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An interpretation of special and general isotopic anomalies in r-process nuclei

My analysis of new discoveries by McCulloch and Wasserburg of Ba and Nd isotopic anomalies in inclusions of the Allende meteorite argues that (1) these anomalies contain special extinct radioactivities resulting from radioactive decay within grains formed in and ejected from the supernova interior, (2) the inclusions studied are fused assemblies of interstellar grains that were never totally vaporized, and (3) theoretical separation into r and s abundances suggests that fluctuations between r and s components has occurred during the accumulation processes. These points lend support to a new chemical picture of the early solar system that I have developed, although many interpretations remain possible. Measurements of the neutron-capture cross sections of Nd isotopes are urgently needed to experimentally validate these conclusions.

Clayton, D. D.↗

Experimental Study of Abiotic Organic Synthesis at High Temperature and Pressure Conditions: Carbon Isotope and Mineral Surface Characterizations

Abiotic organic synthesis processes have been proposed as potential mechanisms for methane generation in subseafloor hydrothermal systems on Earth, and on other planets. To better understand the detailed reaction pathways and carbon isotope fractionations in this process under a wide range of physical and chemical conditions, hydrothermal experiments at high temperature (750 C) and pressure (0.55 GPa) were performed using piston cylinder apparatus. Formic acid was used as the source of CO2 and H2, and magnetite was the mineral catalyst. The chemical and carbon isotopic compositions of dissolved organic products were determined by GC-C-MS-IRMS, while organic intermediaries on the mineral catalyst were characterized by Pyrolysis-GC-MS. Among experimental products, dissolved CO2 was the dominant carbon species with a relative abundance of 88 mol%. Dissolved CH4 and C2H6 were also identified with a mole ratio of CH4 over C2H6 of 15:1. No dissolved CO was detected in the experiment, which might be attributable to the loss of H2 through the Au capsule used in the experiments at high temperature and pressure conditions and corresponding conversion of CO to CO2 by the water-gas shift reaction. Carbon isotope results showed that the 13C values of CH4 and C2H6 were -50.3% and -39.3% (V-PDB), respectively. CO2 derived from decarboxylation of formic acid had a (sigma)C-13 value of -19.2%, which was 3.2% heavier than its source, formic acid. The (sigma)C-13 difference between CO2 and CH4 was 31.1%, which was higher than the value of 9.4% calculated from theoretical isotopic equilibrium predictions at experimental conditions, suggesting the presence of a kinetic isotope effect. This number was also higher than the values (4.6 to 27.1%) observed in similar experiments previously performed at 400 C and 50 MPa with longer reaction times. CH4 is 11.0% less enriched in C-13 than C2H6. Alcohols were observed as carbon compounds on magnetite surfaces by Pyrolysis-GC-MS, which confirms the hypothesis regarding the reaction pathways of hydrothermal abiotic organic synthesis proposed by Fu et al. (2007, 2008). In this proposed pathway, hydroxymethylene (-CHOH) groups serve as organic intermediaries on mineral surfaces while dissolved H2 serves as a chain terminator/breaker to generate short chain hydrocarbons and oxygenated compounds. This pathway is different from the carbide polymerization theory of Fischer- Tropsch-type (FTT) synthesis in a gas phase. The observed increase of (sigma)C-13 values of C1 and C2 alkanes with carbon number in our hydrothermal experiments can be readily interpreted by hydroxymethylene pathway, and might be used to differentiate between hydroxymethylene and carbide polymerization pathways. Carbon isotope analysis of alcohols on mineral catalyst surfaces is under way to provide further constraints on formation of organic compounds by FTT in hydrothermal systems.

Fu, Qi↗

Interstellar oxygen-17

Cases of line emission were observed from the molecular clouds associated with the Orion Nebula and the rho Ophiuchi complex. The emission is attributed to a certain rotational transition of CO consisting of the isotopes C-12 and O-17. This observation signifies the first detection of O-17 outside the solar system. It is pointed out that the relative abundance of O-17 is an important astrophysical quantity because of a possible enrichment during the hot CNO cycle.

