TIMASSS : The IRAS16293-2422 Millimeter And Submillimeter Spectral Survey: Tentative Detection of Deuterated Methyl Formate (DCOOCH3)

High deuterium fractionation is observed in various types of environment such as prestellar cores, hot cores and hot corinos. It has proven to be an efficient probe to study the physical and chemical conditions of these environments. The study of the deuteration of different molecules helps us to understand their formation. This is especially interesting for complex molecules such as methanol and bigger molecules for which it may allow to differentiate between gas-phase and solid-state formation pathways. Methanol exhibits a high deuterium fractionation in hot corinos. Since CH3OH is thought to be a precursor of methyl formate we expect that deuterated methyl formate is produced in such environments. We have searched for the singly-deuterated isotopologue of methyl formate, DCOOCH3, in IRAS 16293-2422, a hot corino well-known for its high degree of methanol deuteration. We have used the IRAM/JCMT unbiased spectral survey of IRAS 16293-2422 which allows us to search for the DCOOCH3 rotational transitions within the survey spectral range (80-280 GHz, 328-366 GHz). The expected emission of deuterated methyl formate is modelled at LTE and compared with the observations.} We have tentatively detected DCOOCH3 in the protostar IRAS 16293-2422. We assign eight lines detected in the IRAM survey to DCOOCH3. Three of these lines are affected by blending problems and one line is affected by calibration uncertainties, nevertheless the LTE emission model is compatible with the observations. A simple LTE modelling of the two cores in IRAS 16293-2422, based on a previous interferometric study of HCOOCH3, allows us to estimate the amount of DCOOCH3 in IRAS 16293-2422. Adopting an excitation temperature of 100 K and a source size of 2\arcsec and 1\farcs5 for the A and B cores, respectively, we find that N(A,DCOOCH3) = N(B,DCOOCH3) ~ 6.10^14 /cm2. The derived deuterium fractionation is ~ 15%, consistent with values for other deuterated species in this source and much greater than that expected from the deuterium cosmic abundance. DCOOCH3, if its tentative detection is confirmed, should now be considered in theoretical models that study complex molecule formation and their deuteration mechanisms. Experimental work is also needed to investigate the different chemical routes leading to the formation of deuterated methyl formate

Detection of doubly-deuterated methanol in the solar-type protostar IRAS16293-2422

We report the first detection of doubly-deuterated methanol (CHD2OH), as well as firm detections of the two singly-deuterated isotopomers of methanol (CH2DOH and CH3OD), towards the solar-type protostar IRAS16293-2422. From the present multifrequency observations, we derive the following abundance ratios: [CHD2OH]/[CH3OH] = 0.2 +/- 0.1, [CH2DOH]/[CH3OH] = 0.9 +/- 0.3, [CH3OD]/[CH3OH] = 0.04 +/- 0.02. The total abundance of the deuterated forms of methanol is greater than that of its normal hydrogenated counterpart in the circumstellar material of IRAS16293-2422, a circumstance not previously encountered. Formaldehyde, which is thought to be the chemical precursor of methanol, possesses a much lower fraction of deuterated isotopomers (~ 20%) with respect to the main isotopic form in IRAS16293-2422. The observed fractionation of methanol and formaldehyde provides a severe challenge to both gas-phase and grain-surface models of deuteration. Two examples of the latter model are roughly in agreement with our observations of CHD2OH and CH2DOH if the accreting gas has a large (0.2-0.3) atomic D/H ratio. However, no gas-phase model predicts such a high atomic D/H ratio, and hence some key ingredient seems to be missing.Comment: 5 pages, 3 figure

First detection of triply-deuterated methanol

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+.Comment: Accepted by A&

2D quantitative analysis of fractures from high-resolution photos for the geomechanical characterization of rock masses

