Multiwavelength Ablation/Ionization and Mass Spectrometric Analysis of 1.88 Ga Gunflint Chert.

The investigation of chemical composition on planetary bodies without significant sample processing is of importance for nearly every mission aimed at robotic exploration. Moreover, it is a necessary tool to achieve the longstanding goal of finding evidence of life beyond Earth, for example, possibly preserved microbial remains within martian sediments. Our Laser Ablation Ionization Mass Spectrometer (LIMS) is a compact time-of-flight mass spectrometer intended to investigate the elemental, isotope, and molecular composition of a wide range of solid samples, including e.g., low bulk density organic remains in microfossils. Here, we present an overview of the instrument and collected chemical spectrometric data at the micrometer level from a Precambrian chert sample (1.88 Ga Gunflint Formation, Ontario, Canada), which is considered to be a martian analogue. Data were collected from two distinct zones-a silicified host area and a carbon-bearing microfossil assemblage zone. We performed these measurements using an ultrafast pulsed laser system (pulse width of ∼180 fs) with multiple wavelengths (infrared [IR]-775 nm, ultraviolet [UV]-387 nm, UV-258 nm) and using a pulsed high voltage on the mass spectrometer to reveal small organic signals. We investigated (1) the chemical composition of the sample and (2) the different laser wavelengths' performance to provide chemical depth profiles in silicified media. Our key findings are as follows: (1) microfossils from the Gunflint chert reveal a distinct chemical composition compared with the host mineralogy (we report the identification of 24 elements in the microfossils); (2) detection of the pristine composition of microfossils and co-occurring fine chemistry (rare earth elements) requires utilization of the depth profiling measurement protocol; and (3) our results show that, for analysis of heterogeneous material from siliciclastic deposits, siliceous sinters, and cherts, the most suitable wavelength for laser ablation/Ionization is UV-258 nm.

On Topological Analysis of fs-LIMS Data. Implications for in Situ Planetary Mass Spectrometry.

In this contribution, we present results of non-linear dimensionality reduction and classification of the fs laser ablation ionization mass spectrometry (LIMS) imaging dataset acquired from the Precambrian Gunflint chert (1.88 Ga) using a miniature time-of-flight mass spectrometer developed for in situ space applications. We discuss the data generation, processing, and analysis pipeline for the classification of the recorded fs-LIMS mass spectra. Further, we define topological biosignatures identified for Precambrian Gunflint microfossils by projecting the recorded fs-LIMS intensity space into low dimensions. Two distinct subtypes of microfossil-related spectra, a layer of organic contamination and inorganic quartz matrix were identified using the fs-LIMS data. The topological analysis applied to the fs-LIMS data allows to gain additional knowledge from large datasets, formulate hypotheses and quickly generate insights from spectral data. Our contribution illustrates the utility of applying spatially resolved mass spectrometry in combination with topology-based analytics in detecting signatures of early (primitive) life. Our results indicate that fs-LIMS, in combination with topological methods, provides a powerful analytical framework and could be applied to the study of other complex mineralogical samples.