Formation and desorption of sulfur chains (H$_2$S$_x$ and S$_x$) in cometary ice: effects of ice composition and temperature

TL;DR

This study experimentally investigates sulfur chain formation in cometary ice, revealing temperature-dependent formation efficiencies and proposing potential links to observed cometary sulfur species detected by the Rosetta mission.

Contribution

It provides the first mass spectra of H$_2$S$_x$ species in ice, demonstrating formation in water-rich environments and suggesting possible identification of cometary sulfur compounds.

Findings

Sulfur chains form efficiently at low temperatures (~10 K).

Short sulfur chains are favored at higher temperatures (~50 K).

Mass spectra of H$_2$S$_x$ (x=2-6) are presented for the first time.

Abstract

The reservoir of sulfur accounting for sulfur depletion in the gas of dense clouds and circumstellar regions is still unclear. One possibility is the formation of sulfur chains, which would be difficult to detect by spectroscopic techniques. This work explores the formation of sulfur chains experimentally, both in pure H$_2$S ice samples and in H$_2$O:H$_2$S ice mixtures. An ultra-high vacuum chamber, ISAC, eqquipped with FTIR and QMS, was used for the experiments. Our results show that the formation of H$_2$S$_x$ species is efficient, not only in pure H$_2$S ice samples, but also in water-rich ice samples. Large sulfur chains are formed more efficiently at low temperatures ($\approx$10 K), while high temperatures ($\approx$50 K) favour the formation of short sulfur chains. Mass spectra of H$_2$S$_x$, x~=~2-6, species are presented for the first time. Their analysis suggests that H$_2$S$_x$ species are favoured in comparison with S$_x$ chains. Nevertheless, the detection of several S$_x^+$ fragments at high temperatures in H$_2$S:H$_2$O ice mixtures suggests the presence of S$_8$ 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) H$_2$S$_4$ and H$_2$S$_5$ to be responsible of those S$_3^+$ and S$_4^+$ cations, respectively, or 2) S$_8$ species, sublimating and being fragmented in the mass spectrometer. If S$_8$ is the parent molecule, then S$_5^+$ and S$_6^+$ cations could be also detected in future missions by broadening the mass spectrometer range.