Encrenaz, P. J.↗

Photochemistry and evolution of Mars' atmosphere - A Viking perspective

Viking measurements of the upper atmosphere of Mars have indicated thermospheric temperatures below 200 K, colder than those originally calculated by remote sensing experiments. It is suggested that dynamical coupling of the upper and lower regions of the Martian atmosphere may account for the variability in thermospheric temperature. The absorption of extreme ultraviolet solar radiation may account for observed ionospheric features, and may provide a source of fast N and O atoms escaping the planet's gravitational field. Measurements of the isotopic composition of O and N may be used to place constraints on models of the evolution of the Martian atmosphere. It is suggested that previous abundance of N2 may have exceeded that of CO2 in the present atmosphere, and that large sources of H2O may exist on the planet. The present degassing rate for nitrogen is felt to be less than the time-averaged degassing rate by at least a factor of 20.

Mcelroy, M. B.↗

High-resolution infrared spectroscopy of Io and possible surface materials

A comparison of new spectra of Io with laboratory-simulated frosts confirms that the dominant materials on Io are SO2 frost in conjunction with a spectrally neutral material presumed to be sulfur. While the 4-micron region spectra are largely explainable in these terms, attention is drawn to a shoulder in the spectrum at 4.04 microns that is suggestive of adsorbed SO2 gas; two shallow, unidentified bands are also noted at 3.85 and 3.91 microns. The isotopic ratios of oxygen and sulfur appear to be normal. The absence of distinct bands in the new spectra in the 5-micron region limits the abundance of sulfate and sulfite compounds.

Howell, Robert R.↗

Requirements for the early atmosphere of Mars from nitrogen isotope ratios

The N escape models of Fox and Dalgarno and Fox required the presence of a dense, early CO2 atmosphere to inhibit fractionation of the N isotopes N-15 and N-14. The computed photochemical escape fluxes are so large at the present that the isotope ratio measured by Viking (about 1.62x terrestrial) can be produced in about 1.5 b.y. This model was refined in several ways. It was updated to incorporate the variation of the escape fluxes with increases in the solar fluxes at earlier times according to the model of Zahnle and Walker. As expected, this exacerbates the problem with overfractionation, but not greatly. Most of the escape and fractionation of the N occurs in the last 1.5 b.y., when the solar flux was only slightly different from the present. The dense early atmosphere must persist only a bit longer in order to reproduce the measured isotope ratio. The model was also modified to take into account changes in the O mixing ratio with time in the past, assuming that the O abundance is proportional to the square root of the solar flux. Although the production rate of O from photodissociation of CO2 scales as the solar flux, the strength of the winds and other mixing processes also increases with the solar flux, resulting in possibly more effective transport of O to the lower atmosphere where it is destroyed by catalytic and three-body recombination mechanisms.

Fox, J. L.↗

Deuterium enrichment of polycyclic aromatic hydrocarbons by photochemically induced exchange with deuterium-rich cosmic ices

The polycyclic aromatic hydrocarbon (PAH) coronene (C24H12) frozen in D2O ice in a ratio of less than 1 part in 500 rapidly exchanges its hydrogen atoms with the deuterium in the ice at interstellar temperatures and pressures when exposed to ultraviolet radiation. Exchange occurs via three different chemical processes: D atom addition, D atom exchange at oxidized edge sites, and D atom exchange at aromatic edge sites. Observed exchange rates for coronene (C24H12)-D2O and d12-coronene (C24D12)-H2O isotopic substitution experiments show that PAHs in interstellar ices could easily attain the D/H levels observed in meteorites. These results may have important consequences for the abundance of deuterium observed in aromatic materials in the interstellar medium and in meteorites. These exchange mechanisms produce deuteration in characteristic molecular locations on the PAHs that may distinguish them from previously postulated processes for D enrichment of PAHs.

