In Situ Geochemical Analysis and Age Dating of Rocks Using Laser Ablation-Miniature Mass Spectrometer

A miniaturized instrument for performing chemical and isotopic analysis of rocks has been developed. The rock sample is ablated by a laser and the neutral species produced are analyzed using the JPL-invented miniature mass spectrometer. The direct sampling of neutral ablated material and the simultaneous measurement of all the elemental and isotopic species are the novelties of this method. In this laser ablation-miniature mass spectrometer (LA-MMS) method, the ablated neutral atoms are led into the electron impact ionization source of the MMS, where they are ionized by a 70-eV electron beam. This results in a secondary ion pulse typically 10-100 microsecond wide, compared to the original 5-10-nanosecond laser pulse duration. Ions of different masses are then spatially dispersed along the focal plane of the magnetic sector of the miniature mass spectrometer and measured in parallel by a modified CCD (charge-coupled device) array detector capable of detecting ions directly. Compared to conventional scanning techniques, simultaneous measurement of the ion pulse along the focal plane effectively offers a 100% duty cycle over a wide mass range. LAMMS offers a more quantitative assessment of elemental composition than techniques that detect laser-ionized species produced directly in the ablation process because the latter can be strongly influenced by matrix effects that vary with the structure and geometry of the surface, the laser beam, and the ionization energies of the elements. The measurement of high-precision isotopic ratios and elemental composition of different rock minerals by LAMMS method has been demonstrated. The LA-MMS can be applied for the absolute age determination of rocks. There is no such instrument available presently in a miniaturized version that can be used for NASA space missions. Work is in progress in the laboratory for geochronology of rocks using LA-MMS that is based on K-Ar radiogenic dating technique

The Sedimentary Cycle on Early Mars

Two decades of intensive research have demonstrated that early Mars (2 Gyr) had an active sedimentary cycle, including well-preserved stratigraphic records, understandable within a source-to-sink framework with remarkable fidelity. This early cycle exhibits first-order similarities to (e.g., facies relationships, groundwater diagenesis, recycling) and first-order differences from (e.g., greater aeolian versus subaqueous processes, basaltic versus granitic provenance, absence of plate tectonics) Earth's record. Mars’ sedimentary record preserves evidence for progressive desiccation and oxidation of the surface over time, but simple models for the nature and evolution of paleoenvironments (e.g., acid Mars, early warm and wet versus late cold and dry) have given way to the view that, similar to Earth, different climate regimes on Mars coexisted on regional scales and evolved on variable timescales, and redox chemistry played a pivotal role. A major accomplishment of Mars exploration has been to demonstrate that surface and subsurface sedimentary environments were both habitable and capable of preserving any biological record

The Sedimentary Cycle on Early Mars

Two decades of intensive research have demonstrated that early Mars (2 Gyr) had an active sedimentary cycle, including well-preserved stratigraphic records, understandable within a source-to-sink framework with remarkable fidelity. This early cycle exhibits first-order similarities to (e.g., facies relationships, groundwater diagenesis, recycling) and first-order differences from (e.g., greater aeolian versus subaqueous processes, basaltic versus granitic provenance, absence of plate tectonics) Earth's record. Mars’ sedimentary record preserves evidence for progressive desiccation and oxidation of the surface over time, but simple models for the nature and evolution of paleoenvironments (e.g., acid Mars, early warm and wet versus late cold and dry) have given way to the view that, similar to Earth, different climate regimes on Mars coexisted on regional scales and evolved on variable timescales, and redox chemistry played a pivotal role. A major accomplishment of Mars exploration has been to demonstrate that surface and subsurface sedimentary environments were both habitable and capable of preserving any biological record

Clay mineral formation under oxidized conditions and implications for paleoenvironments and organic preservation on Mars

