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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 613 records · Page 34

Aeolian removal of dust from photovoltaic surfaces on Mars

It is well documented that Mars is totally engulfed in huge dust storms nearly each Martian year. Dust elevated in these global dust storms, or in any of the numerous local dust storms could settle on photovoltaic surfaces and seriously hamper photovoltaic power system performance. Using a recently developed technique to uniformly dust simulated photovoltaic surfaces, samples were subjected to Martian-like winds in an attempt to determine whether natural aeolian processes on Mars would sweep off the settled dust. The effects of wind velocity, angle of attack, height off the Martian surface, and surface coating material were investigated. Principles which can help to guide the design of photovoltaic arrays bound for the Martian surface were uncovered. Most importantly, arrays mounted with an angle of attack approaching 45 deg show the most efficient clearing. Although the angular dependence is not sharp, horizontally mounted arrays required significantly higher wind velocities to clear off the dust. From the perspective of dust-clearing it appears that the arrays may be erected quite near the ground, but previous studies have suggested that saltation effects can be expected to cause such arrays to be covered by sand if they are set up less than about a meter from the ground. Providing that the surface chemistry of Martian dusts is comparable to our test dust, the materials used for protective coating may be optimized for other considerations such as transparency, and chemical or abrasion resistance. The static threshold velocity is low enough that there are regions on Mars which experience winds strong enough to clear off a photovoltaic array if it is properly oriented. Turbulence fences proved to be an ineffective strategy to keep dust cleared from the photovoltaic surfaces.

Gaier, James R.↗

Remote Recession Sensing of Ablative Heat Shield Materials

Material recession and charring are two major processes determining the performance of ablative heat shield materials. Even in ground testing, the characterization of these two mechanisms relies on measurements of material thickness before and after testing, thus providing only information integrated over the test time. For recession measurements, optical methods such as imaging the sample surface during testing are under investigation but require high alignment and instrument effort, therefore being not established as a standard measurement method. For char depth measurements, the most common method so far consists in investigation of sectioned samples after testing or in the case of Stardust where core extractions were performed to determine char information. In flight, no reliable recession measurements are available, except total recession after recovering the heat shield on ground. Developments of mechanical recession sensors have been started but require substantial on board instrumentation adding mass and complexity. In this work, preliminary experiments to evaluate the feasibility of remote sensing of material recession and possibly char depth through optically observing the emission signatures of seeding materials in the post shock plasma is investigated. It is shown that this method can provide time resolved recession measurements without the necessity of accurate alignment procedures of the optical set-up and without any instrumentation on board of a spacecraft. Furthermore, recession data can be obtained without recovering flight hardware which would be a huge benefit for inexpensive heat shield material testing on board of small re-entry probes, e.g. on new micro-satellite re-entry probes as a possible future application of Cubesats or RBR

instrumentation↗

Directional luminescence control of InGaN/GaN heterostructures using quantum structure lattice arrays

The spontaneous surface luminescence properties of InGaN/GaN quantum structure lattice (QSL) are reported. The QSL consists of a two-dimensional array of InGaN/GaN quantum boxes (QBs) arranged in a rectangular pattern of 200 nm periodicity. The measured angular dependent photoluminescence (PL) spectra show a strong dependence on the in-plane Bragg diffractions between QBs. The maximum PL intensity of the InGaN/GaN QSL array that fulfill the Bragg condition points in the normal direction of the sample surface with a narrow radiation angle of ∼ ±12°. In addition, a small side lobe is also shown at ±40°. For the QSL sample that does not fulfill the Bragg diffraction condition, the radiation pattern shows a conventional cosine distribution. The finite-difference time-domain numerical analysis confirms that the lowest order and higher order Bragg diffractions between QBs determine the main and the small side lobe of the radiation pattern measured in QSLs, respectively.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Implantation of sodium ions into germanium

