S. Kashyap

Evidence for indigenous nitrogen in sedimentary and aeolian deposits from the Curiosity rover investigations at Gale crater, Mars

Significance We present data supporting the presence of an indigenous source of fixed nitrogen on the surface of Mars in the form of nitrate. This fixed nitrogen may indicate the first stage in development of a primitive nitrogen cycle on the surface of ancient Mars and would have provided a biochemically accessible source of nitrogen. The Sample Analysis at Mars (SAM) investigation on the Mars Science Laboratory (MSL) Curiosity rover has detected oxidized nitrogen-bearing compounds during pyrolysis of scooped aeolian sediments and drilled sedimentary deposits within Gale crater. Total N concentrations ranged from 20 to 250 nmol N per sample. After subtraction of known N sources in SAM, our results support the equivalent of 110–300 ppm of nitrate in the Rocknest (RN) aeolian samples, and 70–260 and 330–1,100 ppm nitrate in John Klein (JK) and Cumberland (CB) mudstone deposits, respectively. Discovery of indigenous martian nitrogen in Mars surface materials has important implications for habitability and, specifically, for the potential evolution of a nitrogen cycle at some point in martian history. The detection of nitrate in both wind-drifted fines (RN) and in mudstone (JK, CB) is likely a result of N2 fixation to nitrate generated by thermal shock from impact or volcanic plume lightning on ancient Mars. Fixed nitrogen could have facilitated the development of a primitive nitrogen cycle on the surface of ancient Mars, potentially providing a biochemically accessible source of nitrogen.

Spectral and morphological characteristics of synthetic nanophase iron (oxyhydr)oxides

Nanophase iron (oxyhydr)oxides are ubiquitous on Earth, globally distributed on Mars, and likely present on numerous other rocky solar system bodies. They are often structurally and, therefore, spectrally distinct from iron (oxyhydr)oxide bulk phases. Because their spectra vary with grain size, they can be difficult to identify or distinguish unless multiple analysis techniques are used in tandem. Yet, most literature reports fail to use multiple techniques or adequately parameterize sample morphology, making it difficult to understand how morphology affects spectral characteristics across techniques. Here, we present transmission electron microscopy, Raman, visible and near-infrared, and mid-infrared attenuated total reflectance data on synthetic, nanophase akaganéite, lepidocrocite, goethite, hematite, ferrihydrite, magnetite, and maghemite. Feature positions are tabulated and compared to those for bulk (oxyhydr)oxides and other nanophase iron (oxyhydr)oxides from the literature. The utility and limitations of each technique in analyzing nanophase iron (oxyhydr)oxides are discussed. Raman, mid-infrared, and visible near-infrared spectra show broadening, loss of some spectral features, and shifted positions compared to bulk phases. Raman and mid-infrared spectroscopies are useful in identifying and distinguishing akaganéite, lepidocrocite, goethite, and hematite, though ferrihydrite, magnetite, and maghemite have overlapped band positions. Visible near-infrared spectroscopy can identify and distinguish among ferrihydrite, magnetite, and maghemite in pure spectra, though akaganéite, lepidocrocite, and goethite can have overlapping bands. It is clear from this work that further understanding of variable spectral features in nanophase iron (oxyhydr)oxides must await additional studies to robustly assess effects of morphology. This study establishes a template for future work.

Reduction and Morphological Transformation of Synthetic Nanophase Iron Oxide Minerals by Hyperthermophilic Archaea

Fe(III) (oxyhydr)oxides are electron acceptors for some hyperthermophilic archaea in mildly reducing geothermal environments. However, the kinds of iron oxides that can be used, growth rates, extent of iron reduction, and the morphological changes that occur to minerals are poorly understood. The hyperthermophilic iron-reducing crenarchaea Pyrodictium delaneyi and Pyrobaculum islandicum were grown separately on six different synthetic nanophase Fe(III) (oxyhydr)oxides. For both organisms, growth on ferrihydrite produced the highest growth rates and the largest amounts of Fe(II), although P. delaneyi produced four times more Fe(II) (25 mM) than P. islandicum (6 mM). Both organisms grew on lepidocrocite and akaganéite and produced 2 and 3 mM Fe(II). Modest growth occurred for both organisms on goethite, hematite, and maghemite where ≤1 mM Fe(II) was produced. The diameters of the spherical mineral end-products following P. delaneyi growth increased by 30 nm for ferrihydrite and 50–150 nm for lepidocrocite relative to heated abiotic controls. For akaganéite, spherical particle sizes were the same for P. delaneyi-reacted samples and heated abiotic controls, but the spherical particles were more numerous in the P. delaneyi samples. For P. islandicum, there was no increase in grain size for the mineral end-products following growth on ferrihydrite, lepidocrocite, or akaganéite relative to the heated abiotic controls. High-resolution transmission electron microscopy of lattice fringes and selected-area electron diffraction of the minerals produced by both organisms when grown on ferrihydrite showed that magnetite and/or possibly maghemite were the end-products while the heated abiotic controls only contained ferrihydrite. These results expand the current view of bioavailable Fe(III) (oxyhydr)oxides for reduction by hyperthermophilic archaea when presented as synthetic nanophase minerals. They show that growth and reduction rates are inversely correlated with the iron (oxyhydr)oxide crystallinity and that iron (oxyhydr)oxide mineral transformation takes different forms for these two organisms.