NASA Center ARC↗

Lunar and Planetary Science XXXVI, Part 6

Contents include the following: A Model for Multiple Populations of Presolar Diamonds. Characterization of Martian North Polar Geologic Units Using Mars Odyssey THEMIS Data. Effect of Flow on the Internal Structure of the Martian North Polar Layered Deposits. Elemental Abundance Distributions in Basalt Clays and Meteorites: Is It a Biosignature? Early Results on the Saturn System from the Composite Infrared Spectrometer. NanoSIMS D/H Imaging of Isotopically Primitive Interplanetary Dust Particles. Presolar (Circumstellar and Interstellar) Phases in Renazzo: The Effects of Parent Body Processing. Catastrophic Disruption of Hydrated Targets: Implications for the Hydrated Asteroids and for the Production of Interplanetary Dust Particles. Chemical and Mineralogical Analyses of Particles from the Stratospheric Collections Coinciding with the 2002 Leonid Storm and the 2003 Comet Grigg-Skjellerup Trail Passage. An Analysis of the Solvus in the CaS-MnS System. ESA s SMART-1 Mission at the Moon: First Results, Status and Next Steps. Europa Analog Ice-splitting Measurements and Experiments with Ice-Hunveyor on the Frozen Balaton-Lake, Hungary. Chromium on Eros: Further Evidence of Ordinary Chondrite Composition. Dust Devil Tracks on Mars: Observation and Analysis from Orbit and the Surface. Spatial Variation of Methane and Other Trace Gases Detected on Mars: Interpretation with a General Circulation Model. Mars Water Ice and Carbon Dioxide Seasonal Polar Caps: GCM Modeling and Comparison with Mars Express Omega Observations. Component Separation of OMEGA Spectra with ICA. Clathrate Formation in the Near-Surface Environment of Titan. Space Weathering: A Proposed Laboratory Approach to Explaining the Sulfur Depletion on Eros. Sample Collection from Small Airless Bodies: Examination of Temperature Constraints for the TGIP. Sample Collector for the Hera Near-Earth Asteroid Sample Return Mission. A Rugged Miniature Mass-Spectrometer for Measuring Aqueous Geochemistry on Mars. Martian and Lunar Pyroxene Microstructures Studied by Single-Crystal X-Ray Diffraction.

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Organic Matter in Extraterrestrial Water-Bearing Salt Crystals

Introduction: Direct samples of early Solar System fluids are present in two thermally-metamorphosed ordinary chondrite regolith breccias (Monahans (1998) [H5] and Zag [H3-6]), which were found to contain brine-bearing halite (NaCl) crystals that have been added to the regolith of an S-type asteroid following asteroidal metamorphism [1, 2]. The brine-bearing halite grains were proposed to be formed on an icy C-type asteroids (possibly Ceres), and transferred to an S-type asteroid via cryovolcanic event(s) [3]. A unique aspect of these halites is that they contain abundant organic rich solid inclusions hosted within the halites alongside the water inclusions. Methods: We analyzed in detail the compositions of the organic solids and the amino acid content of the halite crystals with two-step laser desorption/laser ionization mass spectrometry (L(sup 2) MS), Raman spectroscopy, X-ray absorption near edge structure (XANES), nanoscale secondary ion mass spectrometry (NanoSIMS), and ultra-performance liquid chromatography fluorescence detection and quadrupole time of flight hybrid mass spectrometry (UPLC-FD/QToF-MS). Results and Discussion: The L(sup 2) MS results show signatures of low-mass polyaromatic hydro-carbons (PAHs) indicated by sequences of peaks separated by 14 atomic mass units (amu) due to successive addition of methylene (CH2) groups to the PAH skeletons [4]. Raman spectra of the micron-sized solid inclusions of the halites indicate the presence of abundant and highly variable organic matter that include a mixture of short-chain aliphatic compounds and macromolecular carbon. C-XANES analysis identified C-rich areas with peaks at 285.0 eV (aromatic C=C) and 286.6 eV (vinyl-keto C=O). However, there is no 1s-sigma* exciton peak (291.7 eV) that is indicative of the development of graphene structure [5], which suggests the organics were synthesized cold. Na-noSIMS analyses show C-rich and N-rich areas that exhibit similar isotopic values with that of the IOM in the unweathered CR chondrites and less metamorphosed meteorites [6], and are moderately enriched in N-15 (delta N-15 = 106.1-164.5 per mille). The total amino acid distribution and abundance of the Zag matrix (approximately 1,940 parts per billion [ppb]) is comparable to other ordinary chondrites (60-3,330 ppb) [7, 8]. While the Zag matrix is gamma-ABA and EACA-deficient, the halite is shown to exhibit an opposite trend and is almost depleted in amino acids. The striking difference in the amino acid contents between the halite and matrix indicates their separate synthetic origins. Conclusion: Abundant, primitive, and highly-diverse N-15-rich organic compounds were detected in brine-water bearing halite crystals that were synthesized on a cryovolcanically-active asteroid. Our study suggests that the asteroidal parent body where the halite precipitated, potentially Ceres, is a host to abundance large variety organic precursors. Insoluble organic matter and amino acids can be synthesized from similar organic precusors under hydrous conditions [9].We envision that similar organic synthetic processes could have occurred on Ceres that synthesized organic solids as well as biologically relevant molecules.