The donor properties of Na atoms introduced by ion implantation into p-Ge with the resistivity 20-40 {Omega} cm are established for the first time. Na profiles implanted into Ge (the energies 70 and 77 keV and the doses (0.8, 3, 30) Multiplication-Sign 10{sup 14} cm{sup -2}) are studied. The doses and annealing temperatures at which the thermoprobe detects n-type conductivity on the sample surface are established. After implantation, the profiles exhibit an extended tail. The depth of the concentration maximum is in good agreement with the calculated mean projected range of Na ions R{sub p}. Annealing for 30 min at temperatures of 250-700 Degree-Sign C brings about a redistribution of Na atoms with the formation of segregation peaks at a depth, which is dependent on the ion dose, and is accompanied by the diffusion of Na atoms to the surface with subsequent evaporation. After annealing at 700 Degree-Sign C less than 7% of the implanted ions remain in the matrix. The shape of the profile tail portions measured after annealing at temperatures 300-400 Degree-Sign C is indicative of the diffusion of a small fraction of Na atoms into the depth of the sample.

36 MATERIALS SCIENCE↗

Using eigenmodes to perform the inverse problem associated with resonant ultrasound spectroscopy

In principle, resonant ultrasonic spectroscopy (RUS) can be used to characterize any parameter that influences the mechanical resonant response of a sample. Examples include the elastic constants, sample dimensions, and crystal orientation. Extracting the parameter of interest involves performing the inverse problem, which typically entails an iterative routine that compares calculated and measured eigenfrequencies. Here, we propose an alternative method based on laser-based resonant ultrasound spectroscopy (LRUS) that uses the eigenmodes. LRUS uses a pulsed laser to thermoelastically excite ultrasound and an interferometer to detect out-of-plane displacement associated with ultrasonic resonances. By raster scanning the probe along the sample surface, an image of the out-ofplane displacement pattern (i.e., eigenmode) is obtained. As an example of this method, we describe a technique to calculate the crystallographic orientation of a single-crystal high-purity copper sample. The crystallographic orientation is computed by comparing theoretical and experimental eigenmodes. The computed angle is shown to be in very good agreement with the angle obtained using electron backscatter diffraction. In addition, a comparison is made using eigenfrequencies and eigenmodes to calculate the crystallographic orientation. It is found for this particular application, the eigenmode method has superior sensitivity to crystal orientation.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Strain-Mediated Sn Incorporation and Segregation in Compositionally Graded Ge 1– x Sn x Epilayers Grown by MBE at Different Temperatures

We investigated the process of Sn incorporation and surface segregation for compositionally graded Ge 1–x Sn x epilayers grown on high-quality Ge (001) substrates. Here, the growth resulted in pseudomorphic GeSn layers with a ~6% maximal Sn fraction at a constant substrate temperature. The maximal fraction of Sn was increased to 9.0% when the growth temperature was continuously lowered while increasing the Sn flux. The analysis of surface droplets and SIMS profiles of elemental composition give evidence of Sn rejection during the growth, potentially associated with a critical energy of elastic strain. The intentional reduction of the coherent strain by decreasing the Sn flux near the sample surface has been shown to trap a higher fraction of Sn in the Ge 1–x Sn x layer and lower surface segregation. Our results demonstrate that strain relief by misfit dislocations in the compositionally graded layer is inhibited, which leads to Sn segregation. Specifically, the compressive strain in the graded Ge 1–x Sn x epilayer is effectively “zero” near the interface with the Ge substrate and increases up to about –1.5 × 10 –2 near the surface. Thus, although the nucleation of a dislocation may reduce the compressive strain for the top region of the epilayer, it is not beneficial for the bottom region.

