Analysis of archaeal core ether lipids using Time of Flight–Secondary Ion Mass Spectrometry (ToF-SIMS): Exploring a new prospect for the study of biomarkers in geobiology

The capability of Time of Flight–Secondary Ion Mass Spectrometry (ToF‐SIMS) of analysing molecular archaeal biomarkers in geobiological samples was tested and demonstrated. Using a bismuth cluster primary ion source, isopranyl glycerol di‐ and tetraether core lipids were detected in small amounts of total organic extracts from methanotrophic microbial mats, simultaneously and without further chemical treatment and chromatographic separation. ToF‐SIMS was also employed to track the distribution of fossilized ether lipids in a massive carbonate (aragonite) microbialite that precipitated as a result of the microbial anaerobic oxidation of methane. An unambiguous signal was obtained when analysing a freshly broken rock surface (base of a microdrill core). Though some limitation occurred due to µm‐topographical effects (sample roughness), it was possible to display the abundance of high molecular weight (C₈₆) of tetraethers exposed in particular regions of the rock surface. ‘Molecular mapping’ revealed that a part of these molecules was encased within the rock fabric in a cluster‐like distribution that might trace the arrangement of the calcifying microbial colonies in the once active mat system. The results reveal promising perspectives of ToF‐SIMS for (i) the quasi‐nondestructive analysis of lipids in extremely small geobiological samples at low concentrations; (ii) resolving the spatial distribution of these compounds on a µm²‐ to cm²‐scale; and (iii) the more exact assignment of lipid biomarkers to their biological source.