Protonated CO2 in massive star-forming clumps

Interstellar CO2 is an important reservoir of carbon and oxygen, and one of the major constituents of the icy mantles of dust grains, but it is not observable directly in the cold gas because has no permanent dipole moment. Its protonated form, HOCO+, is believed to be a good proxy for gaseous CO2. However, it has been detected in only a few star-forming regions so far, so that its interstellar chemistry is not well understood. We present new detections of HOCO+ lines in 11 high-mass star-forming clumps. Our observations increase by more than three times the number of detections in star-forming regions so far. We have derived beam-averaged abundances relative to H2 in between 0.3 and 3.8 x 10^{-11}. We have compared these values with the abundances of H13CO+, a possible gas-phase precursor of HOCO+, and CH3OH, a product of surface chemistry. We have found a positive correlation with H13CO+, while with CH3OH there is no correlation. We suggest that the gas-phase formation route starting from HCO+ plays an important role in the formation of HOCO+, perhaps more relevant than protonation of CO2 (upon evaporation of this latter from icy dust mantles).Comment: 5 pages, 4 figures, 1 table, accepted for publication in MNRA

Deuteration as an evolutionary tracer in massive-star formation

Theory predicts, and observations confirm, that the column density ratio of a molecule containing D to its counterpart containing H can be used as an evolutionary tracer in the low-mass star formation process. Since it remains unclear if the high-mass star formation process is a scaled-up version of the low-mass one, we investigated whether the relation between deuteration and evolution can be applied to the high-mass regime. With the IRAM-30m telescope, we observed rotational transitions of N2D+ and N2H+ and derived the deuterated fraction in 27 cores within massive star-forming regions understood to represent different evolutionary stages of the massive-star formation process. Results. Our results clearly indicate that the abundance of N2D+ is higher at the pre-stellar/cluster stage, then drops during the formation of the protostellar object(s) as in the low-mass regime, remaining relatively constant during the ultra-compact HII region phase. The objects with the highest fractional abundance of N2D+ are starless cores with properties very similar to typical pre-stellar cores of lower mass. The abundance of N2D+ is lower in objects with higher gas temperatures as in the low-mass case but does not seem to depend on gas turbulence. Our results indicate that the N2D+-to-N2H+ column density ratio can be used as an evolutionary indicator in both low- and high-mass star formation, and that the physical conditions influencing the abundance of deuterated species likely evolve similarly during the processes that lead to the formation of both low- and high-mass stars.Comment: Accepted by A&AL, 4 pages, 2 figures, 2 appendices (one for Tables, one for additional figures

Search for massive protostellar candidates in the southern hemisphere: I. Association with dense gas

(Abridged) We have observed CS and C17O lines, and 1.2 mm cont. emission towards a sample of 130 high-mass protostellar candidates with DEC<-30 deg. This is the first step of the southern extension of a project started more than a decade ago aimed at the identification of massive protostellar candidates. We selected from the IRAS PSC 429 sources which potentially are compact molecular clouds. The sample is divided into two groups: the 298 sources with [25-12]>0.57 and [60-12]>1.30 we call 'High' sources, the remaining 131 we call 'Low' sources. In this paper, we check the association with dense gas and dust in 130 'Low' sources. We find a detection rate of ca. 85% in CS, demonstrating a tight association with dense molecular clumps. Among the sources detected in CS, ca. 76% have also been detected in C17O and ca. 93% in the 1.2 mm cont. Mm-cont. maps show the presence of clumps with diameters 0.2-2 pc and masses from a few Msun to 10^5 Msun; H2 volume densities lie between ca. 10^{4.5} and 10^{5.5} cm^{-3}. The L(bol) are 10^3-10^6 Lsun, consistent with embedded high-mass objects. Based on our results and those found in the literature for other samples, we conclude that our sources are massive objects probably in a stage prior to the formation of an HII region. We propose a scenario in which 'High' and 'Low' sources are both made of a massive clump hosting a high-mass protostellar candidate and a nearby stellar cluster. The difference might be due to the fact that the IRAS 12mu flux, the best discriminant between the two groups, is dominated by the emission from the cluster in 'Lows' and from the massive protostellar object in 'Highs'.Comment: Accepted for publication in Astron. & Astroph.; 34 pages (incl. 14 figures and 8 tables

On the chemical ladder of esters. Detection and formation of ethyl formate in the W51 e2 hot molecular core

