1N. Randazzo,1R. W. Hilts,2R. M. Whittal,2B. Reiz,1V. Olan-Rubio,1C. D. K. Herd,3I. H. Krouse
Meteoritics & Planetary Science (in Press) Open Access Link to Article [doi: 10.1111/maps.701271]
1Department of Earth and Atmospheric Sciences, University of Alberta, Edmonton, Alberta, Canada
2Department of Chemistry, University of Alberta, Edmonton, Alberta, Canada
3School of Science and Technology, Georgia Gwinnett College, Lawrenceville, Georgia, USA
Published by arrangement with John Wiley & Sons
Solvent extraction is a cornerstone of meteoritic organic and inorganic chemistry,yet the assumption that common solvents act as chemically inert media is becomingincreasingly untenable. This study reports that low-molecular-weight alcohols, particularlymethanol and ethanol, are “non-innocent” solvents when used to extract soluble sulfurspecies from carbonaceous chondrites. Laboratory extractions of Tagish Lake and Allendesamples demonstrate that these alcohols readily esterify meteoritic sulfate, producing largequantities of methyl and ethyl sulfate artifacts. Using isotopically labeled methanol(CD 3 OH) in 1:1 water mixtures, it is shown that >99% of the methyl sulfate signalpreviously attributed to indigenous methyl sulfate is actually solvent-derived. Correctedabundances fall from hundreds of nmol g1 reported in earlier studies to < 0.2 nmol g1 ,revealing that intrinsic methyl sulfate is only a trace constituent. Control experimentsindicate that esterification requires both acidic conditions and solid meteoritic matrices,implicating Fe-bearing phyllosilicates and oxides as heterogeneous catalysts. Additionalexperiments confirm that sulfate ester formation does not occur in solution-only systems,underscoring the catalytic role of mineral–solvent interfaces. These findings not onlynecessitate a downward revision of reported organosulfur inventories in carbonaceouschondrites but also highlight a broader issue: solvent-driven reactions can significantly alterthe apparent chemical record of extraterrestrial materials. It is recommended thatisotope-labeled solvents and mixed-solvent systems are employed as standard practice infuture extractions, both to minimize artifact generation and to maximize analyte coverageacross polarity ranges. Recognizing and mitigating solvent reactivity is essential for ensuringthat laboratory analyses faithfully represent intrinsic extraterrestrial chemistry rather thanexperimental artifacts.