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

First interferometric study of enhanced N-fractionation in N2_{2}H+^{+}: the high-mass star-forming region IRAS 05358+3543

Nitrogen (N) fractionation is used as a tool to search for a link between the chemical history of the Solar System and star-forming regions. A large variation of $^{14}$N/$^{15}$N is observed towards different astrophysical sources, and current chemical models cannot reproduce it. With the advent of high angular resolution radiotelescopes it is now possible to search for N-fractionation at core scales. We present IRAM NOEMA observations of the J=1-0 transition of N$_{2}$H$^{+}$, $^{15}$NNH$^{+}$ and N$^{15}$NNH$^{+}$ towards the high-mass protocluster IRAS 05358+3543. We find $^{14}$N/$^{15}$N ratios that span from $\sim$100 up to $\sim$220 and these values are lower or equal than those observed with single-dish observations towards the same source. Since N-fractionation changes across the studied region, this means that it is regulated by local environmental effects. We find also the possibility, for one of the four cores defined in the protocluster, to have a more abundant $^{15}$NNH$^{+}$ with respect to N$^{15}$NNH$^{+}$. This is another indication that current chemical models may be missing chemical reactions or may not take into account other mechanisms, like photodissociation or grain surface chemistry, that could be important.Comment: 19 pages, 8 figures, 6 tables, 3 appendices Accepted in Monthly Notices of the Royal Astronomical Society Letter

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

DC3_3N observations towards high-mass star-forming regions

We present the study of deuteration of cyanoacetylene (HC$_3$N) towards a sample of 28 high-mass star-forming cores divided into different evolutionary stages, from starless to evolved protostellar cores. We report for the first time the detection of DC$_3$N towards 15 high-mass cores. The abundance ratios of DC$_3$N with respect HC$_3$N range in the interval 0.003$-$0.022, lower than those found in low-mas protostars and dark clouds. No significant trend with the evolutionary stage, or with the kinetic temperature of the region, has been found. We compare the level of deuteration of HC$_3$N with those of other molecules towards the same sample, finding weak correlation with species formed only or predominantly in gas phase (N$_2$H$^+$ and HNC, respectively), and no correlation with species formed only or predominantly on dust grains (CH$_3$OH and NH$_3$, respectively). We also present a single-dish map of DC$_3$N towards the protocluster IRAS 05358+3543, which shows that DC$_3$N traces an extended envelope ($\sim$0.37 pc) and peaks towards two cold condensations separated from the positions of the protostars and the dust continuum. The observations presented in this work suggest that deuteration of HC$_3$N is produced in the gas of the cold outer parts of massive star-forming clumps, giving us an estimate of the deuteration factor prior to the formation of denser gas.Comment: Accepted in Monthly Notices of the Royal Astronomical Society -- 11 pages, 7 Figures, 2 Tables. Version with some typos correcte

CHEMOUT: CHEMical complexity in star-forming regions of the OUTer Galaxy III. Nitrogen isotopic ratios in the outer Galaxy

Nitrogen isotopic ratios are a key tool for tracing Galactic stellar nucleosynthesis. We present the first study of the $^{14}$N/$^{15}$N abundance ratio in the outer regions of the Milky Way (namely, for galactocentric distances, $R_{\rm GC}$, from 12 kpc up to 19 kpc), with the aim to study the stellar nucleosynthesis effects in the global Galactic trend. We analysed IRAM 30m observations towards a sample of 35 sources in the context of the CHEMical complexity in star-forming regions of the OUTer Galaxy (CHEMOUT) project. We derived the $^{14}$N/$^{15}$N ratios from HCN and HNC for 14 and 3 sources, respectively, using the $J$ = 1-0 rotational transition of HN$^{13}$C, H$^{15}$NC, H$^{13}$CN, and HC$^{15}$N. The results found in the outer Galaxy have been combined with previous measurements obtained in the inner Galaxy. We find an overall linear decreasing H$^{13}$CN/HC$^{15}$N ratio with increasing $R_{\rm GC}$. This translates to a parabolic $^{14}$N/$^{15}$N ratio with a peak at 11 kpc. Updated Galactic chemical evolution models have been taken into account and compared with the observations. The parabolic trend of the $^{14}$N/$^{15}$N ratio with $R_{\rm GC}$ can be naturally explained (i) by a model that assumes novae as the main $^{15}$N producers on long timescales ($\ge$1 Gyr) and (ii) by updated stellar yields for low- and intermediate-mass stars.Comment: 19 pages, 8 figures, 6 tables, 4 appendix - Accepted for publication in A&

Identification of Histopathological Criteria for the Diagnosis of Canine Cutaneous Progressive Angiomatosis

The term angiomatosis is used to denote a group of well-known to poorly characterized proliferative vascular entities. In animals, cutaneous progressive angiomatosis (CPA) is a disorder with variable prognosis related to the extension and depth of infiltration of the surrounding tissues by vessels. CPA may share some microscopical features with other vascular proliferations such as low-grade well-differentiated capillaritic hemangiosarcoma (HS), making the diagnosis not always straightforward, especially in small biopsies. The aim of this study is to retrospectively assess the most common diagnostic microscopical features of CPA in dogs. In this work, 11 histopathological criteria were analyzed on 31 CPA and 11 primary cutaneous HS in dogs. Features significantly associated with CPA included: lobular growth, interposition of connective tissue and adnexa between the vascular proliferation, presence of nerve fibers, and a mixed vascular proliferative component. Absence of plump/prominent endothelial cells, lack of atypia, and lack of mitoses were also significant factors differentiating CPA from HS. Additional distinctive findings in CPA, although with no statistical association to CPA diagnosis, were vascular shunting, absence of necrosis, and endothelial cell piling up. In conclusion, the combined use of different microscopical clues allowed for the distinction of CPA from HS and was considered useful for the diagnosis of CPA

Effects of Wood Distillate (Pyroligneous Acid) on the Yield Parameters and Mineral Composition of Three Leguminous Crops

The excessive use of chemical fertilizers and pesticides in agriculture is increasing the demand for novel products to improve the quality of crops in a more sustainable way. Wood distillate (WD, pyroligneous acid) is a by-product obtained during the pyrolysis of plant biomass that can be successfully applied in agriculture due to its ability to enhance the growth, size, and weight of edible plant parts. However, there is little information concerning its plant yield-promoting effects on leguminous crops. The present work investigated the effects of WD on the yield, protein content and mineral composition of chickpea (Cicer arietinum L.), lentil (Lens culinaris L.) and bean (Phaseolus vulgaris L.) plants grown in field conditions. The application of WD showed remarkable yield-promoting effects mostly in lentil plants, which significantly increased plant and shoot biomass, the number and weight of both pods and seeds, as well as the total seed protein content. Furthermore, seeds from WD-treated plants differentially increased the concentration of elements with high nutritional value for human health, including Fe, Ca, Mg and K. These results suggest that the effects of WD among the legumes tested are species-specific and that WD could be an optimal candidate to grow high-yielding legumes with improved seed nutritional quality