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All sourcesNASA NTRSDOE OSTI
NASA NTRS2002

A Discussion of Upper Stratospheric Ozone Asymmetry and Ozone Trend Changes

Analyses from SAGE I/II version 6.0 data exhibit upper stratospheric ozone trends which are not significantly different from those in version 5.96 data. Trend calculations show larger downward trends at mid-high latitudes in the Southern Hemisphere than in the Northern Hemisphere, particularly in 1980s. There are also indications of decreasing downward trends with time from 1979 to 1999. We have used a chemical box model and the UARS measurements of long lived gases, CH4, H2O, NO(x), and temperature to show that, with a constant Cl(sub y) trend, a hemispheric ozone trend asymmetry of 1%/decade at 45 deg. around 43 km is expected due to the hemispheric differences of temperature and CH4 during late winter/early. Also ozone trends should have been approximately 1%/decade more negative from 1979-1989 than from 1989-1999 because of the chemical feedbacks. The model results further indicate that both the reported decrease in CH4 and the increase in H2O in HALOE measurements will result in a larger downward ozone trend and a decrease in the hemispheric ozone trend asymmetry.

Li, Jinlong↗
NASA NTRS2000

Development of an automated diode-laser-based multicomponent gas sensor

The implementation and application of a portable fiber-coupled trace-gas sensor for the detection of several trace gases, including CO2, CH4, and H2CO, are reported. This particular sensor is based on a cw fiber-amplified near-infrared (distributed Bragg reflector) diode laser and an external cavity diode laser that are frequency converted in a periodically poled lithium niobate crystal to the mid-IR spectroscopic fingerprint region (3.3-4.4 micrometers). A continuous absorption spectrum of CH4 and H2CO from 3.37 to 3.10 micrometers with a spectral resolution of 40 MHz (approximately 0.0013 cm-1) demonstrated the spectral performance that can be achieved by means of automated wavelength tuning and phase matching with stepper motor control. Autonomous long-term detection of ambient CO2 and CH4 over a 3- and 7-day period was also demonstrated.

NASA Discipline Environmental Health↗
NASA NTRS2004

Using an Extended Kalman Filter Learning Algorithm for Feed-Forward Neural Networks to Describe Tracer Correlations

In this study a new extended Kalman filter (EKF) learning algorithm for feed-forward neural networks (FFN) is used. With the EKF approach, the training of the FFN can be seen as state estimation for a non-linear stationary process. The EKF method gives excellent convergence performances provided that there is enough computer core memory and that the machine precision is high. Neural networks are ideally suited to describe the spatial and temporal dependence of tracer-tracer correlations. The neural network performs well even in regions where the correlations are less compact and normally a family of correlation curves would be required. For example, the CH4-N2O correlation can be well described using a neural network trained with the latitude, pressure, time of year, and CH4 volume mixing ratio (v.m.r.). The neural network was able to reproduce the CH4-N2O correlation with a correlation coefficient between simulated and training values of 0.9997. The neural network Fortran code used is available for download.

Lary, David J.↗
NASA NTRS2006

Line Mixing in Water Vapor and Methane

A multispectrum fitting algorithm has been used to identify line mixing and determine mixing parameters for infrared transitions of H2O and CH4 in the 5-9 micrometer region. Line mixing parameters at room temperature were determined for two pairs of transitions in the v2 fundamental band of H2O-16, for self-broadening and for broadening by H2, He, CO2, N2, O2 and air. Line mixing parameters have been determined from air-broadened CH4 spectra, recorded at temperatures between 210 K and 314 K, in selected R-branch manifolds of the v4 band. For both H2O and CH4, the inclusion of line mixing was seen to have a greater effect on the retrieved values of the line shifts than on the retrieved values of other parameters

