The sample analysis at Mars instrument evolved gas analyzer (SAM-EGA) has detected evolved water, H2, SO2, H2S, NO, CO2, CO, O2, and HCl from two eolian sediments and nine sedimentary rocks from Gale ...Crater, Mars. These evolved gas detections indicate nitrates, organics, oxychlorine phase, and sulfates are widespread with phyllosilicates and carbonates occurring in select Gale Crater materials. Coevolved CO2 (160 +/- 248-2373 +/- 820 μgC(CO2)/g) and CO (11 +/- 3-320 +/- 130 μgC(CO)/g) suggest that organic C is present in Gale Crater materials. Five samples evolved CO2 at temperatures consistent with carbonate (0.32 +/- 0.05-0.70 +/- 0.1 wt % CO3). Evolved NO amounts to 0.002 +/- 0.007-0.06 +/- 0.03 wt % NO3. Evolution of O2 suggests that oxychlorine phases (chlorate/perchlorate) (0.05 +/- 0.025-1.05 +/- 0.44 wt % ClO4) are present, while SO2 evolution indicates the presence of crystalline and/or poorly crystalline Fe and Mg sulfate and possibly sulfide. Evolved H2O (0.9 +/- 0.3-2.5 +/- 1.6 wt % H2O) is consistent with the presence of adsorbed water, hydrated salts, interlayer/structural water from phyllosilicates, and possible inclusion water in mineral/amorphous phases. Evolved H2 and H2S suggest that reduced phases occur despite the presence of oxidized phases (nitrate, oxychlorine, sulfate, and carbonate). SAM results coupled with CheMin mineralogical and Alpha-Particle X-ray Spectrometer elemental analyses indicate that Gale Crater sedimentary rocks have experienced a complex authigenetic/diagenetic history involving fluids with varying pH, redox, and salt composition. The inferred geochemical conditions were favorable for microbial habitability and if life ever existed, there was likely sufficient organic C to support a small microbial population.
Modified clay minerals on Mars
Sedimentary rocks exposed in Gale crater on Mars contain extensive clay minerals. Bristow
et al.
analyzed drill samples collected by the Curiosity rover as it climbed ...up sedimentary layers in the crater. They found evidence of past reactions with liquid water and sulfate brines, which could have percolated through the clay from an overlying sulfate deposit. Similar sulfate deposits are widespread across the planet and represent some of the last sedimentary rocks to form before the planet lost its surface liquid water, so the results inform our understanding of the geologic processes that occurred as Mars dried out.
Science, abg5449, this issue p.
198
Clay minerals examined by the Curiosity rover contain evidence of reactions with sulfate brines as Mars dried out.
Mars’ sedimentary rock record preserves information on geological (and potential astrobiological) processes that occurred on the planet billions of years ago. The
Curiosity
rover is exploring the lower reaches of Mount Sharp, in Gale crater on Mars. A traverse from Vera Rubin ridge to Glen Torridon has allowed
Curiosity
to examine a lateral transect of rock strata laid down in a martian lake ~3.5 billion years ago. We report spatial differences in the mineralogy of time-equivalent sedimentary rocks <400 meters apart. These differences indicate localized infiltration of silica-poor brines, generated during deposition of overlying magnesium sulfate–bearing strata. We propose that destabilization of silicate minerals driven by silica-poor brines (rarely observed on Earth) was widespread on ancient Mars, because sulfate deposits are globally distributed.
