Engineering topics

Mahaffy, Paul R.

Publications and source records attributed to Mahaffy, Paul R..

At least 19 records

NASA NTRS2020

First Detections of Dichlorobenzene Isomers and Trichloromethylpropane from Organic Matter Indigenous to Mars Mudstone in Gale Crater, Mars: Results from the Sample Analysis at Mars Instrument Onboard the Curiosity Rover

Chromatographic analysis of the Cumberland mudstone in Gale crater by the Sample Analysis at Mars (SAM) instrument revealed the detection of two to three isomers of dichlorobenzene. Their individual concentrations were estimated to be in the 0.5–17 ppbw range relative to the sample mass. We also report the first detection of trichloromethylpropane and the confirmation of the detection of chlorobenzene previously reported. Supporting laboratory experiments excluded the SAM internal background as the source of those compounds, thus confirming the organic carbon and chlorine of the newly detected chlorohydrocarbons are indigenous to the mudstone sample. Laboratory experiments also demonstrated that the chlorohydrocarbons were mainly produced from chemical reactions occurring in the SAM ovens between organic molecules and oxychlorines contained in the sample. The results we obtained show that meteoritic organics and tested chemical species (a polycyclic aromatic hydrocarbon, an amino acid, and a carboxylic acid) were plausible organic precursors of the chlorinated aromatic molecules detected with SAM, thus suggesting that they could be among the organic molecules present in the mudstone. Results from this study coupled with previously reported detections of chlorinated aromatics (<300 ppbw) indigenous to the same mudstone highlight that organics can be preserved from the harsh surface conditions even at shallow depth. The detection of new chlorohydrocarbons with SAM confirms that organic molecules should have been available in an environment favorable to life forms, strengthening the habitability aspect of Gale crater. Key Words: Mars—Chlorinated organic molecules—In situ measurements—Sample Analysis at Mars— Mudstone—Gale crater. Astrobiology 20, 292–306.

Szopa, Cyril↗

NASA NTRS2018

Organic Matter Preserved in 3-Billion-Year-Old Mudstones at Gale Crater, Mars

Establishing the presence and state of organic matter, including its possible biosignatures, in martian materials has been an elusive quest, despite limited reports of the existence of organic matter on Mars. We report the in situ detection of organic matter preserved in lacustrine mudstones at the base of the ~3.5-billion-year-old Murray formation at Pahrump Hills, Gale crater, by the Sample Analysis at Mars instrument suite onboard the Curiosity rover. Diverse pyrolysis products, including thiophenic, aromatic, and aliphatic compounds released at high temperatures (500Â° to 820Â°C), were directly detected by evolved gas analysis. Thiophenes were also observed by gas chromatographyâ€“mass spectrometry. Their presence suggests that sulfurization aided organic matter preservation. At least 50 nanomoles of organic carbon persists, probably as macromolecules containing 5% carbon as organic sulfur molecules.

Eigenbrode, Jennifer L.↗

NASA NTRS2017

Nitrogen on Mars: Insights from Curiosity

Recent detection of nitrate on Mars indicates that nitrogen fixation processes occurred in early martian history. Data collected by the Sample Analysis at Mars (SAM) instrument on the Curiosity Rover can be integrated with Mars analog work in order to better understand the fixation and mobility of nitrogen on Mars, and thus its availability to putative biology. In particular, the relationship between nitrate and other soluble salts may help reveal the timing of nitrogen fixation and post-depositional behavior of nitrate on Mars. In addition, in situ measurements of nitrogen abundance and isotopic composition may be used to model atmospheric conditions on early Mars.