42 ENGINEERING↗

Soft X-ray absorption spectroscopy of titanium dioxide nanopowders with cobalt impurities

The charge states of the cobalt ions in TiO{sub 2} nanopowders with the anatase lattice are studied by soft X-ray absorption spectroscopy. It is found that, at a low cobalt impurity concentration (1.8 at %), the cobalt ions with an oxidation state 2+ are mainly located in the tetrahedral (T{sub d}) environment of oxygen ions. Amorphous titanium dioxide exists on the sample surface before heat treatment. Annealing in vacuum or hydrogen leads to the enrichment of the nanoparticle surfaces with Co{sup 2+} ions, a change in the coordination of the remaining part of cobalt ions from octahedral to tetrahedral, stabilization of the anatase structure, and the disappearance of the amorphous phase. The crystal lattice of the samples with a relatively high cobalt concentration (12 at %) is distorted, and annealing does not cause the disappearance of the amorphous phase of TiO{sub 2}. Cobalt is reduced to its metallic state upon hydrogen annealing of the samples with a high cobalt concentration.

36 MATERIALS SCIENCE↗

Airborne flux measurements of ammonia over the southern Great Plains using chemical ionization mass spectrometry

Abstract. Ammonia (NH3) is an abundant trace gas in the atmosphere and an important player in atmospheric chemistry, aerosol formation and the atmosphere–surface exchange of nitrogen. The accurate determination of NH3 emission rates remains a challenge, partly due to the propensity of NH3 to interact with instrument surfaces, leading to high detection limits and slow response times. In this paper, we present a new method for quantifying ambient NH3, using chemical ionization mass spectrometry (CIMS) with deuterated benzene cations as reagents. The setup aimed at limiting sample–surface interactions and achieved a 1σ precision of 10–20 pptv and an immediate 1/e response rate of < 0.4 s, which compares favorably to the existing state of the art. The sensitivity exhibited an inverse humidity dependence, in particular in relatively dry conditions. Background of up to 10 % of the total signal required consideration as well, as it responded on the order of a few minutes. To showcase the method's capabilities, we quantified NH3 mixing ratios from measurements obtained during deployment on a Gulfstream I aircraft during the HI-SCALE (Holistic Interactions of Shallow Clouds, Aerosols, and Land-Ecosystems) field campaign in rural Oklahoma during May 2016. Typical mixing ratios were 1–10 parts per billion by volume (ppbv) for the boundary layer and 0.1–1 ppbv in the lower free troposphere. Sharp plumes of up to tens of ppbv of NH3 were encountered as well. We identified two of their sources as a large fertilizer plant and a cattle farm, and our mixing ratio measurements yielded upper bounds of 350 ± 50 and 0.6 kg NH3 h−1 for their respective momentary source rates. The fast response of the CIMS also allowed us to derive vertical NH3 fluxes within the turbulent boundary layer via eddy covariance, for which we chiefly used the continuous wavelet transform technique. As expected for a region dominated by agriculture, we observed predominantly upward fluxes, implying net NH3 emissions from the surface. The corresponding analysis focused on the most suitable flight, which contained two straight-and-level legs at ∼ 300 m above ground. We derived NH3 fluxes between 1 and 11 mol km−2 h−1 for these legs, at an effective spatial resolution of 1–2 km. The analysis demonstrated how flux measurements benefit from suitably arranged flight tracks with sufficiently long straight-and-level legs, and it explores the detrimental effect of measurement discontinuities. Following flux footprint estimations, comparison to the NH3 area emissions inventory provided by the U.S. Environmental Protection Agency indicated overall agreement but also the absence of some sources, for instance the identified cattle farm. Our study concludes that high-precision CIMS measurements are a powerful tool for in situ measurements of ambient NH3 mixing ratios, and even allow for the airborne mapping of the air–surface exchange of NH3.

58 GEOSCIENCES↗

Surface analysis insight note: Synthetic line shapes, integration regions and relative sensitivity factors

Here, methods for estimating photoemission intensity from X-ray photoelectron spectroscopy data are examined. The role played by “synthetic” bell-shaped curves, integration intervals, background curves, and the use of relative sensitivity factors (RSFs) in reporting percentage atomic concentration for a sample is presented. In particular, photoemission lines with differing energy distributions obtained from the NaCl sample surface are used to demonstrate how a comparison of photoemission intensities is dependent on the line shapes, background curves, and appropriate use of RSFs.

