Modelling the sulphur chemistry evolution in Orion KL

We study the sulphur chemistry evolution in the Orion KL along the gas and grain phases of the cloud. We investigate the processes that dominate the sulphur chemistry and to determine how physical and chemical parameters, such as the final star mass and the initial elemental abundances, influence the evolution of the hot core and of the surrounding outflows and shocked gas (the plateau). We independently modelled the chemistry evolution of both components using the time-dependent gas-grain model UCL_CHEM and considering two different phase calculations. Phase I starts with the collapsing cloud and the depletion of atoms and molecules onto grain surfaces. Phase II starts when a central protostar is formed and the evaporation from grains takes place. We show how the gas density, the gas depletion efficiency, the initial sulphur abundance, the shocked gas temperature and the different chemical paths on the grains leading to different reservoirs of sulphur on the mantles affect sulphur-bearing molecules at different evolutionary stages. We also compare the predicted column densities with those inferred from observations of the species SO, SO2, CS, OCS, H2S and H2CS. The models that reproduce the observations of the largest number of sulphur-bearing species are those with an initial sulphur abundance of 0.1 times the sulphur solar abundance and a density of at least n_H=5x10^6 cm^-3 in the shocked gas region. We conclude that most of the sulphur atoms were ionised during Phase I, consistent with an inhomogeneous and clumpy region where the UV interstellar radiation penetrates leading to sulphur ionisation. We also conclude that the main sulphur reservoir on the ice mantles was H2S. In addition, we deduce that a chemical transition currently takes place in the shocked gas, where SO and SO2 gas-phase formation reactions change from being dominated by O2 to being dominated by OH.Comment: 14 pages, 28 figures, 6 table

A line confusion-limited millimeter survey of Orion KL. III. Sulfur oxide species

We present a study of the sulfur-bearing species detected in a line confusion-limited survey towards Orion KL performed with the IRAM 30m telescope in the range 80-281 GHz. The study is part of an analysis of the line survey divided into families of molecules. Our aim is to derive accurate physical conditions and molecular abundances in the different components of Orion KL from observed SO and SO2 lines. First we assumed LTE conditions obtain rotational temperatures. We then used a radiative transfer model, assuming either LVG or LTE excitation to derive column densities of these molecules in the different components of Orion KL. We have detected 68 lines of SO, 34SO, 33SO, and S18O and 653 lines of SO2, 34SO2, 33SO2, SO18O and SO2 v2=1. We provide column densities for all of them and also upper limits for the column densities of S17O, 36SO, 34S18O, SO17O and 34SO2 v2=1 and for several undetected sulfur-bearing species. In addition, we present 2'x2' maps around Orion IRc2 of SO2 transitions with energies from 19 to 131 K and also maps with four transitions of SO, 34SO and 34SO2. We observe an elongation of the gas along the NE-SW direction. An unexpected emission peak appears at 20.5 km/s in most lines of SO and SO2. A study of the spatial distribution of this emission feature shows that it is a new component ~5" in diameter, which lies ~4" west of IRc2. We suggest the emission from this feature is related to shocks associated to the BN object. The highest column densities for SO and SO2 are found in the high-velocity plateau (a region dominated by shocks) and in the hot core. These values are up to three orders of magnitude higher than the results for the ridge components. We also find high column densities for their isotopologues in both components. Therefore, we conclude that SO and SO2 are good tracers, not only of regions affected by shocks, but also of regions with warm dense gas.Comment: Paper (ref AA/2013/21285) accepted for publication by A&A. 52 Pages, 26 figures, 13 table