Stern, J. C.↗

NASA NTRS2017

Global Distribution and Parameter Dependences of Gravity Wave Activity in the Martian Upper Thermosphere Derived from MAVEN NGIMS Observations

Wavelike perturbations in the Martian upper thermosphere observed by the Neutral Gas Ion Mass Spectrometer (NGIMS) onboard the Mars Atmosphere and Volatile EvolutioN (MAVEN) spacecraft have been analyzed. The amplitudes of small-scale perturbations with apparent wavelengths between approx. 100 and approx. 500 km in the Ar density around the exobase show a clear dependence on temperature (T(sub 0)) of the upper thermosphere. The average amplitude of the perturbations is approx. 10% on the dayside and approx. 20% on the nightside, which is about 2 and 10 times larger than those observed in the Venusian upper thermosphere and in the low-latitude region of Earths upper thermosphere, respectively. The amplitudes are inversely proportional to T(sub 0), suggesting saturation due to convective instability in the Martian upper thermosphere. After removing the dependence on T(sub 0), dependences of the average amplitude on the geographic latitude and longitude and solar wind parameters are found to be not larger than a few percent. These results suggest that the amplitudes of small-scale perturbations are mainly determined by convective breaking saturation in the upper thermosphere on Mars, unlike those on Venus and Earth.

Thermosphere↗

NASA NTRS2017

Initial SAM Calibration Gas Experiments on Mars: Quadrupole Mass Spectrometer Results and Implications

The Sample Analysis at Mars (SAM) instrument suite of the Mars Science Laboratory (MSL) Curiosity rover is equipped to analyze both martian atmospheric gases and volatiles released by pyrolysis of solid surface materials, with target measurements including chemical and isotopic composition (Mahaffy et al., 2012). To facilitate assessment of instrument performance and validation of results obtained on Mars, SAM houses a calibration cell containing CO2, Ar, N2, Xe, and several fluorinated hydrocarbon compounds (Franz et al., 2014; Mahaffy et al., 2012). This report describes the first two experiments utilizing this calibration cell on Mars and gives results from analysis of data acquired with the SAM Quadrupole Mass Spectrometer (QMS). These data support the accuracy of isotope ratios obtained with the QMS (Conrad et al., 2016; Mahaffy et al., 2013) and provide ground-truth for reassessment of analytical constants required for atmospheric measurements, which were reported in previous contributions (Franz et al., 2015, 2014). The most significant implication of the QMS data involves reinterpretation of pre-launch contamination previously believed to affect only CO abundance measurements (Franz et al., 2015) to affect N2 abundances, as well. The corresponding adjustment to the N2 calibration constant presented here brings the atmospheric volume mixing ratios for Ar and N2 retrieved by SAM into closer agreement with those reported by the Viking mission (Owen et al., 1977; Oyama and Berdahl, 1977).

Sample Analysis at Mars Investigation↗

NASA NTRS2016

Perchlorate Formation on Mars Through Surface Radiolysis-Initiated Atmospheric Chemistry: A Potential Mechanism

Recent observations of the Martian surface by the Phoenix lander and the Sample Analysis at Mars indicate the presence of perchlorate (ClO4). The abundance and isotopic composition of these perchlorates suggest that the mechanisms responsible for their formation in the Martian environment may be unique in our solar system. With this in mind, we propose a potential mechanism for the production of Martian perchlorate: the radiolysis of the Martian surface by galactic cosmic rays, followed by the sublimation of chlorine oxides into the atmosphere and their subsequent synthesis to form perchloric acid (HClO4) in the atmosphere, and the surface deposition and subsequent mineralization of HClO4 in the regolith to form surface perchlorates. To evaluate the viability of this mechanism, we employ a one-dimensional chemical model, examining chlorine chemistry in the context of Martian atmospheric chemistry. Considering the chlorine oxide, OClO, we find that an OClO flux as low as 3.2 x 10(exp 7) molecules/sq cm/s sublimated into the atmosphere from the surface could produce sufficient HClO4 to explain the perchlorate concentration on Mars, assuming an accumulation depth of 30 cm and integrated over the Amazonian period. Radiolysis provides an efficient pathway for the oxidation of chlorine, bypassing the efficient Cl/HCl recycling mechanism that characterizes HClO4 formation mechanisms proposed for the Earth but not Mars.

perchlorate↗

NASA NTRS2016

Electron Energetics in the Martian Dayside Ionosphere: Model Comparisons with MAVEN Data

