Extraterrestrial delivery of cyanide may have been crucial for the origin of life on Earth since cyanide is involved in the abiotic synthesis of numerous organic compounds found in extant life; ...however, little is known about the abundance and species of cyanide present in meteorites. Here, we report cyanide abundance in a set of CM chondrites ranging from 50 ± 1 to 2472 ± 38 nmol·g1, which relates to the degree of aqueous alteration of the meteorite and indicates that parent body processing inuenced cyanide abundance. Analysis of the Lewis Cliff 85311 meteorite shows that its releasable cyanide is primarily in the form of FeII (CN)5(CO)3 and FeII(CN)4(CO)22-. Meteoritic delivery of iron cyanocarbonyl complexes to early Earth likely provided an important point source of free cyanide. Iron cyanocarbonyl complexes may have served as precursors to the unusual FeII(CN)(CO) moieties that form the catalytic centers of hydrogenases, which are thought to be among the earliest enzymes.
The Sample Analysis at Mars (SAM) instrument on the Mars Science Laboratory (MSL) rover Curiosity detected evolved gases during thermal analysis of soil samples from the Rocknest aeolian deposit in ...Gale Crater. Major species detected (in order of decreasing molar abundance) were H2O, SO2, CO2, and O2, all at the µmol level, with HCl, H2S, NH3, NO, and HCN present at the tens to hundreds of nmol level. We compute weight % numbers for the major gases evolved by assuming a likely source and calculate abundances between 0.5 and 3 wt.%. The evolution of these gases implies the presence of both oxidized (perchlorates) and reduced (sulfides or H‐bearing) species as well as minerals formed under alkaline (carbonates) and possibly acidic (sulfates) conditions. Possible source phases in the Rocknest material are hydrated amorphous material, minor clay minerals, and hydrated perchlorate salts (all potential H2O sources), carbonates (CO2), perchlorates (O2 and HCl), and potential N‐bearing materials (e.g., Martian nitrates, terrestrial or Martian nitrogenated organics, ammonium salts) that evolve NH3, NO, and/or HCN. We conclude that Rocknest materials are a physical mixture in chemical disequilibrium, consistent with aeolian mixing, and that although weathering is not extensive, it may be ongoing even under current Martian surface conditions.
Key Points
Major volatiles detected by SAM were H2O, SO2, CO2, and O2
Minor volatiles include HCl, H2S, NH3, NO, and HCN
Calculating abundances from counts per second is explained
•We report the technical details of the laser desorption/ionization mass spectrometry mode operation on Mars Organic Molecule Analyzer (MOMA).•The MOMA instrument components were designed/modified ...and miniaturized specifically for Martian environment.•We show here the system-level analytical capabilities of MOMA have met the mission requirements.
The Mars Organic Molecule Analyzer (MOMA), a dual-source, ion trap-based instrument capable of both pyrolysis-gas chromatography mass spectrometry (pyr/GC–MS) and laser desorption/ionization mass spectrometry (LDI-MS), is the core astrobiology investigation on the ExoMars rover. The MOMA instrument will be the first spaceflight mass analyzer to exploit the LDI technique to detect refractory organic compounds and characterize host mineralogy; this mode of analysis will be conducted at Mars ambient conditions. In order to achieve high performance in the Martian environment while keeping the instrument compact and low power, a number of innovative designs and components have been implemented for MOMA. These include a miniaturized linear ion trap (LIT), a fast actuating aperture valve with ion inlet tube, and a Microelectromechanical System (MEMS) Pirani sensor. Advanced analytical capabilities like Stored Waveform Inverse Fourier Transform (SWIFT) for selected ion ejection and tandem mass spectrometry (MS/MS) are realized in LDI-MS mode, and enable the isolation and enhancement of specific mass ranges and structural analysis, respectively. We report here the technical details of these instrument components as well as system-level analytical capabilities, and we review the applications of this technology to Mars and other high-priority targets of planetary exploration.
