Ammonium hydrosulfide (NH4SH) as a potentially significant sulfur sink in interstellar ices

Abstract

Sulfur is depleted with respect to its cosmic standard abundance in dense star-forming regions. It has been suggested that this depletion is caused by the freeze-out of sulfur on interstellar dust grains, but the observed abundances and upper limits of sulfur-bearing ices remain too low to account for all of the missing sulfur. Toward the same environments, a strong absorption feature at 6.85 $\mu$m is observed, but its long-standing assignment to the NH4+ cation remains tentative. We investigate the plausibility of NH4SH salt serving as a sulfur reservoir and a carrier of the 6.85 $\mu$m band in interstellar ices by characterizing its IR signatures and apparent band strengths in water-rich laboratory ice mixtures and using this laboratory data to constrain NH4SH abundances in observations of 4 protostars and 2 cold dense clouds. The observed 6.85 $\mu$m feature is fit well with the laboratory NH4SH:H2O ice spectra. NH4+ column densities obtained from the 6.85 $\mu$m band range from 8-23% with respect to H2O toward the sample of protostars and dense clouds. The redshift of the 6.85 $\mu$m feature correlates with higher abundances of NH4+ with respect to H2O in both the laboratory data presented here and observational data of dense clouds and protostars. The apparent band strength of the SH- feature is likely too low for the feature to be detectable in the spectrally busy 3.9 $\mu$m region, but the 5.3 $\mu$m NH4+ $\nu_{4}$ + SH- R combination mode may be an alternative means of detection. Its tentative assignment adds to mounting evidence supporting the presence of NH4+ salts in ices and is the first tentative observation of the SH- anion toward interstellar ices. If the majority ($\gtrsim$80-85%) of the NH4+ cations quantified toward the investigated sources in this work are bound to SH- anions, then NH4SH salts could account for up to 17-18% of their sulfur budgets.