This paper presents a study of the energetics of the dayside ionosphere of Mars using models and data from several instruments on board the Mars Atmosphere and Volatile EvolutioN spacecraft. In particular, calculated photoelectron fluxes are compared with suprathermal electron fluxes measured by the Solar Wind Electron Analyzer, and calculated electron temperatures are compared with temperatures measured by the Langmuir Probe and Waves experiment. The major heat source for the thermal electrons is Coulomb heating from the suprathermal electron population, and cooling due to collisional rotational and vibrational CO2 dominates the energy loss. The models used in this study were largely able to reproduce the observed high topside ionosphere electron temperatures (e.g., 3000 K at 300 km altitude) without using a topside heat flux when magnetic field topologies consistent with the measured magnetic field were adopted. Magnetic topology affects both suprathermal electron transport and thermal electron heat conduction. The effects of using two different solar irradiance models were also investigated. In particular, photoelectron fluxes and electron temperatures found using the Heliospheric Environment Solar Spectrum Radiation irradiance were higher than those with the Flare Irradiance Spectrum Model-Mars. The electron temperature is shown to affect the O2(+) dissociative recombination rate coefficient, which in turn affects photochemical escape of oxygen from Mars.

magnetic topology↗

NASA NTRS2016

Simultaneous Observations of Atmospheric Tides from Combined in Situ and Remote Observations at Mars from the MAVEN Spacecraft

We report the observations of longitudinal variations in the Martian thermosphere associated with nonmigrating tides. Using the Neutral Gas Ion Mass Spectrometer (NGIMS) and the Imaging Ultraviolet Spectrograph (IUVS) on NASA's Mars Atmosphere and Volatile EvolutioN Mission (MAVEN) spacecraft, this study presents the first combined analysis of in situ and remote observations of atmospheric tides at Mars for overlapping volumes, local times, and overlapping date ranges. From the IUVS observations, we determine the altitude and latitudinal variation of the amplitude of the nonmigrating tidal signatures, which is combined with the NGIMS, providing information on the compositional impact of these waves. Both the observations of airglow from IUVS and the CO2 density observations from NGIMS reveal a strong wave number 2 signature in a fixed local time frame. The IUVS observations reveal a strong latitudinal dependence in the amplitude of the wave number 2 signature. Combining this with the accurate CO2 density observations from NGIMS, this would suggest that the CO2 density variation is as high as 27% at 0-10 deg latitude. The IUVS observations reveal little altitudinal dependence in the amplitude of the wave number 2 signature, varying by only 20% from 160 to 200 km. Observations of five different species with NGIMS show that the amplitude of the wave number 2 signature varies in proportion to the inverse of the species scale height, giving rise to variation in composition as a function of longitude. The analysis and discussion here provide a roadmap for further analysis as additional coincident data from these two instruments become available.

atmospheric tides↗

NASA NTRS2016

Synodic and Semiannual Oscillations of Argon-40 in the Lunar Exosphere

The neutral mass spectrometer on the Lunar Atmosphere and Dust Environment Explorer (LADEE) spacecraft collected a trove of exospheric data, including a set of high-quality measurements of radiogenic Ar-40 over a period of 142 days. Data synthesis studies, using well-established exosphere simulation tools, show that the LADEE argon data are consistent with an exosphere-regolith interaction that is dominated by adsorption and that the desorption process generates the Armand distribution of exit velocities. The synthesis work has uncovered an apparent semiannual oscillation of argon that is consistent with temporal sequestration in the seasonal cold traps created at the poles by the obliquity of the Moon. In addition, the LADEE data provide new insight into the pristine nature of lunar regolith, its spatially varying sorption properties, and the influence of sorption processes on the synodic oscillation of the argon exosphere.

argon-40↗

NASA NTRS2015

In Situ Detection of Organic Molecules on the Martian Surface With the Mars Organic Molecule Analyzer (MOMA) on Exomars 2018