The first frost in the Pipe Nebula

Spectroscopic studies of ices in nearby star-forming regions indicate that ice mantles form on dust grains in two distinct steps, starting with polar ice formation (H2O rich) and switching to apolar ice (CO rich). We test how well the picture applies to more diffuse and quiescent clouds where the formation of the first layers of ice mantles can be witnessed. Medium-resolution near-infrared spectra are obtained toward background field stars behind the Pipe Nebula. The water ice absorption is positively detected at 3.0 micron in seven lines of sight out of 21 sources for which observed spectra are successfully reduced. The peak optical depth of the water ice is significantly lower than those in Taurus with the same visual extinction. The source with the highest water-ice optical depth shows CO ice absorption at 4.7 micron as well. The fractional abundance of CO ice with respect to water ice is 16+7-6 %, and about half as much as the values typically seen in low-mass star-forming regions. A small fractional abundance of CO ice is consistent with some of the existing simulations. Observations of CO2 ice in the early diffuse phase of a cloud play a decisive role in understanding the switching mechanism between polar and apolar ice formation.Comment: 17 pages, 8 figures, accepted by A&

Extended warm gas in Orion KL as probed by methyl cyanide

In order to study the temperature distribution of the extended gas within the Orion Kleinmann-Low nebula, we have mapped the emission by methyl cyanide (CH3CN) in its J=6_K-5_K, J=12_K-11_K, J=13_K-12_K, and J=14_K-13_K transitions at an average angular resolution of ~10 arcsec (22 arcsec for the 6_K-5_K lines), as part of a new 2D line survey of this region using the IRAM 30m telescope. These fully sampled maps show extended emission from warm gas to the northeast of IRc2 and the distinct kinematic signatures of the hot core and compact ridge source components. We have constructed population diagrams for the four sets of K-ladder emission lines at each position in the maps and have derived rotational excitation temperatures and total beam-averaged column densities from the fitted slopes. In addition, we have fitted LVG model spectra to the observations to determine best-fit physical parameters at each map position, yielding the distribution of kinetic temperatures across the region. The resulting temperature maps reveal a region of hot (T > 350 K) material surrounding the northeastern edge of the hot core, whereas the column density distribution is more uniform and peaks near the position of IRc2. We attribute this region of hot gas to shock heating caused by the impact of outflowing material from active star formation in the region, as indicated by the presence of broad CH3CN lines. This scenario is consistent with predictions from C-shock chemical models that suggest that gas-phase methyl cyanide survives in the post-shock gas and can be somewhat enhanced due to sputtering of grain mantles in the passing shock front.Comment: 24 pages, 20 figures, accepted for publication in A&

A combined IRAM and Herschel/HIFI study of cyano(di)acetylene in Orion KL: tentative detection of DC3N

We present a study of cyanoacetylene (HC3N) and cyanodiacetylene (HC5N) in Orion KL, through observations from two line surveys performed with the IRAM 30m telescope and the HIFI instrument on board the Herschel telescope. The frequency ranges covered are 80-280 GHz and 480-1906 GHz. We model the observed lines of HC3N, HC5N, their isotopologues (including DC3N), and vibrational modes, using a non-LTE radiative transfer code. To investigate the chemical origin of HC3N and DC3N in Orion KL, we use a time-dependent chemical model. We detect 40 lines of the ground state of HC3N and 68 lines of its 13C isotopologues. We also detect 297 lines of six vibrational modes of this molecule (nu_7, 2nu_7, 3nu_7, nu_6, nu_5, and nu_6+nu_7) and 35 rotational lines of the ground state of HC5N. We report the first tentative detection of DC3N in a giant molecular cloud with a DC3N/HC3N abundance ratio of 0.015. We provide column densities and isotopic and molecular abundances. We also perform a 2x2" map around Orion IRc2 and we present maps of HC3N lines and maps of lines of the HC3N vibrational modes nu_6 and nu_7. In addition, a comparison of our results for HC3N with those in other clouds allows us to derive correlations between the column density, the FWHM, the mass, and the luminosity of the clouds. The high column densities of HC3N obtained in the hot core, make this molecule an excellent tracer of hot and dense gas. In addition, the large frequency range covered reveals the need to consider a temperature and density gradient in the hot core in order to obtain better line fits. The high D/H ratio (comparable to that obtained in cold clouds) that we derive suggests a deuterium enrichment. Our chemical models indicate that the possible deuterated HC3N present in Orion KL is formed during the gas-phase. This fact provides new hints concerning the processes leading to deuteration.Comment: 50 pages, 33 figures, 13 tables. Accepted for publication in A&

