shift of a few arcseconds with respect to the deuterated methanol emission that likely results from different excitation effects. The deuteration ratios derived along Orion BN/KL are not markedly different from one clump to another. However, various processes such as slow heating due to ongoing star formation, heating by luminous infrared sources, or heating by shocks could be competing to explain some local differences observed for these ratios.
We investigate the deuteration of methanol towards the high-mass star forming region NGC 7538-IRS1. We have carried out a multi-transition study of CH$_3$OH, $^{13}$CH$_3$OH and of the deuterated fllavors, CH$_2$DOH and CH$_3$OD, between 1.0--1.4 mm with the IRAM-30~m antenna. In total, 34 $^{13}$CH$_3$OH, 13 CH$_2$DOH lines and 20 CH$_3$OD lines spanning a wide range of upper-state energies (E$_{up}$) were detected. From the detected transitions, we estimate that the measured D/H does not exceed 1$%$, with a measured CH$_2$DOH/CH$_3$OH and CH$_3$OD/CH$_3$OH of about (32$pm$8)$times$10$^{-4}$ and (10$pm$4)$times$10$^{-4}$, respectively. This finding is consistent with the hypothesis of a short-time scale formation during the pre-stellar phase. We find a relative abundance ratio CH$_2$DOH/CH$_3$OD of 3.2 $pm$ 1.5. This result is consistent with a statistical deuteration. We cannot exclude H/D exchanges between water and methanol if water deuteration is of the order 0.1$%$, as suggested by recent Herschel observations.
We report the first detection in space of the two doubly deuterated isotopologues of methyl acetylene. The species CHD2CCH and CH2DCCD were identified in the dense core L483 through nine and eight, respectively, rotational lines in the 72-116 GHz range using the IRAM 30m telescope. The astronomical frequencies observed here were combined with laboratory frequencies from the literature measured in the 29-47 GHz range to derive more accurate spectroscopic parameters for the two isotopologues. We derive beam-averaged column densities of (2.7 +/- 0.5)e12 cm-2 for CHD2CCH and (2.2 +/- 0.4)e12 cm-2 for CH2DCCD, which translate to abundance ratios CH3CCH/CHD2CCH = 34 +/- 10 and CH3CCH/CH2DCCD = 42 +/- 13. The doubly deuterated isotopologues of methyl acetylene are only a few times less abundant than the singly deuterated ones, concretely around 2.4 times less abundant than CH3CCD. The abundances of the different deuterated isotopologues with respect to CH3CCH are reasonably accounted for by a gas-phase chemical model in which deuteration occurs from the precursor ions C3H6D+ and C3H5D+, when the ortho-to-para ratio of molecular hydrogen is sufficiently low. This points to gas-phase chemical reactions, rather than grain-surface processes, as responsible for the formation and deuterium fractionation of CH3CCH in L483. The abundance ratios CH2DCCH/CH3CCD = 3.0 +/- 0.9 and CHD2CCH/CH2DCCD = 1.25 +/- 0.37 observed in L483 are consistent with the statistically expected values of three and one, respectively, with the slight overabundance of CHD2CCH compared to CH2DCCD being well explained by the chemical model.
The first detection of gas-phase methanol in a protoplanetary disk (TW Hya) is presented. In addition to being one of the largest molecules detected in disks to date, methanol is also the first disk organic molecule with an unambiguous ice chemistry origin. The stacked methanol emission, as observed with ALMA, is spectrally resolved and detected across six velocity channels ($>3 sigma$), reaching a peak signal-to-noise of $5.5sigma$, with the kinematic pattern expected for TW~Hya. Using an appropriate disk model, a fractional abundance of $3times 10^{-12} - 4 times 10^{-11}$ (with respect to H$_2$) reproduces the stacked line profile and channel maps, with the favoured abundance dependent upon the assumed vertical location (midplane versus molecular layer). The peak emission is offset from the source position suggesting that the methanol emission has a ring-like morphology: the analysis here suggests it peaks at $approx 30$~AU reaching a column density $approx 3-6times10^{12}$~cm$^{-2}$. In the case of TW Hya, the larger (up to mm-sized) grains, residing in the inner 50~AU, may thus host the bulk of the disk ice reservoir. The successful detection of cold gas-phase methanol in a protoplanetary disk implies that the products of ice chemistry can be explored in disks, opening a window to studying complex organic chemistry during planetary system formation.
The circumstellar environments of objects on the asymptotic giant branch and beyond are rich in molecular species. Nevertheless, methanol has never been detected in such an object, and is therefore often taken as a clear signpost for a young stellar object. However, we report the first detection of CH3OH in a post-AGB object, HD101584, using ALMA. Its emission, together with emissions from CO, SiO, SO, CS, and H2CO, comes from two extreme velocity spots on either side of the object where a high-velocity outflow appears to interact with the surrounding medium. We have derived molecular abundances, and propose that the detected molecular species are the effect of a post-shock chemistry where circumstellar grains play a role. We further provide evidence that HD101584 was a low-mass, M-type AGB star.
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