The reservoir of sulphur accounting for sulphur depletion in the gas of dense clouds and circumstellar regions is still unclear. One possibility is the formation of sulphur chains, which would be difficult to detect by spectroscopic techniques. This work explores the formation of sulphur chains experimentally, both in pure HS ice samples and in HO:HS ice mixtures. An ultrahigh vacuum chamber, ISAC, eqquipped with FTIR and QMS, was used for the experiments. Our results show that the formation of HS species is efficient, not only in pure HS ice samples, but also in water-rich ice samples. Large sulphur chains are formed more efficiently at low temperatures (10 K), while high temperatures (50 K) favour the formation of short sulphur chains. Mass spectra of HS, x = 2-6, species are presented for the first time. Their analysis suggests that HS species are favoured in comparison with S chains. Nevertheless, the detection of several S fragments at high temperatures in HS:HO ice mixtures suggests the presence of S in the irradiated ice samples, which could sublimate from 260 K. ROSINA instrument data from the cometary Rosetta mission detected mass-to-charge ratios 96 and 128. Comparing these detections with our experiments, we propose two alternatives: (1) HS and HS to be responsible of those S and S cations, respectively, or (2) S species, sublimating and being fragmented in the mass spectrometer. If S is the parent molecule, then S and S cations could be also detected in future missions by broadening the mass spectrometer range.

Context. Gas phase Elemental abundances in molecular CloudS (GEMS) is an IRAM 30-m 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. Aims. This paper aims to constrain the sulfur elemental abundance in Taurus, Perseus, and Orion A based on the GEMS molecular database. The selected regions are prototypes of low-mass, intermediate-mass, and high-mass star-forming regions, respectively, providing useful templates for the study of interstellar chemistry. Methods. We have carried out an extensive chemical modeling of the fractional abundances of CO, HCO+, HCN, HNC, CS, SO, H2S, OCS, and HCS+ to determine the sulfur depletion toward the 244 positions in the GEMS database. These positions sample visual extinctions from AV ∼ 3 mag to >50 mag, molecular hydrogen densities ranging from a few × 103 cm3 to 3 × 106 cm3, and Tk ∼ 10-35 K. We investigate the possible relationship between sulfur depletion and the grain charge distribution in different environments. Results. Most of the positions in Taurus and Perseus are best fitted assuming early-time chemistry, t = 0.1 Myr, ζH2 ∼ (0.51) × 1016 s1, and [S/H] ∼ 1.5 × 106. On the contrary, most of the positions in Orion are fitted with t = 1 Myr and ζH2 ∼ 1017 s1. Moreover, ∼40% of the positions in Orion are best fitted assuming the undepleted sulfur abundance, [S/H] ∼ 1.5 × 105. We find a tentative trend of sulfur depletion increasing with density. Conclusions. 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 ∼20 is required to explain those observed in Taurus and Perseus. We propose that differences in the grain charge distribution might explain these variations. Grains become negatively charged at a visual extinction of AV ∼ 3.5 mag in Taurus and Perseus. At this low visual extinction, the S+ abundance is high, X(S+) > 106, and the electrostatic attraction between S+ and negatively charged grains could contribute to enhance sulfur depletion. In Orion, the net charge of grains remains approximately zero until higher visual extinctions (AV ∼ 5.5 mag), where the abundance of S+ is already low because of the higher densities, thus reducing sulfur accretion. The shocks associated with past and ongoing star formation could also contribute to enhance [S/H].

Context. Sulfur is a biogenic element used as a tracer of the evolution of interstellar clouds to stellar systems. However, most of the expected sulfur in molecular clouds remains undetected. Sulfur disappears from the gas phase in two steps. The first depletion occurs during the translucent phase, reducing the gas-phase sulfur by 7-40 times, while the following freeze-out step occurs in molecular clouds, reducing it by another order of magnitude. This long-standing question awaits an explanation. Aims. The aim of this study is to understand under what form the missing sulfur is hiding in molecular clouds. The possibility that sulfur is depleted onto dust grains is considered. Methods. Experimental simulations mimicking HS ice UV photoprocessing in molecular clouds were conducted at 8 K under ultra-high vacuum. The ice was subsequently warmed up to room temperature. The ice was monitored using infrared spectroscopy, and the desorbing molecules were measured by quadrupole mass spectrometry in the gas phase. Theoretical Monte Carlo simulations were performed for interpretation of the experimental results and extrapolation to the astrophysical and planetary conditions. Results. HS formation was observed during irradiation at 8 K. Molecules HS x with x > 2 were also identified and found to desorb during warm-up, along with S to S 4 species. Larger S x molecules up to S 8 are refractory at room temperature and remained on the substrate forming a residue. Monte Carlo simulations were able to reproduce the molecules desorbing during warming up, and found that residues are chains of sulfur consisting of 6-7 atoms. Conclusions. Based on the interpretation of the experimental results using our theoretical model, it is proposed that S + in translucent clouds contributes notoriously to S depletion in denser regions by forming long S chains on dust grains in a few times 10 4 yr. We suggest that the S to S 4 molecules observed in comets are not produced by fragmentation of these large chains. Instead, they probably come either from UV photoprocessing of HS-bearing ice produced in molecular clouds or from short S chains formed during the translucent cloud phase.