The identification of discontinuity sets and their properties is among the key factors for the geomechanical characterization of rock masses, which is fundamental for performing stability analyses, and for planning prevention and mitigation measures as well. In practice, discontinuity data are collected throughout difficult and time-consuming field surveys, especially when dealing with areas of wide extension, difficult accessibility, covered by dense vegetation, or with adverse weather conditions. Consequently, even experienced operators may introduce sampling errors or misinterpretations, leading to biased geomechanical models for the investigated rock mass. In the last decades, new remote techniques such as photogrammetry, Light Detection and Ranging (LiDAR), Unmanned Aerial Vehicle (UAV) and InfraRed Thermography (IRT) have been introduced to overcome the limits of conventional surveys. We propose here a new tool for extracting information on the fracture pattern in rock masses, based on remote sensing methods, with particular reference to the analysis of high-resolution georeferenced photos. The first step consists in applying the Structure from Motion (SfM) technique on photos acquired by means of digital cameras and UAV techniques. Once aligned and georeferenced, the orthophotos are exported in a GIS software, to draw the fracture traces at an appropriate scale. We developed a MATLAB routine to extract information on the geostructural setting of rock masses by performing a quantitative 2D analysis of the fracture traces, based on formulas reported in the literature. The code was written by testing few experimental and simple traces and was successively validated on an orthophoto from a real case study. Currently, the script plots the fracture traces as polylines and calculates their orientation (strike) and length. Subsequently, it detects the main discontinuity sets by fitting an experimental composite Gaussian curve on histograms showing the number of discontinuities according to their orientation, and splitting the curve in simpler Gaussian curves, with peaks corresponding to the main discontinuity sets. Then, for each set, a linear scanline intersecting the highest number of traces is plotted, and the apparent and real spacing are calculated. In a second step, a grid of circular scanlines covering the whole area where the traces are located is plotted, and the mean trace intensity, trace density and trace length estimators are calculated. It is expected to test the presented tools on other case studies, in order to optimize them and calculate additional metrics, such as persistence and block sizes, useful to the geomechanical characterization of rock masses. As a future perspective, a similar approach could be investigated for 3D analyses from point clouds

Deuterium chemistry in the Orion Bar PDR - "warm" chemistry starring CH2D+

High levels of deuterium fractionation in gas-phase molecules are usually associated with cold regions, such as prestellar cores. Significant fractionation ratios are also observed in hot environments such as hot cores or hot corinos, where they are believed to be produced by the evaporation of the icy mantles surrounding dust grains, and thus are remnants of a previous cold (either gas-phase or grain surface) chemistry. The recent detection of DCN towards the Orion Bar, in a clump at a characteristic temperature of 70K, has shown that high deuterium fractionation can also be detected in PDRs. The Orion Bar clumps thus appear as a good environment for the observational study of deuterium fractionation in luke-warm gas, allowing to validate chemistry models in a different temperature range, where dominating fractionation processes are predicted to be different than in cold gas (< 20K). We aimed at studying observationally in detail the chemistry at work in the Orion Bar PDR, to understand if DCN is produced by ice mantle evaporation, or is the result of warm gas-phase chemistry, involving the CH2D+ precursor ion (which survives higher temperatures than the usual H2D+ precursor). Using the APEX and the IRAM 30m telescopes, we targetted selected deuterated species towards two clumps in the Orion Bar. We confirmed the detection of DCN and detected two new deuterated molecules (DCO+ and HDCO) towards one clump in the Orion Bar PDR. Significant deuterium fractionations are found for HCN and H2CO, but a low fractionation in HCO+. We also give upper limits for other molecules relevant for the deuterium chemistry. (...) We show evidence that warm deuterium chemistry driven by CH2D+ is at work in the clumps.Comment: 14 pages, accepted for publication in A&

Deuterated water in the solar-type protostars NGC 1333 IRAS 4A and IRAS 4B

Aims. The aim of this paper is to study deuterated water in the solar-type protostars NGC1333 IRAS4A and IRAS4B, to compare their HDO abundance distribution with other star-forming regions, and to constrain their HDO/H2O ratios. Methods. Using the Herschel/HIFI instrument as well as ground-based telescopes, we observed several HDO lines covering a large excitation range (Eup/k=22-168 K) towards these protostars and an outflow position. Non-LTE radiative transfer codes were then used to determine the HDO abundance profiles in these sources. Results. The HDO fundamental line profiles show a very broad component, tracing the molecular outflows, in addition to a narrower emission component and a narrow absorbing component. In the protostellar envelope of NGC1333 IRAS4A, the HDO inner (T>100 K) and outer (T<100 K) abundances with respect to H2 are estimated at 7.5x10^{-9} and 1.2x10^{-11}, respectively, whereas, in NGC1333 IRAS4B, they are 1.0x10^{-8} and 1.2x10^{-10}, respectively. Similarly to the low-mass protostar IRAS16293-2422, an absorbing outer layer with an enhanced abundance of deuterated water is required to reproduce the absorbing components seen in the fundamental lines at 465 and 894 GHz in both sources. This water-rich layer is probably extended enough to encompass the two sources as well as parts of the outflows. In the outflows emanating from NGC1333 IRAS4A, the HDO column density is estimated at about (2-4)x10^{13} cm^{-2}, leading to an abundance of about (0.7-1.9)x10^{-9}. An HDO/H2O ratio between 7x10^{-4} and 9x10^{-2} is derived in the outflows. In the warm inner regions of these two sources, we estimate the HDO/H2O ratios at about 1x10^{-4}-4x10^{-3}. This ratio seems higher (a few %) in the cold envelope of IRAS4A, whose possible origin is discussed in relation to formation processes of HDO and H2O.Comment: 16 pages, 13 figure