Prenatal exposure to NO2 and ultrasound measures of fetal growth in the Spanish INMA cohort

__Background:__ Air pollution exposure during pregnancy has been associated with impaired fetal growth. However, few studies have measured fetal biometry longitudinally, remaining unclear as to whether there are windows of special vulnerability. __Objective:__ The aim was to investigate the impact of nitrogen dioxide (NO2) exposure on fetal and neonatal biometry in the Spanish INMA study. Methods: Biparietal diameter (BPD), femur length (FL), abdominal circumference (AC), and estimated fetal weight (EFW) were evaluated for up to 2,478 fetuses in each trimester of pregnancy. Size at 12, 20, and 34 weeks of gestation and growth between these points, as well as anthropometry at birth, were assessed by SD scores derived using cohort-specific growth curves. Temporally adjusted land-use regression was used to estimate exposure to NO2 at home addresses for up to 2,415 fetuses. Associations were investigated by linear regression in each cohort and subsequent meta-analysis. __Results:__ A 10-μg/m3 increase in average exposure to NO2 during weeks 0-12 was associated with reduced growth at weeks 0-12 in AC (-2.1%; 95% CI: -3.7, -0.6) and EFW (-1.6%; 95% CI: -3.0, -0.3). The same exposure was inversely associated with reduced growth at weeks 20-34 in BPD (-2.6%; 95% CI: -3.9, -1.2), AC (-1.8%; 95% CI: -3.3, -0.2), and EFW (-2.1%; 95% CI: -3.7, -0.2). A less consistent pattern of association was observed for FL. The negative association of this exposure with BPD and EFW was significantly stronger in smoking versus nonsmoking mothers. __Conclusi

Gas phase Elemental abundances in Molecular cloudS (GEMS) VII. Sulfur elemental abundance

Gas phase Elemental abundances in molecular CloudS (GEMS) is an IRAM 30m large program aimed at determining the elemental abundances of carbon (C), oxygen (O), nitrogen (N), and sulfur (S) in a selected set of prototypical star-forming filaments. In particular, the elemental abundance of S remains uncertain by several orders of magnitude and its determination is one of the most challenging goals of this program. We have carried out an extensive chemical modeling of the fractional abundances of CO, HCO$^+$, HCN, HNC, CS, SO, H$_2$S, OCS, and HCS$^+$ to determine the sulfur depletion toward the 244 positions in the GEMS database. These positions sample visual extinctions from A$_V$ $\sim$ 3 mag to $>$50 mag, molecular hydrogen densities ranging from a few 10$^3$~cm$^{-3}$ to 3$\times$10$^6$~cm$^{-3}$, and T$_k$ $\sim$ 10$-$35 K. Most of the positions in Taurus and Perseus are best fitted assuming early-time chemistry, t=0.1 Myr, $\zeta_{H_2}$$\sim$ (0.5$-$1)$\times$10$^{-16}$ s$^{-1}$, and [S/H]$\sim$1.5$\times$10$^{-6}$. On the contrary, most of the positions in Orion are fitted with t=1~Myr and $\zeta_{H_2}$$\sim$ 10$^{-17}$ s$^{-1}$. Moreover, $\sim$40% of the positions in Orion are best fitted assuming the undepleted sulfur abundance, [S/H]$\sim$1.5$\times$10$^{-5}$. Our results suggest that sulfur depletion depends on the environment. While the abundances of sulfur-bearing species are consistent with undepleted sulfur in Orion, a depletion factor of $\sim$20 is required to explain those observed in Taurus and Perseus. We propose that differences in the grain charge distribution in the envelopes of the studied clouds might explain these variations. The shocks associated with past and ongoing star formation could also contribute to enhance [S/H] in Orion.Comment: 22 pages, 15 figures, Astronomy and Astrophysics, in pres