The Mars Organic Molecule Analyzer (MOMA) investigation on the 2018 ExoMars rover will examine the chemical composition of samples acquired from depths of up to two meters below the martian surface, where organics may be protected from radiative and oxidative degradation. The MOMA instrument is centered around a miniaturized linear ion trap (LIT) that facilitates two modes of operation: i) pyrolysisgas chromatography mass spectrometry (pyrGC-MS); and, ii) laser desorptionionization mass spectrometry (LDI-MS) at ambient Mars pressures. The LIT also enables the structural characterization of complex molecules via complementary analytical capabilities, such as multi-frequency waveforms (i.e., SWIFT) and tandem mass spectrometry (MSMS). When combined with the complement of instruments in the rovers Pasteur Payload, MOMA has the potential to reveal the presence of a wide range of organics preserved in a variety of mineralogical environments, and to begin to understand the structural character and potential origin of those compounds.

ExoMars2018↗

NASA NTRS2015

Volatile and Isotopic Imprints of Ancient Mars

The science investigations enabled by Curiosity rover's instruments focus on identifying and exploring the habitability of the Martian environment. Measurements of noble gases, organic and inorganic compounds, and the isotopes of light elements permit the study of the physical and chemical processes that have transformed Mars throughout its history. Samples of the atmosphere, volatiles released from soils, and rocks from the floor of Gale Crater have provided a wealth of new data and a window into conditions on ancient Mars.

Ancients↗

NASA NTRS2014

The Neutral Gas and Ion Mass Spectrometer on the Mars Atmosphere and Volatile Evolution Mission

The Neutral Gas and Ion Mass Spectrometer (NGIMS) of the Mars Atmosphere and Volatile Evolution Mission (MAVEN) is designed to measure the composition, structure, and variability of the upper atmosphere of Mars. The NGIMS complements two other instrument packages on the MAVEN spacecraft designed to characterize the neutral upper atmosphere and ionosphere of Mars and the solar wind input to this region of the atmosphere. The combined measurement set is designed to quantify atmosphere escape rates and provide input to models of the evolution of the martian atmosphere. The NGIMS is designed to measure both surface reactive and inert neutral species and ambient ions along the spacecraft track over the 125-500 km altitude region utilizing a dual ion source and a quadrupole analyzer.

Gas↗

NASA NTRS2014

Liquid Chromatography-Mass Spectrometry Interface for Detection of Extraterrestrial Organics

The OASIS (Organics Analyzer for Sampling Icy surfaces) microchip enables electrospray or thermospray of analyte for subsequent analysis by the OASIS time-of-flight mass spectrometer. Electrospray of buffer solution containing the nucleobase adenine was performed using the microchip and detected by a commercial time-of-flight mass spectrometer. Future testing of thermospray and electrospray capability will be performed using a test fixture and vacuum chamber developed especially for optimization of ion spray at atmosphere and in low pressure environments.

extraterrestrial organics↗

NASA NTRS2014

The Neutral Mass Spectrometer on the Lunar Atmosphere and Dust Environment Explorer Mission

The Neutral Mass Spectrometer (NMS) of the Lunar Atmosphere and Dust Environment Explorer (LADEE) Mission is designed to measure the composition and variability of the tenuous lunar atmosphere. The NMS complements two other instruments on the LADEE spacecraft designed to secure spectroscopic measurements of lunar composition and in situ measurement of lunar dust over the course of a 100-day mission in order to sample multiple lunation periods. The NMS utilizes a dual ion source designed to measure both surface reactive and inert species and a quadrupole analyzer. The NMS is expected to secure time resolved measurements of helium and argon and determine abundance or upper limits for many other species either sputtered or thermally evolved from the lunar surface.