Gold nanoparticles supported on functionalized silica as catalysts for alkyne hydroamination: A chemico-physical insight

Highly stable gold nanoparticles anchored on propynylcarbamate-functionalized silica (Au/SiO2@Yne) have been efficiently utilized for the heterogeneous hydroamination of phenylacetylene with aniline under different reaction conditions. In order to ascertain the eventual influence of surface silanol groups on the system activity and selectivity tailored modifications of Au/SiO2@Yne catalysts were pursued according to two different strategies, involving respectively functionalization with trimethylethoxysilane (Au/SiO2@Yne-TMS) or post-treatment with triethylamine (Au/SiO2@Yne-NEt3). The prepared materials were analysed by several complementary techniques such as Solid State NMR (SS NMR), Transmission Electron Microscopy (TEM), X-ray Photoelectron Spectroscopy (XPS), X-ray Diffraction (XRD). A comparison of the resulting catalytic activities with that of the pristine Au/SiO2@Yne revealed a significant improvement for Au/SiO2@Yne-NEt3 in terms of both conversion and selectivity. Recycling and stability studies showed a catalytic activity decrease after the first run, due to the formation of polyphenylacetylene (PPhA) oligomers shielding the active sites. PPhA removal by sonication in acetone fully restored the catalytic activity and empowered the system with a good operational stability, a very crucial issue in view of eventual practical applications

Search for solid HDO in low-mass protostars

We present ground-based 2.1 to 4.2 microns observations of four low-mass protostars. We searched for the 4.1 microns OD stretch band, characteristic of solid HDO in grain mantles. We did not detect solid HDO in any of the four sources, but we derive 3-sigma upper limits from 0.5% to 2% for the HDO/H2O ratio depending on the source. These ratios provide strong constraints to solid-state deuteration models when compared to deuterium fractionation values observed in the gas phase. We discuss various scenarios that could lead to such a low water deuteration compared to the high formaldehyde and methanol deuteration observed in the gas phase.Comment: 8 pages, 6 figures Accepted for publication in A&

Testing grain surface chemistry : a survey of deuterated formaldehyde and methanol in low-mass Class 0 protostars

Context : Despite the low cosmic abundance of deuterium (D/H ~ 1e-5), large degrees of deuterium fractionation in molecules are observed in star forming regions with enhancements that can reach 13 orders of magnitude, which current models have difficulties to account for. Aims : Multi-isotopologue observations are a very powerful constraint for chemical models. The aim of our observations is to understand the processes forming the observed large abundances of methanol and formaldehyde in low-mass protostellar envelopes (gas-phase processes ? chemistry on the grain surfaces ?) and better constrain the chemical models. Methods : Using the IRAM 30m single-dish telescope, we observed deuterated formaldehyde (HDCO and D2CO) and methanol (CH2DOH, CH3OD, and CHD2OH) towards a sample of seven low-mass class 0 protostars. Using population diagrams, we then derive the fractionation ratios of these species (abundance ratio between the deuterated molecule and its main isotopologue) and compare them to the predictions of grain chemistry models. Results : These protostars show a similar level of deuteration as in IRAS16293-2422, where doubly-deuterated methanol -- and even triply-deuterated methanol -- were first detected. Our observations point to the formation of methanol on the grain surfaces, while formaldehyde formation cannot be fully pined down. While none of the scenarii can be excluded (gas-phase or grain chemistry formation), they both seem to require abstraction reactions to reproduce the observed fractionations.Comment: 21 pages, 12 figures, accepted by A&

The solar type protostar IRAS16293-2422: new constraints on the physical structure

Context: The low mass protostar IRAS16293-2422 is a prototype Class 0 source with respect to the studies of the chemical structure during the initial phases of life of Solar type stars. Aims: In order to derive an accurate chemical structure, a precise determination of the source physical structure is required. The scope of the present work is the derivation of the structure of IRAS16293-2422. Methods: We have re-analyzed all available continuum data (single dish and interferometric, from millimeter to MIR) to derive accurate density and dust temperature profiles. Using ISO observations of water, we have also reconstructed the gas temperature profile. Results: Our analysis shows that the envelope surrounding IRAS16293-2422 is well described by the Shu "inside-out" collapsing envelope model or a single power-law density profile with index equal to 1.8. In contrast to some previous studies, our analysis does not show evidence of a large (>/- 800 AU in diameter) cavity. Conclusions: Although IRAS16293-2422 is a multiple system composed by two or three objects, our reconstruction will be useful to derive the chemical structure of the large cold envelope surrounding these objects and the warm component, treated here as a single source, from single-dish observations of molecular emission