42 ENGINEERING↗

Atmospheric Electron-induced X-Ray Spectrometer (AEXS) Instrument Development

Introduction: This paper describes the progress in data acquisition and establishing the observational capability of the AEXS instrument. The AEXS is a miniature instrument[1-4] based on the excitation of characteristic X-Ray Fluorescence (XRF) and luminescence spectra using a focused electron beam which enables nondestructive evaluation of sample surfaces in planetary ambient atmospheres. In situ operation is obtained through the use of a thin electron transmissive membrane to isolate the vacuum of the AEXS source from the outside ambient atmosphere. Thus eliminating the need for a vacuum pumped sample chamber as is common in all laboratory SEM s. The transmitted electrons impinge on the sample exciting XRF spectra from the irradiated spot on in-situ or collected samples with sub-mm to cm-scale spatial resolution at Mars atmospheric pressure. The AEXS system (Fig 1) consists of a high-energy (>10keV) electron gun encapsulated by the isolation membrane, an XRF detection and analyzer system, and a high voltage power supply. The XRF data are analyzed to determine the elemental abundance for the irradiated spots. The approach to demonstrating a proof of concept of the AEXS has been through 1) demonstrating the viability of microfabricated membranes, 2) assembling AEXS setups with increasingly integrated functional components, and 3) simulating the AEXS observational capabilities. The development of the instrument is described in detail in the poster paper[4] at this conference. This paper focuses on describing the progress of the AEXS instrument to acquire XRF data and using commercially available software to analyze the data streams and determine the accuracy, precision and resolution of the analysis compared to the certified elemental abundance.

Urgiles, E.↗

The Search for Lunar Mantle Rocks Exposed on the Surface of the Moon

The lunar surface is ancient and well-preserved, recording Solar System history and planetary evolution processes. Ancient basin-scale impacts excavated lunar mantle rocks, which are still expected to be present on the surface. Sampling these rocks would provide insight into fundamental planetary processes, including differentiation and magmatic evolution. There is contention among lunar scientists as to what lithologies make up the upper lunar mantle, and where they may have been exposed on the surface. We review dynamical models of lunar differentiation in the context of recent experiments and spacecraft data, assessing candidate lithologies, their distribution, and implications for lunar evolution.

Geochemistry↗

Influence of In doping on the structural, photo-luminescence and alcohol response characteristics of the SnO{sub 2} nanoparticles

Graphical abstract: When the sample is exposed to air, the atmospheric oxygen O{sub 2} adsorbs on the sample surface in the form of ionic species O{sup −} by capturing electrons from the conduction band. The adsorbed ionic species O{sup −} react with the test alcohol molecules and are responsible for sensing mechanism. - Highlights: • In-doped SnO{sub 2} samples show smaller crystallinity with crystallite size: ∼7–9 nm. • EDX analyses confirm the incorporation of indium ions in the SnO{sub 2} lattice. • Raman spectra are consistent with the results of XRD and SAED pattern. • Alcohol response has been found to increase with the indium dopant concentration. • 3 at% In-doped sample exhibits maximum response (96.5%) to propan-2-ol at 250 °C. - Abstract: Undoped and In-doped SnO{sub 2} nanoparticles were synthesized by the co-precipitation method. Upon In doping, the samples exhibit reduced crystallinity as compared to the undoped SnO{sub 2}. The Raman spectra of the undoped samples exhibit three fundamental peaks at 467.3, 633.4 and 774.6 cm{sup −1} corresponding to E{sub g}, A{sub 1g} and B{sub 2g} vibration modes, respectively. The PL spectra show two strong emission bands at the wavelengths 417 nm and 479 nm, along with five weak emission peaks in the visible region. Alcohol response characteristics of the In-doped SnO{sub 2} samples were investigated for various concentrations (10–50 ppm) at different operating temperatures (150–250 °C). Among all the samples examined, the 3 at% In-doped SnO{sub 2} sample shows maximum response (96.5%) to propan-2-ol, followed by ethanol (92%) and methanol (90%) at the operating temperature of 250 °C for 50 ppm concentration. For each test alcohol, the response has been found to increase with the In dopant concentration.