Chan, Q. H. S.↗

Low Total Abundances and a Predominance of n-ω-Amino Acids in Enstatite Chondrites: Implications for Thermal Stability of Amino Acids in the Inner Solar System

Investigating the organic contents of enstatite chondrite meteorites may offer insights into both early inner solar system and early Earth chemistry. Enstatite chondrite meteorites have highly reduced and anhydrous compositions, and their bulk isotopic compositions closely resemble terrestrial values, suggesting that their parent body asteroids accreted within the inner protoplanetary disk and were a primary contributor during Earth’s late accretion (Javoy et al., 1995; Piani et al., 2020). Here, we present the first report of amino acids in enstatite chondrite meteorite samples. Three EH3 meteorites were analyzed (Dominion Range 14021, Larkman Nunatak 12001, and Larkman Nunatak 06252). The acid-hydrolyzed water extracts of the meteorites contained low abundances (1.5 – 215.9 pmol/g) of n-ω-amino acids (glycine, β-alanine, γ-amino-n-butyric acid (γ-ABA), δ-amino-n-valeric acid (δ-AVA), and ε-amino-n-caproic acid (ε-ACA)), but amino acids were not present above detection limits in the non-hydrolyzed samples. The low amino acid abundances and the predominance of n-ω-amino acids resembles amino acid distributions previously observed for thermally altered chondrites. These results suggest that the parent body asteroid was not conducive to the synthesis and/or preservation of α-amino acids, or free amino acids in general, and that EH3 chondrite-like material may not have been a primary contributor of diverse or abundant free amino acids to the early Earth.

Danielle N Simkus↗

Low total abundances and a predominance of n-ω-amino acids in enstatite chondrites: Implications for thermal stability of amino acids in the inner solar system

Investigating the organic contents of enstatite chondrite meteorites may offer insights into both early inner solar system and early Earth chemistry. Enstatite chondrite meteorites have highly reduced and anhydrous compositions, and their bulk isotopic compositions closely resemble terrestrial values, suggesting that their parent body asteroids accreted within the inner protoplanetary disk and were a primary contributor during Earth’s late accretion (Javoy, 1995; Piani et al., 2020). Here, we present the first report of amino acids in enstatite chondrite meteorite samples. Three EH3 meteorites were analyzed (Dominion Range [DOM] 14021, Larkman Nunatak [LAR] 12001, and Larkman Nunatak 06252). The acid-hydrolyzed water extracts of the meteorites contained low abundances (1.5–215.9 pmol per g) of n-ω-amino acids (glycine, β-alanine, γ-amino-n-butyric acid [γ- ABA], δ-amino-n-valeric acid [δ-AVA], and ϵ-amino-n-caproic acid [ϵ-ACA]), but amino acids were not present above detection limits in the nonhydrolyzed samples. The low amino acid abundances and the predominance of n-ω-amino acids resemble amino acid distributions previously observed for thermally altered chondrites. These results suggest that the parent body asteroid was not conducive to the synthesis and/or preservation of α-amino acids, or free amino acids in general, and that EH3 chondrite-like material may not have been a primary contributor of diverse or abundant free amino acids to the early Earth.

Danielle N. Simkus↗

The Amino Acid Composition of the Sutter's Mill Carbonaceous Chondrite

In contrast to the Murchison meteorite which had a complex distribution of amino acids with a total C2 to Cs amino acid abundance of approx.14,000 parts-per-billion (ppb) [2], the Sutters Mill meteorite was found to be highly depleted in amino acids. Much lower abundances (approx.30 to 180 ppb) of glycine, beta-alanine, L-alanine and L-serine were detected in SM2 above procedural blank levels indicating that this meteorite sample experienced only minimal terrestrial amino acid contamination after its fall to Earth. Carbon isotope measurements will be necessary to establish the origin of glycine and beta-alanine in SM2. Other non-protein amino acids that are rare on Earth, yet commonly found in other CM meteorites such as aaminoisobutyric acid (alpha-AIB) and isovaline, were not identified in SM2. However, traces of beta-AIB (approx.1 ppb) were detected in SM2 and could be" extraterrestrial in origin. The low abundances of amino acids in the Sutter's Mill meteorite is consistent with mineralogical evidence that at least some parts of the Sutter's Mill meteorite parent body experienced extensive aqueous and/or thermal alteration.

