Detection and quantification of organosulfur species in the Tagish Lake Meteorite by highly sensitive LC-MS

Abstract

We analyzed the methanol extracts of six pristine specimens of the Tagish Lake meteorite (TL1, TL4, TL5A, TL6, TL7, and TL10a) and heated and unheated samples of Allende using high-performance liquid chromatography coupled with high-resolution, accurate mass–mass spectrometry (HPLC-HRAM-MS). All samples contained ppm levels of sulfate and methyl sulfate. The most abundant organosulfur compound in the methanol extracts of the Tagish Lake and Allende samples was methyl sulfate, which was likely formed primarily via an esterification reaction between intrinsic sources of methanol and sulfate. A homologous series of polythionic acids was also observed in the extracts of the Tagish Lake specimens and Allende. The polythionic acids were the most abundant soluble inorganic sulfur species found in the meteorites. Our results were confirmed using retention time, accurate mass, isotope matching, and tandem mass spectrometry (MS/MS). Hydroxymethanesulfonic acid, previously reported in Tagish Lake, was found only in an unheated Allende sample and in low abundance. Here, we propose possible sulfate formation pathways that begin with interstellar dimethyl sulfide, dimethyl disulfide, methyl sulfide, or methanethiol via cold, nebular processes within the interstellar medium and continue via MSA as an intermediary compound ending within planetary bodies with sulfate and methyl sulfate as the final products.