36 MATERIALS SCIENCE↗

Liquid contact resonance atomic force microscopy via experimental reconstruction of the hydrodynamic function

We present a method to correct for surface-coupled inertial and viscous fluid loading forces in contact resonance (CR) atomic force microscopy (AFM) experiments performed in liquid. Based on analytical hydrodynamic theory, the method relies on experimental measurements of the AFM cantilever's free resonance peaks near the sample surface. The free resonance frequencies and quality factors in both air and liquid allow reconstruction of a continuous hydrodynamic function that can be used to adjust the CR data in liquid. Validation experiments utilizing thermally excited free and in-contact spectra were performed to assess the accuracy of our approach. Results show that the method recovers the air frequency values within approximately 6%. Knowledge of fluid loading forces allows current CR analysis techniques formulated for use in air and vacuum environments to be applied to liquid environments. Our technique greatly extends the range of measurement environments available to CR-AFM.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

ARPA-E PNDIODES "PN Junctions by Ion Implantation" Project (Final Report)

Electricity accounts for nearly 40% of the energy generated in the United States, of which 65% is lost to electrical system inefficiency before reaching end-use sectors. Power electronics will play a growing role in this distribution and end-use, with up to 80% of electricity estimated to pass through power electronics from generation to consumption by 2030. This gives technical improvements in power electronics enormous potential to drive efficiency gains throughout the U.S. economy. Current Si-based power architectures including MOSFETs and IGBTs are limited by high losses, low switching frequency, and poor high-temperature performance. Given the material properties of GaN, devices can exhibit a given turn-on resistance and breakdown voltage with a minute fraction of the area of a Si device—all with higher switching speeds. While n-type doping of III-nitrides has reached a high level of maturity and integration into commercialized products, p-type doping presents distinct challenges that requires continued research. The success of the next generation of GaN-based power devices depends in large part on the ability to form selective-area p-type regions, which can be accomplished by ion implantation of the prevailing acceptor dopant, Mg. This approach is relatively inexpensive and is a fab-ready processing step for creation of current-generation power electronic devices including BJTs, IGBTs, and diode rectifiers. However, ion implantation induces lattice damage and creates point defects within the material, which negatively impacts dopant activation annealing. These forms of damage may be removed by high-temperature annealing, however short annealing time and higher pressures are required to prevent decomposition of the material. We approach this challenge through an innovative combination of approaches toward obtaining high-conductivity p-type GaN. By the novel employment of a gyrotron, a microwave source that can be shaped into a highly localized beam to dissipate very high power in a semiconductor target, a wafer of GaN can be annealed in short (<2 s) ‘pulses’ at temperatures of 1450 °C (2640 °F) to achieve p-type activation without appreciable surface degradation. The p-type activation of Mg-implanted GaN can be further aided by co-implantation with N, believed to enhance the removal of point defects that compensate the acceptors dopant. Elevation to such high temperatures for even a short time induces degradation of GaN-to overcome, we have implemented additional measures to retain high-quality crystalline GaN while removing implant damage and activating Mg dopant. A bilayer cap of AlN is deposited by a combination of chemical and physical vapor deposition to protect the GaN surface. To prevent decomposition of GaN loss of N during annealing, a custom vessel—to contain pressurized N while allowing injection of microwave energy—is employed. By detailed study of the interaction of various measures that are implemented to protect the sample surface (GaN), activate the implanted dopants, and mitigate damage of the lattice heating damage during annealing, we are able to achieve p-type GaN and observe recovery of the crystal and removal of substantial density of defects created during the implantation process.