Glavin, D. P.↗

Markov Chain Monte Carlo Predictions of Neutron-rich Lanthanide Properties as a Probe of r -process Dynamics

Lanthanide element signatures are key to understanding many astrophysical observables, from merger kilonova light curves to stellar and solar abundances. To learn about the lanthanide element synthesis that enriched our solar system, we apply the statistical method of Markov Chain Monte Carlo to examine the nuclear masses capable of forming the r-process rare-earth abundance peak. We describe the physical constraints we implement with this statistical approach and demonstrate the use of the parallel chains method to explore the multidimensional parameter space. We apply our procedure to three moderately neutron-rich astrophysical outflows with distinct types of r-process dynamics. We show that the mass solutions found are dependent on outflow conditions and are related to the r-process path. We describe in detail the mechanism behind peak formation in each case. We then compare our mass predictions for neutron-rich neodymium and samarium isotopes to the latest experimental data from the CPT at CARIBU. Here, we find our mass predictions given outflows that undergo an extended (n,γ)⇌(γ,n) equilibrium to be those most compatible with both observational solar abundances and neutron-rich mass measurements.

79 ASTRONOMY AND ASTROPHYSICS↗

Chondrites and the Protoplanetary Disk, Part 2

Contents include the following: On the Dynamical Evolution of a Nebula and Its Effect on Dust Coagulation and the Formation of Centimeter-sized Particles. The Mineralogy and Grain Properties of the Disk Surfaces in Three Herbig Ae/Be Stars. Astrophysical Observations of Disk Evolution Around Solar Mass Stars. The Systematic Petrology of Chondrites: A Consistent Approach to Assist Classification and Interpretation. Understanding Our Origins: Formation of Sun-like Stars in H II Region Environments. Chondrule Crystallization Experiments. Formation of SiO2-rich Chondrules by Fractional Condensation. Refractory Forsterites from Murchison (CM2) and Yamato 81020 (CO3.0) Chondrites: Cathodoluminescence, Chemical Compositions and Oxygen Isotopes. Apparent I-Xe Cooling Rates of Chondrules Compared with Silicates from the Colomera Iron Meteorite. Chondrule Formation in Planetesimal Bow Shocks: Physical Processes in the Near Vicinity of the Planetesimal. Genetic Relationships Between Chondrules, Rims and Matrix. Chondrite Fractionation was Cosmochemical; Chondrule Fractionation was Geochemical. Chondrule Formation and Accretion of Chondrite Parent Bodies: Environmental Constraints. Amoeboid Olivine Aggregates from the Semarkona LL3.0 Chondrite. The Evolution of Solids in Proto-Planetary Disks. New Nickel Vapor Pressure Measurements: Possible Implications for Nebular Condensates. Chemical, Mineralogical and Isotopic Properties of Chondrules: Clues to Their Origin. Maximal Size of Chondrules in Shock-Wave Heating Model: Stripping of Liquid Surface in Hypersonic Rarefied Gas Flow. The Nature and Origin of Interplanetary Dust: High Temperature Components. Refractory Relic Components in Chondrules from Ordinary Chondrites. Constraints on the Origin of Chondrules and CAIs from Short-lived and Long-lived Radionuclides. The Genetic Relationship Between Refractory Inclusions and Chondrules. Contemporaneous Chondrule Formation Between Ordinary and Carbonaceous Chondrites. Chondrules and Isolated Grains in the Fountain Hills Bencubbinite. Implications of Chondrule Formation in a Gas of Solar Composition. Implications of Meteoritic Cl-36 Abundance for the Origin of Short-lived Radionuclides in the Early Solar System. Size Sorting and the Chondrule Size Spectrum. Comparative Study of Refractory Inclusions from Different Groups of Chondrites. In Situ Investigation of Mg Isotope Distributions in an Allende CAI by Combined LA-ICPMS and SIMS Analyses Photochemical Speciation of Oxygen Isotopes in the Solar Nebula.

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Isotopic measurements of the cosmic ray nuclei at 1.7 GeV/n and 0.5 GeV/n

Results are presented on the mean isotopic composition of cosmic ray nuclei, or the average neutron excess for the elements Be to Si. At 1.7 GeV/nucleon they have been obtained by comparing the abundances measured above a rigidity threshold at Palestine, Texas, with abundances measured above an equivalent velocity threshold at Cape Girardeau Missouri. At 0.5 GeV/nucleon the results are obtained by analysing the variation in the chemical composition with energy in the energy region around the geomagnetic cut-off.