The detection of organic molecules with increasing complexity and potential biological relevance is opening the possibility to understand the formation of the building blocks of life in the interstellar medium. One of the families of molecules with astrobiological interest are the esters, whose simplest member, methyl formate, is rather abundant in star-forming regions. The next step in the chemical complexity of esters is ethyl formate, C$_2$H$_5$OCHO. Only two detections of this species have been reported so far, which strongly limits our understanding of how complex molecules are formed in the interstellar medium. We have searched for ethyl formate towards the W51 e2 hot molecular core, one of the most chemically rich sources in the Galaxy and one of the most promising regions to study prebiotic chemistry, especially after the recent discovery of the P$-$O bond, key in the formation of DNA. We have analyzed a spectral line survey towards the W51 e2 hot molecular core, which covers 44 GHz in the 1, 2 and 3 mm bands, carried out with the IRAM 30m telescope. We report the detection of the trans and gauche conformers of ethyl formate. A Local Thermodynamic Equilibrium analysis indicates that the excitation temperature is 78$\pm$10 K and that the two conformers have similar source-averaged column densities of (2.0$\pm$0.3)$\times$10$^{16}$ cm$^{-2}$ and an abundance of $\sim$10$^{-8}$. We compare the observed molecular abundances of ethyl formate with different competing chemical models based on grain surface and gas-phase chemistry. We propose that grain-surface chemistry may have a dominant role in the formation of ethyl formate (and other complex organic molecules) in hot molecular cores, rather than reactions in the gas phase.Comment: Accepted in A&A; 11 pages, 6 figures, 7 Table

First ALMA maps of HCO, an important precursor of complex organic molecules, towards IRAS 16293-2422

The formyl radical HCO has been proposed as the basic precursor of many complex organic molecules such as methanol (CH$_3$OH) or glycolaldehyde (CH$_2$OHCHO). Using ALMA, we have mapped, for the first time at high angular resolution ($\sim$1$^{\prime\prime}$, $\sim$140 au), HCO towards the Solar-type protostellar binary IRAS 16293$-$2422, where numerous complex organic molecules have been previously detected. We also detected several lines of the chemically related species H$_2$CO, CH$_3$OH and CH$_2$OHCHO. The observations revealed compact HCO emission arising from the two protostars. The line profiles also show redshifted absorption produced by foreground material of the circumbinary envelope that is infalling towards the protostars. Additionally, IRAM 30m single-dish data revealed a more extended HCO component arising from the common circumbinary envelope. The comparison between the observed molecular abundances and our chemical model suggests that whereas the extended HCO from the envelope can be formed via gas-phase reactions during the cold collapse of the natal core, the HCO in the hot corinos surrounding the protostars is predominantly formed by the hydrogenation of CO on the surface of dust grains and subsequent thermal desorption during the protostellar phase. The derived abundance of HCO in the dust grains is high enough to produce efficiently more complex species such as H$_2$CO, CH$_3$OH, and CH$_2$OHCHO by surface chemistry. We found that the main formation route of CH$_2$OHCHO is the reaction between HCO and CH$_2$OH.Comment: Accepted in Monthly Notices of the Royal Astronomical Society; 19 pages, 12 figures, 7 table

The L1157-B1 astrochemical laboratory: testing the origin of DCN

L1157-B1 is the brightest shocked region of the large-scale molecular outflow, considered the prototype of chemically rich outflows, being the ideal laboratory to study how shocks affect the molecular gas. Several deuterated molecules have been previously detected with the IRAM 30m, most of them formed on grain mantles and then released into the gas phase due to the shock. We aim to observationally investigate the role of the different chemical processes at work that lead to formation the of DCN and test the predictions of the chemical models for its formation. We performed high-angular resolution observations with NOEMA of the DCN(2-1) and H13CN(2-1) lines to compute the deuterated fraction, Dfrac(HCN). We detected emission of DCN(2-1) and H13CN(2-1) arising from L1157-B1 shock. Dfrac(HCN) is ~4x10$^{-3}$ and given the uncertainties, we did not find significant variations across the bow-shock. Contrary to HDCO, whose emission delineates the region of impact between the jet and the ambient material, DCN is more widespread and not limited to the impact region. This is consistent with the idea that gas-phase chemistry is playing a major role in the deuteration of HCN in the head of the bow-shock, where HDCO is undetected as it is a product of grain-surface chemistry. The spectra of DCN and H13CN match the spectral signature of the outflow cavity walls, suggesting that their emission result from shocked gas. The analysis of the time dependent gas-grain chemical model UCL-CHEM coupled with a C-type shock model shows that the observed Dfrac(HCN) is reached during the post-shock phase, matching the dynamical timescale of the shock. Our results indicate that the presence of DCN in L1157-B1 is a combination of gas-phase chemistry that produces the widespread DCN emission, dominating in the head of the bow-shock, and sputtering from grain mantles toward the jet impact region.Comment: Accepted for publication in A&A. 7 pages, 5 Figures, 1 Tabl