24 POWER TRANSMISSION AND DISTRIBUTION↗

Airborne flux measurements of ammonia over the Southern Great Plains using chemical ionization mass spectrometry

Ammonia (NH 3 ) is an abundant trace gas in the atmosphere and an important player in atmospheric chemistry, aerosol formation and the atmosphere-surface exchange of nitrogen. It is recognized as a major source of aerosol pollution, and it may limit the formation of cloud nuclei in remote or cold parts of the atmosphere. For soil and plants, NH 3 -mediated nitrogen can act as a harmful pollutant or as a desirable nutrient, mostly in natural and agricultural settings, respectively. Agriculture is also the main source of atmospheric NH 3 via volatilization from fertilizers and manure processing in livestock farming. The accurate determination of NH 3 emission rates remains a challenge, partly due to the propensity of NH 3 to interact with instrument surfaces leading to high detection limits and slow response times. In this paper, we present a new method for quantifying ambient NH 3 , using chemical ionization mass spectrometry (CIMS) with deuterated benzene cations as reagents. The setup aimed at limiting sample-surface interactions and achieved a 1-σ precision of 10–20 pptv and an immediate 1/e response rate < 0.4 s, which compares favorably to the existing state of the art. The sensitivity exhibited an inverse humidity dependence, in particular in relatively dry conditions. Background of up to 10 % of the total signal required consideration as well, as it responded on the order of a few minutes. To showcase the method’s capabilities, we quantified NH3 mixing ratios from measurements obtained during deployment on a Gulfstream I aircraft during the HI-SCALE (Holistic Interactions of Shallow Clouds, Aerosols and Land Ecosystems) field campaign in rural Oklahoma during May 2016. Typical mixing ratios were 1–10 parts per billion by volume (ppbv) for the boundary layer and 0.1–1 ppbv in the lower free troposphere. Sharp plumes of up to 10s of ppbv of NH3 were encountered as well. We identified two of their sources as a large fertilizer plant and a cattle farm, and our mixing ratio measurements yielded upper bounds of 350 ± 50 and 0.6 kg NH 3 h –1 for their respective momentary source rates. The fast response of the CIMS also allowed us to derive vertical NH 3 fluxes within the turbulent boundary layer via eddy covariance, for which we chiefly used the continuous wavelet transform technique. As expected for a region dominated by agriculture, we observed predominantly upward fluxes, implying net NH 3 emissions from surface. The corresponding analysis focused on the most suitable flight, which contained two straight-and-level legs at ~300 m above ground. We derived NH 3 fluxes between –4 and 18 mol km –2 h –1 for these legs, at an effective spatial resolution of 1–2 km. The analysis demonstrated how flux measurements benefit from suitably arranged flight tracks with sufficiently long straight-and-level legs, and explores the detrimental effect of measurement discontinuities. Following flux footprint estimations, comparison to the NH 3 area emissions inventory provided by the US Environmental Protection Agency indicated overall agreement, but also the absence of some sources, for instance the identified cattle farm. Our study concludes that high-precision CIMS measurements are a powerful tool for in-situ measurements of ambient NH 3 mixing ratios, and even allow for the airborne mapping of the air-surface exchange of NH 3 .

54 ENVIRONMENTAL SCIENCES↗

Recent results from the Viking Labeled Release experiment on Mars

The Labeled Release (LR) life detection experiment seeks detection of heterotrophic metabolism by monitoring radio-active gas evolution following the addition of a radioactive nutrient containing seven C-14 labeled organic substrates to surface material. LR results obtained on Mars prior to conjunction showed rapid evolution of radioactive counts upon addition of the nutrient to a fresh surface sample. The responses at both landing sites were quite similar. The additional results summarized in the present paper provide further information on the gas kinetics following a second injection of nutrient and on the effect of 'cold sterilization' of the Martian surface material. Specifically, it is shown that the production of gas from the LR nutrient is remarkably uniform; after reaction approaches completion, addition of more nutrient results in a net loss of the radioactive gas; the reactant in the Mars soil is completely inhibited by heating the soil to 160 C, and is largely inhibited by heating to 46 C. In contrast, exposure to 18 C for 2 sol (1 sol = 24.6 hr) does not appear to inhibit the reaction.