Evidence from recent Mars missions indicates the presence of perchlorate salts up to 1 wt % level in the near-surface materials. Mixed perchlorates and other oxychlorine species may complicate the ...detection of organic molecules in bulk martian samples when using pyrolysis techniques. To address this analytical challenge, we report here results of laboratory measurements with laser desorption mass spectrometry, including analyses performed on both commercial and Mars Organic Molecule Analyzer (MOMA) breadboard instruments. We demonstrate that the detection of nonvolatile organics in selected spiked mineral-matrix materials by laser desorption/ionization (LDI) mass spectrometry is not inhibited by the presence of up to 1 wt % perchlorate salt. The organics in the sample are not significantly degraded or combusted in the LDI process, and the parent molecular ion is retained in the mass spectrum. The LDI technique provides distinct potential benefits for the detection of organics in situ on the martian surface and has the potential to aid in the search for signs of life on Mars.
Abstract
Geochronology is an indispensable tool for reconstructing the geologic history of planets, essential to understanding the formation and evolution of our solar system. Bombardment chronology ...bounds models of solar system dynamics, as well as the timing of volatile, organic, and siderophile element delivery. Absolute ages of magmatic products provide constraints on the dynamics of magma oceans and crustal formation, as well as the longevity and evolution of interior heat engines and distinct mantle/crustal source regions. Absolute dating also relates habitability markers to the timescale of evolution of life on Earth. However, the number of terrains important to date on worlds of the inner solar system far exceeds our ability to conduct sample return from all of them. In preparation for the upcoming Decadal Survey, our team formulated a set of medium-class (New Frontiers) mission concepts to three different locations (the Moon, Mars, and Vesta) where sites that record solar system bombardment, magmatism, and habitability are uniquely preserved and accessible. We developed a notional payload to directly date planetary surfaces, consisting of two instruments capable of measuring radiometric ages, an imaging spectrometer, optical cameras to provide site geologic context and sample characterization, a trace-element analyzer to augment sample contextualization, and a sample acquisition and handling system. Landers carrying this payload to the Moon, Mars, and Vesta would likely fit into the New Frontiers cost cap in our study (∼$1B). A mission of this type would provide crucial constraints on planetary history while also enabling a broad suite of complementary investigations.
Geochronology, or determination of absolute ages for geologic events, underpins many inquiries into the formation and evolution of planets and our Solar System. Absolute ages of ancient and recent ...magmatic products provide strong constraints on the dynamics of magma oceans and crustal formation, as well as the longevity and evolution of interior heat engines and distinct mantle/crustal source regions. Absolute dating also relates habitability markers to the timescale of evolution of life on Earth. However, the number of geochronologically-significant terrains across the inner Solar System far exceeds our ability to conduct sample return from all of them. In preparation for the upcoming Decadal Survey, our team formulated a set of medium-class (New Frontiers) mission concepts to three different locations (the Moon, Mars, and Vesta) where sites that record Solar System bombardment, magmatism, and/or habitability are uniquely preserved and accessible. We developed a notional payload to directly date planetary surfaces, consisting of two instruments capable of measuring radiometric ages in situ, an imaging spectrometer, optical cameras to provide site geologic context and sample characterization, a trace element analyzer to augment sample contextualization, and a sample acquisition and handling system. Landers carrying this payload to the Moon, Mars, and Vesta would likely fit into the New Frontiers cost cap in our study (~$1B). A mission of this type would provide crucial constraints on planetary history while also enabling a broad suite of investigations such as basic geologic characterization, geomorphologic analysis, ground truth for remote sensing analyses, analyses of major, minor, trace, and volatile elements, atmospheric and other long-lived monitoring, organic molecule analyses, and soil and geotechnical properties.
Oxygen Fugacity of Global Ocean Island Basalts Willhite, Lori N.; Arevalo, Ricardo; Piccoli, Philip ...