Moon↗

NASA NTRS2014

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↗

NASA NTRS2014

The Deuterium to Hydrogen Ratio in the Water that Formed the Yellowknife Bay Mudstones in Gale Crater

A suite of isotope ratios of light elements in the present martian atmosphere (13C/12C, 15N/14N, 18O/16O, 38Ar/36Ar, and D/H) are all substantially enriched in the heavy element suggesting atmospheric loss to space over the past billions of years with preferential loss of the lighter isotope from each pair. In situ measurements from MSL's Sample Analysis at Mars (SAM) instrument [e.g. 1,2,3] have considerably refined previous measurements from the Viking mass spectrometers [e.g. 4], from remote spectroscopic observations [e.g. 5,6], and from martian meteorite studies [e.g. 7,8]. The persistence of habitable environments such as the ancient Yellowknife Bay lake recently revealed by measurements from the Curiosity rover [9] depends on the surface temperatures and the duration of an atmosphere thicker than that at present. Current and planned measurements from orbit with the Mars Express and MAVEN missions respectively intend to study the processes of atmospheric escape including solar wind interaction, sputtering, thermal escape, and dissociative recombination, and determine or refine the current rate of atmospheric loss caused by these and other mechanisms. The goal of these programs is to understand the physical processes sufficiently well so that robust extrapolations over the past billions of years can be made D/H is measured by both the Tunable Laser Spectrometer (TLS) and the Quadrupole Mass Spectrometer (QMS) of the SAM suite. to predict the atmospheric and surface conditions on early Mars. However, the study of the history of martian atmospheric evolution will be greatly facilitated if we are able to also directly measure the isotopic composition of volatiles captured in rocks that are representative of the ancient atmosphere. To date, D/H is one of the most promising candidates for this study since water is the most abundant volatile thermally released from the Yellowknife Bay phylosilicates discovered by the SAM and CheMin experiments of MSL and its

Yellowknife Bay↗

NASA NTRS2014

Detection and Quantification of Nitrogen Compounds in the First Drilled Martian Solid Samples by the Sample Analysis at Mars (SAM) Instrument Suite on the Mars Science Laboratory (MSL)

The Sampl;e Analysis at Mars (sam) instrument suite on the Mars Science Laboratory (MSL) Curiosity Rover detected both reduced and oxidized nitrogen bearing compounds during the pyrolysis of surface materials from the three sites at Gale Crater. Preliminary detections of nitrogen species include No, HCN, ClCN, and TFMA ((trifluoro-N-methyl-acetamide), Confirmation of indigenous Martian nitrogen-bearing compounds requires quantifying N contribution from the terrestrial derivatization reagents carried for SAM's wet chemistry experiment that contribute to the SAM background. Nitrogen species detected in the SAM solid sample analyses can also be produced during laboratory pyrolysis experiments where these reagents are heated in the presence of perchlorate a compound that has also been identified by SAM in Mars solid samples.

Stern, Jennifer C.↗

NASA NTRS2014

Performance of the Linear Ion Trap Mass Spectrometer for the Mars Organic Molecule Analyzer (MOMA) Investigation on the 2018 Exomars Rover

The 2018 ExoMars rover mission includes the Mars Organic Molecule Analyzer (MOMA) investigation. MOMA will examine the chemical composition of samples acquired from depths of up to two meters below the martian surface, where organics may be protected from degradation derived from cosmic radiation and/or oxidative chemical reactions. When combined with the complement of instruments in the rover's Pasteur Payload, MOMA has the potential to reveal the presence of a wide range of organics preserved in a variety of mineralogical environments, and to begin to understand the structural character and potential origin of those compounds. The MOMA investigation is led by the Max Planck Institute for Solar System Research (MPS) with the mass spectrometer subsystem provided by NASA GSFC. MOMA's linear ion trap mass spectrometer (ITMS) is designed to analyze molecular composition of: (i) gas evolved from pyrolyzed powder samples and separated in a gas chromatograph; and, (ii) ions directly desorbed from crushed solid samples at Mars ambient pressure, as enabled by a pulsed UV laser system, fast-actuating aperture valve and capillary ion inlet. Breadboard ITMS and associated electronics have been advanced to high end-to-end fidelity in preparation for flight hardware delivery to Germany in 2015.

linear ion trap mass spectrometer↗