Levin, G. V.↗

Advanced Curation: Solving Current and Future Sample Return Problems

Advanced Curation is a wide-ranging and comprehensive research and development effort at NASA Johnson Space Center that identifies and remediates sample related issues. For current collections, Advanced Curation investigates new cleaning, verification, and analytical techniques to assess their suitability for improving curation processes. Specific needs are also assessed for future sample return missions. For each need, a written plan is drawn up to achieve the requirement. The plan draws while upon current Curation practices, input from Curators, the analytical expertise of the Astromaterials Research and Exploration Science (ARES) team, and suitable standards maintained by ISO, IEST, NIST and other institutions. Additionally, new technologies are adopted on the bases of need and availability. Implementation plans are tested using customized trial programs with statistically robust courses of measurement, and are iterated if necessary until an implementable protocol is established. Upcoming and potential NASA missions such as OSIRIS-REx, the Asteroid Retrieval Mission (ARM), sample return missions in the New Frontiers program, and Mars sample return (MSR) all feature new difficulties and specialized sample handling requirements. The Mars 2020 mission in particular poses a suite of challenges since the mission will cache martian samples for possible return to Earth. In anticipation of future MSR, the following problems are among those under investigation: What is the most efficient means to achieve the less than 1.0 ng/sq cm total organic carbon (TOC) cleanliness required for all sample handling hardware? How do we maintain and verify cleanliness at this level? The Mars 2020 Organic Contamination Panel (OCP) predicts that organic carbon, if present, will be present at the "one to tens" of ppb level in martian near-surface samples. The same samples will likely contain wt% perchlorate salts, or approximately 1,000,000x as much perchlorate oxidizer as organic carbon. The chemical kinetics of this reaction are poorly understood at present under the conditions of cached or curated martian samples. Among other parameters, what is the maximum temperature allowed during storage in order to preserve native martian organic compounds for analysis? What is the best means to collect headspace gases from cached martian (and other) samples? This gas will contain not only martian atmosphere but also off-gassed volatiles from the cached solids.

Fries, M.↗

Effects of gas–wall interactions on measurements of semivolatile compounds and small polar molecules

Recent work has quantified the delay times in measurements of volatile organic compounds (VOCs) caused by the partitioning between the gas phase and the surfaces of the inlet tubing and instrument itself. In this study we quantify wall partitioning effects on time responses and transmission of multifunctional, semivolatile, and intermediate-volatility organic compounds (S/IVOCs) with saturation concentrations ( C * ) between 10 0 and 10 4 µg m -3 . The instrument delays of several chemical ionization mass spectrometer (CIMS) instruments increase with decreasing C * , ranging from seconds to tens of minutes, except for the NO 3 - CIMS where it is always on the order of seconds. Six different tubing materials were tested. Teflon, including PFA, FEP, and conductive PFA, performs better than metals and Nafion in terms of both delay time and transmission efficiency. Analogous to instrument responses, tubing delays increase as C * decreases, from less than a minute to >100 min . The delays caused by Teflon tubing vs. C * can be modeled using the simple chromatography model of Pagonis et al. (2017). The model can be used to estimate the equivalent absorbing mass concentration ( C w ) of each material, and to estimate delays under different flow rates and tubing dimensions. We also include time delay measurements from a series of small polar organic and inorganic analytes in PFA tubing measured by CIMS. Small polar molecules behave differently than larger organic ones, with their delays being predicted by their Henry's law constants instead of their C * , suggesting the dominance of partitioning to small amounts of water on sampling surfaces as a result of their polarity and acidity properties. PFA tubing has the best performance for gas-only sampling, while conductive PFA appears very promising for sampling S/IVOCs and particles simultaneously. The observed delays and low transmission both affect the quality of gas quantification, especially when no direct calibration is available. Improvements in sampling and instrument response are needed for fast atmospheric measurements of a wide range of S/IVOCs (e.g., by aircraft or for eddy covariance). These methods and results are also useful for more general characterization of surface–gas interactions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