Evolved gas analysis (EGA) data from the Sample Analysis at Mars (SAM) instrument suite indicated Fe‐rich smectite, carbonate, oxidized organics, Fe/Mg sulfate, and chloride in sedimentary rocks from ...the Glen Torridon (GT) region of Gale crater that displayed phyllosilicate spectral signatures from orbit. SAM evolved H2O data indicated that the primary phyllosilicate in all GT samples was an Fe‐rich dioctahedral smectite (e.g., nontronite) with lesser amounts of a phyllosilicate such as mixed layer talc‐serpentine or greenalite‐minnesotaite. CO2 data supported the identification of siderite in several samples, and CO2 and CO data was also consistent with trace oxidized organic compounds such as oxalate salts. SO2 data indicated trace and/or amorphous Fe sulfates in all samples and one sample may contain Fe sulfides. SO2 data points to significant Mg sulfates in two samples, and lesser amounts in several other samples. A lack of evolved O2 indicated the absence of oxychlorine salts and Mn3+/Mn4+ oxides. The lack of, or very minor, evolved NO revealed absent or very trace nitrate/nitrite salts. HCl data suggested chloride salts in GT samples. Constraints from EGA data on mineralogy and chemistry indicated that the environmental history of GT involved alteration with fluids of variable redox potential, chemistry and pH under a range of fluid‐to‐rock ratio conditions. Several of the fluid episodes could have provided habitable environmental conditions and carbon would have been available to any past microbes though the lack of significant N could have been a limiting factor for microbial habitability in the GT region.
Plain Language Summary
The Mars Science Laboratory Curiosity rover carried out a comprehensive investigation of the sedimentary rocks in the Glen Torridon (GT) region in Gale crater, Mars, to better understand Martian geologic history. The rover’s Sample Analysis at Mars instrument suite was used to heat samples from GT and detect gases that were evolved to help identify the volatile‐bearing mineralogy of the samples. Results indicated the presence of Fe‐rich smectite, carbonate, oxidized organics, Fe and Mg sulfate, and chloride while oxychlorine salts, Mn3+/Mn4+ oxides, and nitrate/nitrite salts were either not detected or occurred in trace amounts. This mineralogy data implied that geochemical conditions and fluid‐to‐rock ratios varied over time and that the conditions of GT depositional and diagenetic environments would have been amenable to microbial life with sufficient carbon but nitrogen abundances could have been limiting.
Key Points
Sample Analysis at Mars data indicated Fe‐smectite, carbonate, oxidized organics, Fe/Mg sulfates, and chlorides in Glen Torridon (GT) rocks
GT’s environmental history involved fluids of variable redox potential and chemistry under a range of fluid‐to‐rock ratios
Fluid episodes could have provided habitable environments and carbon was present, but nitrogen could have been a limiting factor
Data returned by NASA’s Mars Science Laboratory Curiosity rover showed evidence for abundant secondary materials, including Fe‐oxides, phyllosilicates, and an amorphous component on and below Vera ...Rubin ridge in the Murray formation. We used equilibrium thermochemical modeling to test the hypothesis that altered sediments were deposited as detrital igneous grains and subsequently underwent diagenesis. Chemical compositions of the Murray formations’ altered components were calculated using data returned by the chemistry and mineralogy X‐ray diffraction instrument and the alpha particle X‐ray spectrometer on board Curiosity. Reaction of these alteration compositions with a CO2‐poor and oxidizing dilute aqueous solution was modeled at 25–100 °C, with 10–50% Fe3+/Fetot of the host rock. The modeled alteration assemblages included abundant phyllosilicates and Fe‐oxides at water‐to‐rock ratios >100. Modeled alteration abundances were directly comparable to observed abundances of hematite and clay minerals at a water‐to‐rock ratio of 10,000, for system temperatures of 50–100 °C with fluid pH ranging from 7.9 to 9.3. Modeling results suggest that the hematite–clay mineral assemblage is primarily the result of enhanced groundwater flow compared to the Sheepbed mudstone observed at Yellowknife Bay, and underwent further, localized alteration to produce the mineralogy observed by Curiosity.
Following K‐Ar dating of a mudstone and a sandstone, a third sample has been dated by the Curiosity rover exploring Gale Crater. The Mojave 2 mudstone, which contains relatively abundant jarosite, ...yielded a young K‐Ar bulk age of 2.57 ± 0.39 Ga (1σ precision). A two‐step heating experiment was implemented in an effort to resolve the K‐Ar ages of primary and secondary mineralogical components within the sample. This technique involves measurement of 40Ar released in low‐temperature (500°C) and high‐temperature (930°C) steps, and a model of the potassium distribution within the mineralogical components of the sample. Using this method, the high‐temperature step yields a K‐Ar model age of 4.07 ± 0.63 Ga associated with detrital plagioclase, compatible with the age obtained on the Cumberland mudstone by Curiosity. The low‐temperature step, associated with jarosite mixed with K‐bearing evaporites and/or phyllosilicates, gave a youthful K‐Ar model age of 2.12 ± 0.36 Ga. The interpretation of this result is complicated by the potential for argon loss after mineral formation. Comparison with the results on Cumberland and previously published constraints on argon retentivity of the individual phases likely to be present suggests that the formation age of the secondary materials, correcting for plausible extents of argon loss, is still less than 3 Ga, suggesting post‐3 Ga aqueous processes occurred in the sediments in Gale Crater. Such a result is inconsistent with K‐bearing mineral formation in Gale Lake and instead suggests postdepositional fluid flow at a time after surface fluvial activity on Mars is thought to have largely ceased.