Clay mineral-bearing locations have been targeted for martian exploration as potentially habitable environments and as possible repositories for the preservation of organic matter. Although organic matter has been detected at Gale Crater, Mars, its concentrations are lower than expected from meteoritic and indigenous igneous and hydrothermal reduced carbon. We conducted synthesis experiments motivated by the hypothesis that some clay mineral formation may have occurred under oxidized conditions conducive to the destruction of organics. Previous work has suggested that anoxic and/or reducing conditions are needed to synthesize the Fe-rich clay mineral nontronite at low temperatures. In contrast, our experiments demonstrated the rapid formation of Fe-rich clay minerals of variable crystallinity from aqueous Fe^(3+) with small amounts of aqueous Mg^(2+). Our results suggest that Fe-rich clay minerals such as nontronite can form rapidly under oxidized conditions, which could help explain low concentrations of organics within some smectite-containing rocks or sediments on Mars

In Situ Potassium-Argon Geochronology Using Fluxed Fusion and a Double Spike

A document highlights an Li-based fluxing agent that enables sample fusion and quantitative Ar-release at relatively low temperatures (900-1,000 C), readily achievable with current flight resistance furnace designs. A solid, double spike containing known quantities of Ar-39 and K-41 was developed that, when added in known amounts to a sample, enables the extraction of a Ar-40/K-40 ratio for age estimation without a sample mass measurement. The use of a combination of a flux and a double spike as a means of solving the mechanical hurdles to an in situ K-Ar geochronology measurement has never been proposed before. This methodology and instrument design would provide a capability for assessing the ages of rocks and minerals on the surfaces of planets and other rocky terrestrial bodies in the solar system

Origin of acidic surface waters and the evolution of atmospheric chemistry on early Mars

Observations from in situ experiments and planetary orbiters have shown that the sedimentary rocks found at Meridiani Planum, Mars were formed in the presence of acidic surface waters. The water was thought to be brought to the surface by groundwater upwelling, and may represent the last vestiges of the widespread occurrence of liquid water on Mars. However, it is unclear why the surface waters were acidic. Here we use geochemical calculations, constrained by chemical and mineralogical data from the Mars Exploration Rover Opportunity, to show that Fe oxidation and the precipitation of oxidized iron (Fe^(3+)) minerals generate excess acid with respect to the amount of base anions available in the rocks present in outcrop. We suggest that subsurface waters of near-neutral pH and rich in Fe^(2+) were rapidly acidified as iron was oxidized on exposure to O_2 or photo-oxidized by ultraviolet radiation at the martian surface. Temporal variation in surface acidity would have been controlled by the availability of liquid water, and as such, low-pH fluids could be a natural consequence of the aridification of the martian surface. Finally, because iron oxidation at Meridiani would have generated large amounts of gaseous H_2, ultimately derived from the reduction of H_2O, we conclude that surface geochemical processes would have affected the redox state of the early martian atmosphere

Evidence for plunging river plume deposits in the Pahrump Hills member of the Murray formation, Gale crater, Mars

Recent robotic missions to Mars have offered new insights into the extent, diversity and habitability of the Martian sedimentary rock record. Since the Curiosity rover landed in Gale crater in August 2012, the Mars Science Laboratory Science Team has explored the origins and habitability of ancient fluvial, deltaic, lacustrine and aeolian deposits preserved within the crater. This study describes the sedimentology of a ca 13 m thick succession named the Pahrump Hills member of the Murray formation, the first thick fine‐grained deposit discovered in situ on Mars. This work evaluates the depositional processes responsible for its formation and reconstructs its palaeoenvironmental setting. The Pahrump Hills succession can be sub‐divided into four distinct sedimentary facies: (i) thinly laminated mudstone; (ii) low‐angle cross‐stratified mudstone; (iii) cross‐stratified sandstone; and (iv) thickly laminated mudstone–sandstone. The very fine grain size of the mudstone facies and abundant millimetre‐scale and sub‐millimetre‐scale laminations exhibiting quasi‐uniform thickness throughout the Pahrump Hills succession are most consistent with lacustrine deposition. Low‐angle geometric discordances in the mudstone facies are interpreted as ‘scour and drape’ structures and suggest the action of currents, such as those associated with hyperpycnal river‐generated plumes plunging into a lake. Observation of an overall upward coarsening in grain size and thickening of laminae throughout the Pahrump Hills succession is consistent with deposition from basinward progradation of a fluvial‐deltaic system derived from the northern crater rim into the Gale crater lake. Palaeohydraulic modelling constrains the salinity of the ancient lake in Gale crater: assuming river sediment concentrations typical of floods on Earth, plunging river plumes and sedimentary structures like those observed at Pahrump Hills would have required lake densities near freshwater to form. The depositional model for the Pahrump Hills member presented here implies the presence of an ancient sustained, habitable freshwater lake in Gale crater for at least ca 10^3 to 10^7 Earth years