Context. Studying gas chemistry in protoplanetary disks is key to understanding the process of planet formation. Sulfur chemistry in particular is poorly understood in interstellar environments, and the location of the main reservoirs remains unknown. Protoplanetary disks in Taurus are ideal targets for studying the evolution of the composition of planet forming systems. Aims. We aim to elucidate the chemical origin of sulfur-bearing molecular emission in protoplanetary disks, with a special focus on H2S emission, and to identify candidate species that could become the main molecular sulfur reservoirs in protoplanetary systems. Methods. We used IRAM 30 m observations of nine gas-rich young stellar objects (YSOs) in Taurus to perform a survey of sulfur-bearing and oxygen-bearing molecular species. In this paper we present our results for the CS 3-2 (ν0 = 146.969 GHz), H2CO 21,1-11,0 (ν0 = 150.498 GHz), and H2S 11,0-10,1 (ν0 = 168.763 GHz) emission lines. Results. We detected H2S emission in four sources out of the nine observed, significantly increasing the number of detections toward YSOs. We also detected H2CO and CS in six out of the nine. We identify a tentative correlation between H2S 11,0-10,1 and H2CO 21,1-11,0 as well as a tentative correlation between H2S 11,0-10,1 and H2O 818-707. By assuming local thermodynamical equilibrium, we computed column densities for the sources in the sample, with N(o-H2S) values ranging between 2.6 × 1012 cm-2 and 1.5 × 1013 cm-2.

Context. The chemical and physical evolution of starless and pre-stellar cores are of paramount importance to understanding the process of star formation. The Taurus Molecular Cloud cores TMC 1-C and TMC 1-CP share similar initial conditions and provide an excellent opportunity to understand the evolution of the pre-stellar core phase. Aims. We investigated the evolutionary stage of starless cores based on observations towards the prototypical dark cores TMC 1-C and TMC 1-CP. Methods. We mapped the prototypical dark cores TMC 1-C and TMC 1-CP in the CS 3 → 2, C34S 3 → 2, 13CS 2 → 1, DCN 1 → 0, DCN 2 → 1, DNC 1 → 0, DNC 2 → 1, DN13C 1 → 0, DN13C 2 → 1, N2H+ 1 → 0, and N2D+ 1 → 0 transitions. We performed a multi-transitional study of CS and its isotopologs, DCN, and DNC lines to characterize the physical and chemical properties of these cores. We studied their chemistry using the state-of-the-art gas-grain chemical code NAUTILUS and pseudo time-dependent models to determine their evolutionary stage. Results. The central nH volume density, the N2H+ column density, and the abundances of deuterated species are higher in TMC 1-C than in TMC 1-CP, yielding a higher N2H+ deuterium fraction in TMC 1-C, thus indicating a later evolutionary stage for TMC 1-C. The chemical modeling with pseudo time-dependent models and their radiative transfer are in agreement with this statement, allowing us to estimate a collapse timescale of ~1 Myr for TMC 1-C. Models with a younger collapse scenario or a collapse slowed down by a magnetic support are found to more closely reproduce the observations towards TMC 1-CP. Conclusions. Observational diagnostics seem to indicate that TMC 1-C is in a later evolutionary stage than TMC 1-CP, with a chemical age ~1 Myr. TMC 1-C shows signs of being an evolved core at the onset of star formation, while TMC 1-CP appears to be in an earlier evolutionary stage due to a more recent formation or, alternatively, a collapse slowed down by a magnetic support.