Key Points
A third radiometric age dating experiment has been conducted on Mars
The model formation age of plagioclase is greater than 4 Ga, while the model age for jarosite is less than 3 Ga
The young jarosite age suggests the presence of liquid water in Gale Crater during the Amazonian period, most likely in the subsurface
Life detection in the solar system relies on the unambiguous identification of signatures of life and habitability. Organic molecules are essential to life as we know it, and yet many organic ...compounds are ubiquitous in the solar system and can be synthesized abiotically; thus, their presence alone is not indicative of life. On Earth, chemical signatures of life's processes are often left behind in minerals through the biologically induced formation of secondary minerals or intermediary organic complexes. In natural rocks biomolecules and organic species often co-occur with minerals, and their overlapping peaks can create difficulties in interpretation. In the process of identifying the minerals and organic species in our basaltic samples we noticed signatures for cyanates co-occurring with organic molecules. Cyanates are an overlooked group of nitrogen compounds in which C is bonded to N (e.g., OCN− or SCN−) that often co-occur with urea and ammonium in environments where microorganisms are present. These compounds are common in many terrestrial and oceanic environments and play an important role in biogeochemical nitrogen cycling. In natural systems, these compounds form as the result of multiple biogeochemical pathways, often from the interaction of microbes with a chemically active environment. These interactions leave behind signatures in the form biotic breakdown products such as urea or ammonium and organic reaction byproducts that are observable with spectroscopic methods. To explore these relationships, we used field-portable Raman spectrometers and laboratory micro-Raman imaging to characterize and compare samples collected from two different terrestrial basaltic environments, a lava tube on Mauna Loa, Hawaii, dominated by the precipitation of sulfate minerals and a geothermal stream at Hveragil, Iceland dominated by the precipitation of carbonate minerals. The Raman (RS) measurements were complemented by laser induced breakdown spectroscopy (LIBS), Long-wave Infrared (IR) LIBS, with the addition of gas chromatograph mass spectrometry (GC–MS) and inductively coupled plasma-mass spectrometry (ICP-MS) to identify cyanate compounds, biomolecules, and other nitrogenous compounds related to the breakdown or production of cyanate in host basalts and secondary precipitates. The RS data suggest that the reason for RS cyanate signatures in the carbonate samples could be due to luminescence artifacts while those detected in the host basalts may be due to hydrolysis chemistry. The cyanate signatures detected in the lava tube samples dominated by sulfates do not seem to be luminescence artifacts but may in fact be evidence of an active microbial nitrogen cycle. Our results inform the spectroscopic detection of cyanates in planetary analog environments and the challenges in their identification. Further work is needed to understand their potential as biosignatures on other planetary bodies.
•Basaltic environs have detectable features useful to search for life beyond Earth.•N-compounds (cyanates) are observed with secondary minerals and organic molecules.•Raman spectroscopy, LIBS, GC–MS, ICP-MS are complementary for life detection.
Activated carbon filters are used to limit engine damage by siloxanes when biogas is utilised to provide electricity. However, carbon filter siloxane removal performance is poorly understood as until ...recently, it had not been possible to measure siloxanes on-line. In this study, on-line Fourier Transform Infrared (FTIR) spectroscopy was developed to measure siloxane concentration in real biogas both upstream (86.1–157.5mgm−3) and downstream (2.2–4.3mgm−3) of activated carbon filters. The FTIR provided reasonable precision upstream of the carbon vessel with a root mean square error of 10% using partial least squares analysis. However, positive interference from volatile organic carbons was observed in downstream gas measurements limiting precision at the outlet to an RMSE of 1.5mgm−3 (47.8%). Importantly, a limit of detection of 3.2mgm−3 was identified which is below the recommended siloxane limit and evidences the applicability of on-line FTIR for this application.
