Search

We report deep ultraviolet (DUV) Raman and Fluorescence spectra obtained on a SHERLOC (Scanning Habitable Environments with Raman and Luminescence for Organics and Chemicals) analog instrument for 51 pure organic compounds, including 5 carboxylic acids, 10 polycyclic aromatic hydrocarbons, 24 amino acids, 6 nucleobases, and 6 different grades of macromolecular carbon from humic acid to graphite. Organic mixtures were not investigated. We discuss how the DUV fluorescence and Raman spectra exhibited by different organic compounds allow for detection, classification, and identification of organics by SHERLOC. We find that 1- and 2-ring aromatic compounds produce detectable fluorescence within SHERLOC's spectral range (250-355 nm), but fluorescence spectra are not unique enough to enable easy identification of particular compounds. However, both aromatic and aliphatic compounds can be identified by their Raman spectra, with the number of Raman peaks and their positions being highly specific to chemical structure, within SHERLOC's reported spectral uncertainty of ±5 cm -1 . For compounds that are not in the Library, classification is possible by comparing the general number and position of dominant Raman peaks with trends for different kinds of organic compounds.

The NASA Mars 2020 Perseverance rover is currently exploring Jezero crater, a Noachian-Hesperian locality that once hosted a delta-lake system with high habitability and biosignature preservation potential. Perseverance conducts detailed appraisals of rock targets using a synergistic payload capable of geological characterization from kilometer to micron scales. The highest-resolution textural and chemical information will be provided by correlated WATSON (imaging), SHERLOC (deep-UV Raman and fluorescence spectroscopy), and PIXL (X-ray lithochemistry) analyses, enabling the distributions of organic and mineral phases within rock targets to be comprehensively established. Herein, we analyze Paleoarchean microbial mats from the ∼3.42 Ga Buck Reef Chert (Barberton greenstone belt, South Africa)-considered astrobiological analogues for a putative ancient martian biosphere-following a WATSON-SHERLOC-PIXL protocol identical to that conducted by Perseverance on Mars during all sampling activities. Correlating deep-UV Raman and fluorescence spectroscopic mapping with X-ray elemental mapping, we show that the Perseverance payload has the capability to detect thermally and texturally mature organic materials of biogenic origin and can highlight organic-mineral interrelationships and elemental colocation at fine spatial scales. We also show that the Perseverance protocol obtains very similar results to high-performance laboratory imaging, Raman spectroscopy, and μXRF instruments. This is encouraging for the prospect of detecting microscale organic-bearing textural biosignatures on Mars using the correlative micro-analytical approach enabled by WATSON, SHERLOC, and PIXL; indeed, laminated, organic-bearing samples such as those studied herein are considered plausible analogues of biosignatures from a potential Noachian-Hesperian biosphere. Were similar materials discovered at Jezero crater, they would offer opportunities to reconstruct aspects of the early martian carbon cycle and search for potential fossilized traces of life in ancient paleoenvironments. Such samples should be prioritized for caching and eventual return to Earth.

The search for organic biosignatures on Mars will depend on finding material protected from the destructive ambient radiation. Solar ultraviolet can induce photochemical degradation of organic compounds, but certain clays have been shown to preserve organic material. We examine how the SHERLOC instrument on the upcoming Mars 2020 mission will use deep-ultraviolet (UV) (248.6 nm) Raman and fluorescence spectroscopy to detect a plausible biosignature of adenosine 5'-monophosphate (AMP) adsorbed onto Ca-montmorillonite clay. We found that the spectral signature of AMP is not altered by adsorption in the clay matrix but does change with prolonged exposure to the UV laser over dosages equivalent to 0.2-6 sols of ambient martian UV. For pure AMP, UV exposure leads to breaking of the aromatic adenine unit, but in the presence of clay the degradation is limited to minor alteration with new Raman peaks and increased fluorescence consistent with formation of 2-hydroxyadenosine, while 1 wt % Mg perchlorate increases the rate of degradation. Our results confirm that clays are effective preservers of organic material and should be considered high-value targets, but that pristine biosignatures may be altered within 1 sol of martian UV exposure, with implications for Mars 2020 science operations and sample caching.

A prototype rover carrying an astrobiology payload was developed and deployed at analog field sites to mature generalized system architectures capable of searching for biosignatures in extreme terrain across the Solar System. Specifically, the four-legged Limbed Excursion Mechanical Utility Robot (LEMUR) 3 climbing robot with microspine grippers carried three instruments: a micro-X-ray fluorescence instrument based on the Mars 2020 mission's Planetary Instrument for X-ray Lithochemistry provided elemental chemistry; a deep-ultraviolet fluorescence instrument based on Mars 2020's Scanning Habitable Environments with Raman and Luminescence for Organics and Chemicals mapped organics in bacterial communities on opaque substrates; and a near-infrared acousto-optic tunable filter-based point spectrometer identified minerals and organics in the 1.6-3.6 μm range. The rover also carried a light detection and ranging and a color camera for both science and navigation. Combined, this payload detects astrobiologically important classes of rock components (elements, minerals, and organics) in extreme terrain, which, as demonstrated in this work, can reveal a correlation between textural biosignatures and the organics or elements expected to preserve them in a habitable environment. Across >10 field tests, milestones were achieved in instrument operations, autonomous mobility in extreme terrain, and system integration that can inform future planetary science mission architectures. Contributions include (1) system-level demonstration of mock missions to the vertical exposures of Mars lava tube caves and Mars canyon walls, (2) demonstration of multi-instrument integration into a confocal arrangement with surface scanning capabilities, and (3) demonstration of automated focus stacking algorithms for improved signal-to-noise ratios and reduced operation time.