Gas phase Elemental abundances in Molecular CloudS (GEMS) is an IRAM 30 m Large Program designed to provide estimates of the S, C, N, and O depletions and gas ionization degree, X(e-), in a selected set of star-forming filaments of Taurus, Perseus, and Orion. Our immediate goal is to build up a complete and large database of molecular abundances that can serve as an observational basis for estimating X(e-) and the C, O, N, and S depletions through chemical modeling. We observed and derived the abundances of 14 species (13CO, C18O, HCO+, H13CO+, HC18O+, HCN, H13CN, HNC, HCS+, CS, SO, 34SO, H2S, and OCS) in 244 positions, covering the AV ~3 to ~100 mag, n(H2) ~ a few 103 to 106 cm-3, and Tk ~10 to ~30 K ranges in these clouds, and avoiding protostars, HII regions, and bipolar outflows. A statistical analysis is carried out in order to identify general trends between different species and with physical parameters. Relations between molecules reveal strong linear correlations which define three different families of species: (1) 13CO and C18O isotopologs; (2) H13CO+, HC18O+, H13 CN, and HNC; and (3) the S-bearing molecules. The abundances of the CO isotopologs increase with the gas kinetic temperature until TK ~ 15 K. For higher temperatures, the abundance remains constant with a scatter of a factor of ~3. The abundances of H13 CO+, HC18 O+, H13 CN, and HNC are well correlated with each other, and all of them decrease with molecular hydrogen density, following the law ∝ n(H2)-0.8  ±  0.2. The abundances of S-bearing species also decrease with molecular hydrogen density at a rate of (S-bearing/H)gas ∝ n(H2)-0.6  ±  0.1. The abundances of molecules belonging to groups 2 and 3 do not present any clear trend with gas temperature. At scales of molecular clouds, the C18O abundance is the quantity that better correlates with the cloud mass. We discuss the utility of the 13CO/C18O, HCO+/H13CO+, and H13 CO+/H13CN abundance ratios as chemical diagnostics of star formation in external galaxies.

Context. Sulphur is one of the most abundant elements in the Universe. Surprisingly, sulphuretted molecules are not as abundant as expected in the interstellar medium and the identity of the main sulphur reservoir is still an open question. Aims. Our goal is to investigate the H2S chemistry in dark clouds, as this stable molecule is a potential sulphur reservoir. Methods. Using millimeter observations of CS, SO, H2S, and their isotopologues, we determine the physical conditions and H2S abundances along the cores TMC 1-C, TMC 1-CP, and Barnard 1b. The gas-grain model NAUTILUS is used to model the sulphur chemistry and explore the impact of photo-desorption and chemical desorption on the H2S abundance. Results. Our modeling shows that chemical desorption is the main source of gas-phase H2S in dark cores. The measured H2S abundance can only be fitted if we assume that the chemical desorption rate decreases by more than a factor of 10 when nH > 2 × 104. This change in the desorption rate is consistent with the formation of thick H2O and CO ice mantles on grain surfaces. The observed SO and H2S abundances are in good agreement with our predictions adopting an undepleted value of the sulphur abundance. However, the CS abundance is overestimated by a factor of 5-10. Along the three cores, atomic S is predicted to be the main sulphur reservoir. Conclusions. The gaseous H2S abundance is well reproduced, assuming undepleted sulphur abundance and chemical desorption as the main source of H2S. The behavior of the observed H2S abundance suggests a changing desorption efficiency, which would probe the snowline in these cold cores. Our model, however, highly overestimates the observed gas-phase CS abundance. Given the uncertainty in the sulphur chemistry, we can only conclude that our data are consistent with a cosmic elemental S abundance with an uncertainty of a factor of 10.

GEMS is an IRAM 30 m Large Program whose aim is determining the elemental depletions and the ionization fraction in a set of prototypical star-forming regions. This paper presents the first results from the prototypical dark cloud Taurus molecular cloud (TMC) 1. Extensive millimeter observations have been carried out with the IRAM 30 m telescope (3 and 2 mm) and the 40 m Yebes telescope (1.3 cm and 7 mm) to determine the fractional abundances of CO, HCO ⁺ , HCN, CS, SO, HCS ⁺ , and N ₂ H ⁺ in three cuts which intersect the dense filament at the well-known positions TMC 1-CP, TMC 1-NH3, and TMC 1-C, covering a visual extinction range from A _V ~ 3 to ~20 mag. Two phases with differentiated chemistry can be distinguished: (i) the translucent envelope with molecular hydrogen densities of 1-5 × 10 ³ cm ^-3 ; and (ii) the dense phase, located at A _V > 10 mag, with molecular hydrogen densities >10 ⁴ cm ^-3 . Observations and modeling show that the gas phase abundances of C and O progressively decrease along the C ⁺ /C/CO transition zone (A _V ~ 3 mag) where C/H ~ 8 × 10 ^-5 and C/O ~ 0.8-1, until the beginning of the dense phase at A _V ~ 10 mag. This is consistent with the grain temperatures being below the CO evaporation temperature in this region. In the case of sulfur, a strong depletion should occur before the translucent phase where we estimate an S/ H ~ (0.4-2.2) × 10 ^-6 , an abundance ~7-40 times lower than the solar value. A second strong depletion must be present during the formation of the thick icy mantles to achieve the values of S/H measured in the dense cold cores (S H ~ 8 × 10 ^-8 ). Based on our chemical modeling, we constrain the value of ζ _{H 2} to ~(0.5-1.8) × 10 ^-16 s ^-1 in the translucent cloud.