Title: SO2 and OCS toward high-mass protostars: A comparative study between ice and gas

Summary:

We investigate the chemical history of interstellar OCS and SO2 by deriving a statistically-significant sample of gas-phase column densities towards massive protostars and comparing to observations of gas and ices towards other sources spanning from dark clouds to comets.

We analyze a subset of 26 line-rich massive protostars observed by ALMA as part of the ALMAGAL survey. Column densities are derived for OCS and

SO2 from their rare isotopologues O13CS and 34SO2 towards the compact gas around the hot core. We find that gas-phase column density ratios of OCS and SO2 with respect to methanol remain fairly constant as a function of luminosity between low- and high-mass sources, despite their very different physical conditions. The derived gaseous OCS and SO2 abundances relative to CH3OH are overall similar to protostellar ice values, with a significantly larger scatter for SO2 than for OCS.

Cometary and dark-cloud ice values agree well with protostellar gas-phase ratios for OCS, whereas higher abundances of SO2 are generally seen in comets compared to the other sources. Gaseous SO2/OCS ratios are consistent with ices toward dark clouds, protostars, and comets, albeit with some scatter. The constant gas-phase column density ratios throughout low and high-mass sources indicate an early stage formation before intense environmental differentiation begins. Icy protostellar values are similar to the gas phase medians, compatible with an icy origin of these species followed by thermal sublimation. The larger spread in SO2 compared to OCS ratios w.r.t. CH3OH is likely due to a more water-rich chemical environment associated with the former, as opposed to a CO-rich origin of the latter. Post-sublimation gas-phase processing of SO2 can also contribute to the large spread. Comparisons to ices in dark clouds and comets point to a significant inheritance of OCS from earlier to later evolutionary stages.

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Title: Formation of S-bearing complex organic molecules in interstellar clouds via ice reactions with C2H2, HS, and atomic H

Summary:

The chemical network governing interstellar sulfur has been the topic of unrelenting discussion for the past decades due to the conspicuous discrepancy between its expected and observed abundances in different interstellar environments. More recently, the astronomical detections of CH3CH2SH and CH2CS highlighted the importance of interstellar formation routes for sulfur-bearing organic molecules with two carbon atoms. In this work, we perform a laboratory investigation of the solid-state chemistry resulting from the interaction between C2H2 molecules and SH radicals -- both thought to be present in interstellar icy mantles -- at 10 K. Reflection absorption infrared spectroscopy and quadrupole mass spectrometry combined with temperature-programmed desorption experiments are employed as analytical techniques. We confirm that SH radicals can kick-start a sulfur reaction network under interstellar cloud conditions and identify at least six sulfurated

products: CH3CH2SH, CH2CHSH, HSCH2CH2SH, H2S2, and tentatively CH3CHS and CH2CS. Complementarily, we utilize computational calculations to pinpoint the reaction routes that play a role in the chemical network behind our experimental results. The main sulfur-bearing organic molecule formed under our experimental conditions is CH3CH2SH and its formation yield increases with the ratios of H to other reactants. It serves as a sink to the sulfur budget within the network, being formed at the expense of the other unsaturated products. The astrophysical implications of the chemical network proposed here are discussed.

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Title: Formation of carbonyl sulfide (OCS) via SH radicals in interstellar CO-rich ice under dense cloud conditions

Summary:

Carbonyl sulfide (OCS) is widely observed in the gas phase towards star-forming regions and was the first of the only two sulfur-bearing species detected in interstellar ices so far. However, the chemical network governing its formation is still not fully understood. While the sulfurization of CO and the oxidation of CS are often invoked to form OCS, other mechanisms could have a significant contribution. In particular, the multistep reaction involving CO and SH is a good candidate to forming OCS in dense cloud environments. We aim to constrain the viability of the CO + SH route to forming solid OCS in the interstellar medium, in a similar manner as CO + OH is known to produce CO2 ice. This is achieved by conducting a systematic laboratory investigation of the targeted reactions on interstellar ice analogues under dense cloud conditions. An ultrahigh vacuum chamber is utilized to simultaneously deposit CO, H2S, and atomic H at 10 K. SH radicals produced in situ via hydrogen abstraction from H2S react with CO to form OCS. OCS is efficiently formed through surface reactions involving CO, H2S, and H atoms. The suggested underlying mechanism behind OCS formation is CO + SH -> HSCO followed by HSCO + H -> OCS + H2. The OCS yield reduces slowly, but remains significant with increasing CO:H2S mixing ratios (CO:H2S = 1:1, 5:1, 10:1, and 20:1). Our experiments provide unambiguous evidence that OCS can be formed from CO + SH in the presence of H atoms. This route remains efficient for large H2S dilutions (5% w.r.t CO), suggesting that it is a viable mechanism in interstellar ices. Given that SH radicals can be created in clouds throughout a wide evolutionary timescale, this mechanism could have a non-negligible contribution to forming interstellar OCS ice.

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