Evidence for plunging river plume deposits in the Pahrump Hills member of the Murray formation, Gale crater, Mars

Recent robotic missions to Mars have offered new insights into the extent, diversity and habitability of the Martian sedimentary rock record. Since the Curiosity rover landed in Gale crater in August 2012, the Mars Science Laboratory Science Team has explored the origins and habitability of ancient fluvial, deltaic, lacustrine and aeolian deposits preserved within the crater. This study describes the sedimentology of a ca 13 m thick succession named the Pahrump Hills member of the Murray formation, the first thick fine‐grained deposit discovered in situ on Mars. This work evaluates the depositional processes responsible for its formation and reconstructs its palaeoenvironmental setting. The Pahrump Hills succession can be sub‐divided into four distinct sedimentary facies: (i) thinly laminated mudstone; (ii) low‐angle cross‐stratified mudstone; (iii) cross‐stratified sandstone; and (iv) thickly laminated mudstone–sandstone. The very fine grain size of the mudstone facies and abundant millimetre‐scale and sub‐millimetre‐scale laminations exhibiting quasi‐uniform thickness throughout the Pahrump Hills succession are most consistent with lacustrine deposition. Low‐angle geometric discordances in the mudstone facies are interpreted as ‘scour and drape’ structures and suggest the action of currents, such as those associated with hyperpycnal river‐generated plumes plunging into a lake. Observation of an overall upward coarsening in grain size and thickening of laminae throughout the Pahrump Hills succession is consistent with deposition from basinward progradation of a fluvial‐deltaic system derived from the northern crater rim into the Gale crater lake. Palaeohydraulic modelling constrains the salinity of the ancient lake in Gale crater: assuming river sediment concentrations typical of floods on Earth, plunging river plumes and sedimentary structures like those observed at Pahrump Hills would have required lake densities near freshwater to form. The depositional model for the Pahrump Hills member presented here implies the presence of an ancient sustained, habitable freshwater lake in Gale crater for at least ca 10^3 to 10^7 Earth years

Methane bursts as a trigger for intermittent lake-forming climates on post-Noachian Mars

Lakes existed on Mars later than 3.6 billion years ago, according to sedimentary evidence for deltaic deposition. The observed fluviolacustrine deposits suggest that individual lake-forming climates persisted for at least several thousand years (assuming dilute flow). But the lake watersheds’ little-weathered soils indicate a largely dry climate history, with intermittent runoff events. Here we show that these observational constraints, although inconsistent with many previously proposed triggers for lake-forming climates, are consistent with a methane burst scenario. In this scenario, chaotic transitions in mean obliquity drive latitudinal shifts in temperature and ice loading that destabilize methane clathrate. Using numerical simulations, we find that outgassed methane can build up to atmospheric levels sufficient for lake-forming climates, if methane clathrate initially occupies more than 4% of the total volume in which it is thermodynamically stable. Such occupancy fractions are consistent with methane production by water–rock reactions due to hydrothermal circulation on early Mars. We further estimate that photochemical destruction of atmospheric methane curtails the duration of individual lake-forming climates to less than a million years, consistent with observations. We conclude that methane bursts represent a potential pathway for intermittent excursions to a warm, wet climate state on early Mars