Display omitted
•FTIR spectroscopy was used to measure siloxanes in biogas at full scale.•Interference from bulk and trace gases is identified up/downstream of carbon filter.•LOD of 3.2mgm−3 is achieved, demonstrating industrial relevance.•Cost savings are estimated to be up to £0.007kwh−1.
Curiosity investigated active eolian sands near linear dunes during Phase 2 of the Bagnold Dunes campaign in Gale crater, Mars. Ogunquit Beach, a sample scooped from a large‐ripple trough within the ...Mount Desert Island ripple field and delivered to the Chemistry and Mineralogy (CheMin) X‐ray diffraction instrument, is dominated by basaltic igneous minerals and X‐ray amorphous materials. CheMin mineralogy of the Gobabeb sample acquired at a large‐ripple crest on the Namib barchan dune during Phase 1 is similar to Ogunquit Beach. Ogunquit Beach, however, contains more plagioclase and Gobabeb contains more olivine. Compact Reconnaissance Imaging Spectrometer for Mars (CRISM)‐based estimates of mineralogy at the optical surface of Namib Dune and Mount Desert Island demonstrate that surface sands are enriched in olivine and depleted in plagioclase over Mount Desert Island relative to Namib Dune. Differences between CheMin‐derived and CRISM‐derived mineralogies suggest sorting by grain size on bedform to dune field scales. Crystal chemistry from CheMin suggests contributions from multiple igneous sources and the local bedrock.
Plain Language Summary
Remote sensing data from orbit indicate that wind‐blown sands in the Bagnold Dune Field in Gale crater, Mars, are sorted by their composition. The Mars Science Laboratory Curiosity rover studied the Bagnold Dune Field at two locations to investigate the chemical and mineral composition of the sands and why they are sorted across the dune field. Data from Curiosity show distinct differences between the minerals in the upwind portion of the dune field compared to the downwind portion, but these differences are not the same as those observed from orbit. The scale and location of the sampling by Curiosity compared to orbiters explains the discrepancy between the two techniques. Results from both techniques suggest subtle differences in mineralogy within a single dune and across the dune field that can be explained by sorting from wind and contribution from the erosion of local bedrock.
Key Points
The mineralogy of active eolian sands were measured by the Curiosity rover at two locations in the Bagnold Dune Field in Gale crater, Mars
X‐ray diffraction data from the CheMin instrument of two sand samples indicate differences in plagioclase and olivine abundances
The mineralogy derived from CheMin and CRISM can be used in concert to characterize sediment sorting and sources across the Bagnold Dunes
In this study, online Fourier transform infrared (FTIR) spectroscopy has been used to generate the first comprehensive characterization of full-scale carbon contactors for siloxane removal from ...biogas. Using FTIR, two clear operational regions within the exhaustion cycle were evidenced: an initial period of pseudo-steady state where the outlet siloxane concentration was consistently below the proposed siloxane limits; and a second period characterized by a progressive rise in outlet siloxane concentration during and after breakthrough. Due to the sharp breakthrough front identified, existing detection methods (which comprise field sampling coupled with laboratory-based chromatographic determination) are insufficiently responsive to define breakthrough, thus carbon contactors currently remain in service while providing limited protection to the combined heat and power engine. Integration of the exhaustion cycle to breakthrough identified average specific media capacities of 8.5-21.5 g
siloxane
, which are lower than that has been reported for vapour phase granular activated carbon (GAC). Further speciation of the biogas phase identified co-separation of organic compounds (alkanes and aromatics), which will inevitably reduce siloxane capacity. However, comparison of the five full-scale contactors identified that greater media capacity was accessible through operating contactors at velocities sufficient to diminish axial dispersion effects. In addition to enabling significant insight into gas phase GAC contactors, the use of FTIR for online control of GAC for siloxane removal is also presented.
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