We used a deep-ultraviolet fluorescence mapping spectrometer, coupled to a drill system, to scan from the surface to 105 m depth into the Greenland ice sheet. The scan included firn and glacial ice and demonstrated that the instrument is able to determine small (mm) and large (cm) scale regions of organic matter concentration and discriminate spectral types of organic matter at high resolution. Both a linear point cloud scanning mode and a raster mapping mode were used to detect and localize microbial and organic matter "hotspots" embedded in the ice. Our instrument revealed diverse spectral signatures. Most hotspots were <20 mm in diameter, clearly isolated from other hotspots, and distributed stochastically; there was no evidence of layering in the ice at the fine scales examined (100 μm per pixel). The spectral signatures were consistent with organic matter fluorescence from microbes, lignins, fused-ring aromatic molecules, including polycyclic aromatic hydrocarbons, and biologically derived materials such as fulvic acids. In situ detection of organic matter hotspots in ice prevents loss of spatial information and signal dilution when compared with traditional bulk analysis of ice core meltwaters. Our methodology could be useful for detecting microbial and organic hotspots in terrestrial icy environments and on future missions to the Ocean Worlds of our Solar System.

The molecules feeding life's emergence are thought to have been provided through the hydrothermal interactions of convecting carbonic ocean waters with minerals comprising the early Hadean oceanic crust. Few laboratory experiments have simulated ancient hydrothermal conditions to test this conjecture. We used the JPL hydrothermal flow reactor to investigate CO 2 reduction in simulated ancient alkaline convective systems over 3 days (T = 120°C, P  = 100 bar, pH = 11). H 2 -rich hydrothermal simulant and CO 2 -rich ocean simulant solutions were periodically driven in 4-h cycles through synthetic mafic and ultramafic substrates and Fe>Ni sulfides. The resulting reductants included micromoles of HS - and formate accompanied possibly by micromoles of acetate and intermittent minor bursts of methane as ascertained by isotopic labeling. The formate concentrations directly correlated with the CO 2 input as well as with millimoles of Mg 2 + ions, whereas the acetate did not. Also, tens of micromoles of methane were drawn continuously from the reactor materials during what appeared to be the onset of serpentinization. These results support the hypothesis that formate may have been delivered directly to a branch of an emerging acetyl coenzyme-A pathway, thus obviating the need for the very first hydrogenation of CO 2 to be made in a hydrothermal mound. Another feed to early metabolism could have been methane, likely mostly leached from primary CH 4 present in the original Hadean crust or emanating from the mantle. That a small volume of methane was produced sporadically from the 13 CO 2 -feed, perhaps from transient occlusions, echoes the mixed results and interpretations from other laboratories. As serpentinization and hydrothermal leaching can occur wherever an ocean convects within anhydrous olivine- and sulfide-rich crust, these results may be generalized to other wet rocky planets and moons in our solar system and beyond.

Terrestrial icy environments have been found to preserve organic material and contain habitable niches for microbial life. The cryosphere of other planetary bodies may therefore also serve as an accessible location to search for signs of life. The Wireline Analysis Tool for the Subsurface Observation of Northern ice sheets (WATSON) is a compact deep-UV fluorescence spectrometer for nondestructive ice borehole analysis and spatial mapping of organics and microbes, intended to address the heterogeneity and low bulk densities of organics and microbial cells in ice. WATSON can be either operated standalone or integrated into a wireline drilling system. We present an overview of the WATSON instrument and results from laboratory experiments intended to determine (i) the sensitivity of WATSON to organic material in a water ice matrix and (ii) the ability to detect organic material under various thicknesses of ice. The results of these experiments show that in bubbled ice the instrument has a depth of penetration of 10 mm and a detection limit of fewer than 300 cells. WATSON incorporates a scanning system that can map the distribution of organics and microbes over a 75 by 25 mm area. WATSON demonstrates a sensitive fluorescence mapping technique for organic and microbial detection in icy environments including terrestrial glaciers and ice sheets, and planetary surfaces including Europa, Enceladus, or the martian polar caps.