A high resolution study of complex organic molecules in hot cores

We present the results of a line identification analysis using data from the IRAM Plateau de Bure Inferferometer, focusing on six massive star-forming hot cores: G31.41+0.31, G29.96-0.02, G19.61-0.23, G10.62-0.38, G24.78+0.08A1 and G24.78+0.08A2. We identify several transitions of vibrationally excited methyl formate (HCOOCH$_3$) for the first time in these objects as well as transitions of other complex molecules, including ethyl cyanide (C$_2$H$_5$CN), and isocyanic acid (HNCO). We also postulate a detection of one transition of glycolaldehyde (CH$_2$(OH)CHO) in two new hot cores. We find G29.96-0.02, G19.61-0.23, G24.78+0.08A1 and 24.78+0.08A2 to be chemically very similar. G31.41+0.31, however, is chemically different: it manifests a larger chemical inventory and has significantly larger column densities. We suggest that it may represent a different evolutionary stage to the other hot cores in the sample, or it may surround a star with a higher mass. We derive column densities for methyl formate in G31.41+0.31, using the rotation diagram method, of $\times$10$^{17}$ cm$^{-2}$ and a T$_{rot}$ of $\sim$170 K. For G29.96-0.02, G24.78+0.08A1 and G24.78+0.08A2, glycolaldehyde, methyl formate and methyl cyanide all seem to trace the same material and peak at roughly the same position towards the dust emission peak. For G31.41+0.31, however, glycolaldehyde shows a different distribution to methyl formate and methyl cyanide and seems to trace the densest, most compact inner part of hot cores.Comment: Accepted to MNRA

Mid-J CO Shock Tracing Observations of Infrared Dark Clouds I

Infrared dark clouds (IRDCs) are dense, molecular structures in the interstellar medium that can harbour sites of high-mass star formation. IRDCs contain supersonic turbulence, which is expected to generate shocks that locally heat pockets of gas within the clouds. We present observations of the CO J = 8-7, 9-8, and 10-9 transitions, taken with the Herschel Space Observatory, towards four dense, starless clumps within IRDCs (C1 in G028.37+00.07, F1 and F2 in G034.43+0007, and G2 in G034.77-0.55). We detect the CO J = 8-7 and 9-8 transitions towards three of the clumps (C1, F1, and F2) at intensity levels greater than expected from photodissociation region (PDR) models. The average ratio of the 8-7 to 9-8 lines is also found to be between 1.6 and 2.6 in the three clumps with detections, significantly smaller than expected from PDR models. These low line ratios and large line intensities strongly suggest that the C1, F1, and F2 clumps contain a hot gas component not accounted for by standard PDR models. Such a hot gas component could be generated by turbulence dissipating in low velocity shocks.Comment: 14 pages, 8 figures, 5 tables, accepted by A&A, minor updates to match the final published versio

Physical properties of high-mass clumps in different stages of evolution

(Abridged) Aims. To investigate the first stages of the process of high-mass star formation, we selected a sample of massive clumps previously observed with the SEST at 1.2 mm and with the ATNF ATCA at 1.3 cm. We want to characterize the physical conditions in such sources, and test whether their properties depend on the evolutionary stage of the clump. Methods. With ATCA we observed the selected sources in the NH3(1,1) and (2,2) transitions and in the 22 GHz H2O maser line. Ammonia lines are a good temperature probe that allow us to accurately determine the mass and the column-, volume-, and surface densities of the clumps. We also collected all data available to construct the spectral energy distribution of the individual clumps and to determine if star formation is already occurring, through observations of its most common signposts, thus putting constraints on the evolutionary stage of the source. We fitted the spectral energy distribution between 1.2 mm and 70 microns with a modified black body to derive the dust temperature and independently determine the mass. Results. The clumps are cold (T~10-30 K), massive (M~10^2-10^3 Mo), and dense (n(H2)>~10^5 cm^-3) and they have high column densities (N(H2)~10^23 cm^-2). All clumps appear to be potentially able to form high-mass stars. The most massive clumps appear to be gravitationally unstable, if the only sources of support against collapse are turbulence and thermal pressure, which possibly indicates that the magnetic field is important in stabilizing them. Conclusions. After investigating how the average properties depend on the evolutionary phase of the source, we find that the temperature and central density progressively increase with time. Sources likely hosting a ZAMS star show a steeper radial dependence of the volume density and tend to be more compact than starless clumps.Comment: Published in A&A, Vol. 556, A1