Linking the dust and chemical evolution: Taurus and Perseus -- New collisional rates for HCN, HNC, and their C, N, and H isotopologues

HCN, HNC, and their isotopologues are ubiquitous molecules that can serve as chemical thermometers and evolutionary tracers to characterize star-forming regions. Despite their importance in carrying information that is vital to studies of the chemistry and evolution of star-forming regions, the collision rates of some of these molecules have not been available for rigorous studies in the past. We perform an up-to-date gas and dust chemical characterization of two different star-forming regions, TMC 1-C and NGC 1333-C7, using new collisional rates of HCN, HNC, and their isotopologues. We investigated the possible effects of the environment and stellar feedback in their chemistry and their evolution. With millimeter observations, we derived their column densities, the C and N isotopic fractions, the isomeric ratios, and the deuterium fractionation. The continuum data at 3 mm and 850 $\mu$m allowed us to compute the emissivity spectral index and look for grain growth as an evolutionary tracer. The H$^{13}$CN/HN$^{13}$C ratio is anticorrelated with the deuterium fraction of HCN, thus it can readily serve as a proxy for the temperature. The spectral index $(\beta\sim 1.34-2.09)$ shows a tentative anticorrelation with the H$^{13}$CN/HN$^{13}$C ratio, suggesting grain growth in the evolved, hotter, and less deuterated sources. Unlike TMC 1-C, the south-to-north gradient in dust temperature and spectral index observed in NGC 1333-C7 suggests feedback from the main NGC 1333 cloud. With this up-to-date characterization of two star-forming regions, we found that the chemistry and the physical properties are tightly related. The dust temperature, deuterium fraction, and the spectral index are complementary evolutionary tracers. The large-scale environmental factors may dominate the chemistry and evolution in clustered star-forming regions.Comment: 25 pages, 20 figure

Bench-to-bedside review : targeting antioxidants to mitochondria in sepsis

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Gas phase Elemental abundances in Molecular cloudS (GEMS) : III. Unlocking the CS chemistry: the CS plus O reaction

Context. Carbon monosulphide (CS) is among the most abundant gas-phase S-bearing molecules in cold dark molecular clouds. It is easily observable with several transitions in the millimeter wavelength range, and has been widely used as a tracer of the gas density in the interstellar medium in our Galaxy and external galaxies. However, chemical models fail to account for the observed CS abundances when assuming the cosmic value for the elemental abundance of sulfur. Aims. The CS+O -> CO + S reaction has been proposed as a relevant CS destruction mechanism at low temperatures, and could explain the discrepancy between models and observations. Its reaction rate has been experimentally measured at temperatures of 150-400 K, but the extrapolation to lower temperatures is doubtful. Our goal is to calculate the CS+O reaction rate at temperatures Methods. We performed ab initio calculations to obtain the three lowest potential energy surfaces (PES) of the CS+O system. These PESs are used to study the reaction dynamics, using several methods (classical, quantum, and semiclassical) to eventually calculate the CS + O thermal reaction rates. In order to check the accuracy of our calculations, we compare the results of our theoretical calculations for T similar to 150-400 K with those obtained in the laboratory. Results. Our detailed theoretical study on the CS+O reaction, which is in agreement with the experimental data obtained at 150-400 K, demonstrates the reliability of our approach. After a careful analysis at lower temperatures, we find that the rate constant at 10 K is negligible, below 10(-15) cm(3) s(-1), which is consistent with the extrapolation of experimental data using the Arrhenius expression. Conclusions. We use the updated chemical network to model the sulfur chemistry in Taurus Molecular Cloud 1 (TMC 1) based on molecular abundances determined from Gas phase Elemental abundances in Molecular CloudS (GEMS) project observations. In our model, we take into account the expected decrease of the cosmic ray ionization rate, zeta(H2), along the cloud. The abundance of CS is still overestimated when assuming the cosmic value for the sulfur abundance.Peer reviewe