Geochemistry, geophysics, geosystems,
January 2024, 2024-01-00, 20240101, Letnik:
25, Številka:
1
Journal Article
Recenzirano
Odprti dostop
Mantle plumes contain heterogenous chemical components and sample variable depths of the mantle, enabling glimpses into the compositional structure of Earth's interior. In this study, we evaluated ...ocean island basalts (OIB) from nine plume locations to provide a global and systematic assessment of the relationship between fO2 and He‐Sr‐Nd‐Pb‐W‐Os isotopic compositions. Ocean island basalts from the Pacific (Austral Islands, Hawaii, Mangaia, Samoa, Pitcairn), Atlantic (Azores, Canary Islands, St. Helena), and Indian Oceans (La Réunion) reveal that fO2 in OIB is heterogeneous both within and among hotspots. Taken together with previous studies, global OIB have elevated and heterogenous fO2 (average = +0.5 ∆FMQ; 2SD = 1.5) relative to prior estimates of global mid‐ocean ridge basalts (MORB; average = −0.1 ∆FMQ; 2SD = 0.6), though many individual OIB overlap MORB. Specific mantle components, such as HIMU and enriched mantle 2 (EM2), defined by radiogenic Pb and Sr isotopic compositions compared to other OIB, respectively, have distinctly high fO2 based on statistical analysis. Elevated fO2 in OIB samples of these components is associated with higher whole‐rock CaO/Al2O3 and olivine CaO content, which may be linked to recycled carbonated oceanic crust. EM1‐type and geochemically depleted OIB are generally not as oxidized, possibly due to limited oxidizing potential of the recycled material in the enriched mantle 1 (EM1) component (e.g., sediment) or lack of recycled materials in geochemically depleted OIB. Despite systematic offset of the fO2 among EM1‐, EM2‐, and HIMU‐type OIB, geochemical indices of lithospheric recycling, such as Sr‐Nd‐Pb‐Os isotopic systems, generally do not correlate with fO2.
Plain Language Summary
Rocks from Earth's surface are mixed back into the interior during crustal recycling as a result of plate tectonics and subduction. For example, plate tectonics results in subduction of oceanic crust back into the mantle. Recycling of surface materials might oxidize the interior of the Earth. Mantle plumes, which are buoyantly rising portions of the mantle that create ocean islands such as Hawaii, Iceland, and Samoa, have the chemical and isotopic characteristics associated with recycled materials in their sources. Here we investigate rocks from mantle plumes that have heterogeneous isotopic compositions as a result of incorporating different types of recycled material to test whether their oxygen fugacity varies systematically with the type of recycled crust in their source. We show that some types of mantle plume‐derived rocks, called HIMU and enriched mantle 2 characterized by their extreme isotopic compositions, are more oxidized than the enriched mantle 1 or typical geochemically depleted rocks from mantle plumes and from spreading centers in the oceans. These results link certain recycled materials to oxidation of Earth's mantle.
Key Points
Oxygen fugacity generally does not correlate with radiogenic isotopic compositions that trace recycled material in mantle‐derived rocks
HIMU and enriched mantle 2 ocean island basalts are more oxidized than enriched mantle 1 or geochemically depleted ocean island basalts and mid‐ocean ridge basalts
This collection of articles represents the fourth in a series of reviews in which authors have aimed at capturing the key advances in a range of analytical fields (Hergt et al. 2005, 2006, 2008). The ...publication period under review is 2008–2009 and the intention here is to provide readers with a summary of the most influential developments published during this period, across a broad range of topics appropriate to the Earth and environmental sciences. Most authors comment on the ways in which the emphases of research in their specific fields of examination have changed over time. All note an increase in rigour and focus on data quality. Whether advances have taken place in instrumentation, sample manipulation or data deconvolution, there are a large number of dedicated scientists out there contributing to the high quality of geochemical data employed in geological and environmental research.
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