Multi-Excitation Raman Spectroscopy of Carbonaceous Matter within Opaline Silica Sinters from Mars-Analog Hot Spring Settings: Implications for the Search for Extraterrestrial Biosignatures.

Silica sinters are promising astrobiology targets in the search for signs of past extraterrestrial life on Mars. Although terrestrial sinter morphologic features may serve as potential biosignatures at the macroscale, identification of carbonaceous matter (CM) within silica would offer substantial support for interpreting martian silica deposits as having a biologic association. Raman spectroscopy provides a means to identify both minerals and organics in situ. This technique has been employed to analyze CM in terrestrial sinters that consist of microcrystalline quartz and has also been deployed previously on Mars to search for organics. However, martian silica deposits are dominated by opaline silica rather than quartz, and a thorough examination of CM within terrestrial opaline silica by Raman spectroscopy is generally lacking. We investigated opaline silica sinters from northern Chile, an exceptional terrestrial analog for Mars, by Raman spectroscopy with multiple excitations. Our results show that strong fluorescence from opaline silica modifies CM Raman spectral signatures across excitation wavelengths. CM Raman spectra within opaline silica sinters vary both among facies and within individual samples, and they differ from those in Archean cherts. This study demonstrates that reliable interpretation of CM Raman spectra requires attention to host-matrix influences, excitation wavelength, and curve-fitting procedures.