Juliusson, E.↗

Origin and loss of the volatiles of the terrestrial planets

How the terrestrial planets obtained their original endorsement of volatiles and proceeded to lose them selectively is the theme of this paper. Where good and convincing answers to these questions are still not available, the principal issues are becoming better and better understood, and thus many of the decisive measurements and calculations needed to obtain them can be well defined. In this paper our present inventories of volatiles such as the noble gases, hydrogen compounds and atmophiles such as CO2, N2, and O2 will be presented. Careful attention will be given to isotopic ratios and their significance. Escape processes past and present - blow off impact erosion, thermal and non-thermal loss of neutral and ionic species will be discussed, and the contribution of each to volatile loss assessed. It will be argued that our understanding of these processes is adequate to explain the present level of fractionation of many of the noble gases and their isotopes on all the terrestrial planets. It will also be argued that we are close to understanding loss of hydrogen well enough to assess reasonably the early abundance of water on early Venus and Mars.

Donahue, T. M.↗

PHYS: Division of Physical Chemistry 258 - Properties and Origins of Cometary and Asteroidal Organic Matter Delivered to the Early Earth

Comets and asteroids may have contributed much of the Earth's water and organic matter. The Earth accretes approximately 4x10(exp 7) Kg of dust and meteorites from these sources every year. The least altered meteorites contain complex assemblages of organic compounds and abundant hydrated minerals. These carbonaceous chondrite meteorites probably derive from asteroids that underwent hydrothermal processing within the first few million years after their accretion. Meteorite organics show isotopic and chemical signatures of low-T ion-molecule and grain-surface chemistry and photolysis of icy grains that occurred in cold molecular clouds and the outer protoplanetary disk. These signatures have been overprinted by aqueously mediated chemistry in asteroid parent bodies, forming amino acids and other prebiotic molecules. Comets are much richer in organic matter but it is less well characterized. Comet dust collected in the stratosphere shows larger H and N isotopic anomalies than most meteorites, suggesting better preservation of primordial organics. Rosetta studies of comet 67P coma dust find complex organic matter that may be related to the macromolecular material that dominates the organic inventory of primitive meteorites. The exogenous organic material accreting on Earth throughout its history is made up of thousands of molecular species formed in diverse processes ranging from circumstellar outflows to chemistry at near absolute zero in dark cloud cores and the formative environment within minor planets. NASA and JAXA are currently flying sample return missions to primitive, potentially organic-rich asteroids. The OSIRIS-REx and Hayabusa2 missions will map their target asteroids, Bennu and Ryugu, in detail and return regolith samples to Earth. Laboratory analyses of these pristine asteroid samples will provide unprecedented views of asteroidal organic matter relatively free of terrestrial contamination within well determined geological context. Studies of extraterrestrial materials and returned samples are essential to understand the origins of Solar System organic material and the roles of comets and asteroids to providing the starting materials for the emergence of life.

Messenger, Scott↗

Analytical Techniques for Retrieval of Atmospheric Composition with the Quadrupole Mass Spectrometer of the Sample Analysis at Mars Instrument Suite on Mars Science Laboratory

The Sample Analysis at Mars (SAM) instrument suite is the largest scientific payload on the Mars Science Laboratory (MSL) Curiosity rover, which landed in Mars׳ Gale Crater in August 2012. As a miniature geochemical laboratory, SAM is well-equipped to address multiple aspects of MSL׳s primary science goal, characterizing the potential past or present habitability of Gale Crater. Atmospheric measurements support this goal through compositional investigations relevant to martian climate evolution. SAM instruments include a quadrupole mass spectrometer, a tunable laser spectrometer, and a gas chromatograph that are used to analyze martian atmospheric gases as well as volatiles released by pyrolysis of solid surface materials (Mahaffy et al., 2012). This report presents analytical methods for retrieving the chemical and isotopic composition of Mars׳ atmosphere from measurements obtained with SAM׳s quadrupole mass spectrometer. It provides empirical calibration constants for computing volume mixing ratios of the most abundant atmospheric species and analytical functions to correct for instrument artifacts and to characterize measurement uncertainties. Finally, we discuss differences in volume mixing ratios of the martian atmosphere as determined by SAM (Mahaffy et al., 2013) and Viking (Owen et al., 1977, Oyama and Berdahl, 1977) from an analytical perspective. Although the focus of this paper is atmospheric observations, much of the material concerning corrections for instrumental effects also applies to reduction of data acquired with SAM from analysis of solid samples.

quadropole mass spectometer↗