This paper presents a reformulation of the submarine alkaline hydrothermal theory for the emergence of life in response to recent experimental findings. The theory views life, like other self-organizing systems in the Universe, as an inevitable outcome of particular disequilibria. In this case, the disequilibria were two: (1) in redox potential, between hydrogen plus methane with the circuit-completing electron acceptors such as nitrite, nitrate, ferric iron, and carbon dioxide, and (2) in pH gradient between an acidulous external ocean and an alkaline hydrothermal fluid. Both CO2 and CH4 were equally the ultimate sources of organic carbon, and the metal sulfides and oxyhydroxides acted as protoenzymatic catalysts. The realization, now 50 years old, that membrane-spanning gradients, rather than organic intermediates, play a vital role in life's operations calls into question the idea of "prebiotic chemistry." It informs our own suggestion that experimentation should look to the kind of nanoengines that must have been the precursors to molecular motors-such as pyrophosphate synthetase and the like driven by these gradients-that make life work. It is these putative free energy or disequilibria converters, presumably constructed from minerals comprising the earliest inorganic membranes, that, as obstacles to vectorial ionic flows, present themselves as the candidates for future experiments. Key Words: Methanotrophy-Origin of life. Astrobiology 14, 308-343. The fixation of inorganic carbon into organic material (autotrophy) is a prerequisite for life and sets the starting point of biological evolution. (Fuchs, 2011 ) Further significant progress with the tightly membrane-bound H(+)-PPase family should lead to an increased insight into basic requirements for the biological transport of protons through membranes and its coupling to phosphorylation. (Baltscheffsky et al., 1999 ).

If life ever evolved on the surface of Mars, it is unlikely that it would still survive there today, but as Mars evolved from a wet planet to an arid one, the subsurface environment may have presented a refuge from increasingly hostile surface conditions. Since the last glacial maximum, the Mojave Desert has experienced a similar shift from a wet to a dry environment, giving us the opportunity to study here on Earth how subsurface ecosystems in an arid environment adapt to increasingly barren surface conditions. In this paper, we advocate studying the vadose zone ecosystem of the Mojave Desert as an analogue for possible subsurface biospheres on Mars. We also describe several examples of Mars-like terrain found in the Mojave region and discuss ecological insights that might be gained by a thorough examination of the vadose zone in these specific terrains. Examples described include distributary fans (deltas, alluvial fans, etc.), paleosols overlain by basaltic lava flows, and evaporite deposits.

The concept that life emerged where alkaline hydrogen-bearing submarine hot springs exhaled into the most ancient acidulous ocean was used as a working hypothesis to investigate the nature of precipitate membranes. Alkaline solutions at 25-70°C and pH between 8 and 12, bearing HS(-)±silicate, were injected slowly into visi-jars containing ferrous chloride to partially simulate the early ocean on this or any other wet and icy, geologically active rocky world. Dependent on pH and sulfide content, fine tubular chimneys and geodal bubbles were generated with semipermeable walls 4-100 μm thick that comprised radial platelets of nanometric mackinawite [FeS]±ferrous hydroxide [∼Fe(OH)(2)], accompanied by silica and, at the higher temperature, greigite [Fe(3)S(4)]. Within the chimney walls, these platelets define a myriad of micropores. The interior walls of the chimneys host iron sulfide framboids, while, in cases where the alkaline solution has a pH>11 or relatively low sulfide content, their exteriors exhibit radial flanges with a spacing of ∼4 μm that comprise microdendrites of ferrous hydroxide. We speculate that this pattern results from outward and inward radial flow through the chimney walls. The outer Fe(OH)(2) flanges perhaps precipitate where the highly alkaline flow meets the ambient ferrous iron-bearing fluid, while the intervening troughs signal where the acidulous iron-bearing solutions could gain access to the sulfidic and alkaline interior of the chimneys, thereby leading to the precipitation of the framboids. Addition of soluble pentameric peptides enhances membrane durability and accentuates the crenulations on the chimney exteriors. These dynamic patterns may have implications for acid-base catalysis and the natural proton motive force acting through the matrix of the porous inorganic membrane. Thus, within such membranes, steep redox and pH gradients would bear across the nanometric platelets and separate the two counter-flowing solutions, a condition that may have led to the onset of an autotrophic metabolism through the reduction of carbon dioxide.

A principal goal of astrobiology is to detect and inventory the population of organic compounds on extraterrestrial bodies. Targets of specific interest include the wealth of icy worlds that populate our Solar System. One potential technique for in situ detection of organics trapped in water ice matrices involves ultraviolet-stimulated emission from these compounds. Here, we report a preliminary investigation into the feasibility of this concept. Specifically, fluorescence and phosphorescence of pure benzene ice and 1% mixtures of benzene, toluene, p-xylene, m-xylene, and o-xylene in water ice, respectively, were studied at temperatures ranging from ∼17 K up to 160 K. Spectra were measured from 200-500 nm (50,000-20,000 cm(-1)) while ice mixtures were excited at 248.6 nm. The temperature dependence of the fluorescence and phosphorescence intensities was found to be independent of the thermal history and phase of the ice matrix in all cases examined. All phosphorescent emissions were found to decrease in intensity with increasing temperature. Similar behavior was observed for fluorescence in pure benzene, while the observed fluorescence intensity in water ices was independent of temperature., (© Mary Ann Liebert, Inc.)