Smith, M. A. H.↗
NASA NTRS2007

Cyanobacteria for Human Habitation beyond Earth

In light of the President s Moon/Mars initiative, lunar exploration has once again become a priority for NASA. In order to establish permanent bases on the Moon and proceed with human exploration of Mars, two key problems will be addressed: first, the production of O2 and second, the production of methane (CH4). While O2 is required for life support systems (LSS), both liquid O2 and CH4 are needed as an oxidizer and a propellant, respectively for the Lunar Surface Access Module (LSAM) and the Crew Exploration Vehicle (CEV). Unlike previous propulsion systems, the new CEV will use liquid oxygen (LO2) as an oxidizer and liquid methane (LCH4) as a propellant. Existing technology (e.g. hydrogen reduction) for the production of liquid oxygen from lunar regolith is very energy intensive and requires high temperature reactors. We propose an alternative approach using iron-tolerant cyanobacteria. We have found that iron-tolerant cyanobacteria (IT CB) are capable of etching iron-bearing minerals, which may lead to bonds breaking between Fe and O of common lunar mare basalt Fe-oxides including ilmenite, pseudobrookite, ferropseudobrookite, and armalcolite with the subsequent release of both Fe, Ti and oxygen as byproducts. We also propose to use CB biomass for CH4 production as carbon stock and a propellant. Both processes can be accomplished in an energy and cost effective manner because sunlight will be used as an energy source and allows the reactions at ambient temperatures between 10-60 C. Current evaluations include assessing the thermodynamics of such biogenic reactions using a variety of nutrients and atmospheric parameters, as well as assessing the rates and species variation effects of the driving reactions.

Brown, Igor↗
NASA NTRS2006

Iron-Tolerant Cyanobacteria for Human Habitation beyond Earth

In light of the President's Moon/Mars initiative, lunar exploration has once again become a priority for NASA. In order to establish permanent bases on the Moon and proceed with human exploration of Mars, two key problems will be addressed: first, the production of O2 and second, the production of methane (CH4). While O2 is required for life support systems (LSS), both liquid O2 and CH4 are needed as an oxidizer and a propellant, respectively for the Lunar Surface Access Module (LSAM) and the Crew Exploration Vehicle (CEV). Unlike previous propulsion systems, the new CEV will use liquid oxygen (LO2) as an oxidizer and liquid methane (LCH4) as a propellant. Existing technology (e.g. hydrogen reduction) for the production of liquid oxygen from lunar regolith is very energy intensive and requires high temperature reactors. We propose an alternative approach using iron-tolerant cyanobacteria. We have found that iron-tolerant cyanobacteria (IT CB) are capable of etching iron-bearing minerals, which may lead to bonds breaking between Fe and O of common lunar mare basalt Feoxides including ilmenite, pseudobrookite, ferropseudobrookite, and armalcolite with the subsequent release of both Fe, Ti and oxygen as by-products. We also propose to use CB biomass for CH4 production as carbon stock and a propellant. Both processes can be accomplished in an energy and cost effective manner because sunlight will be used as an energy source and allows the reactions at ambient temperatures between 10-60 C. Current evaluations include assessing the thermodynamics of such biogenic reactions using a variety of nutrients and atmospheric parameters, as well as assessing the rates and species variation effects of the driving reactions.

Brown, Igor↗
NASA NTRS2007

Data Fusion for Earth Science Remote Sensing

Beginning in 2004, NASA has supported the development of an international network of ground-based remote sensing installations for the measurement of greenhouse gas columns. This collaboration has been successful and is currently used in both carbon cycle investigations and in the efforts to validate the GOSAT space-based column observations of CO2 and CH4. With the support of a grant, this research group has established a network of ground-based column observations that provide an essential link between the satellite observations of CO2, CO, and CH4 and the extensive global in situ surface network. The Total Carbon Column Observing Network (TCCON) was established in 2004. At the time of this report seven sites, employing modern instrumentation, were operational or were expected to be shortly. TCCON is expected to expand. In addition to providing the most direct means of tying the in situ and remote sensing data sets together, TCCON provides a means of testing the retrieval algorithms of SCIAMACHY and GOSAT over the broadest variation in atmospheric state. TCCON provides a critically maintained and long timescale record for identification of temporal drift and spatial bias in the calibration of the space-based sensors. Finally, the global observations from TCCON are improving our understanding of how to use column observations to provide robust estimates of surface exchange of C02 and CH4 in advance of the launch of OCO and GOSAT. TCCON data are being used to better understand the impact of both regional fluxes and long-range transport on gradients in the C02 column. Such knowledge is essential for identifying the tools required to best use the space-based observations. The technical approach and methodology of retrieving greenhouse gas columns from near-IR solar spectra, data quality and process control are described. Additionally, the impact of and relevance to NASA of TCCON and satellite validation and carbon science are addressed.

data fusion↗
NASA NTRS2009

The Impact of Tropical Recirculation on Polar Composition

We derive the tropical modal age of air from an analysis of the water vapor tape recorder. We combine the observationally derived modal age with mean age of air from CO2 and SF6 to create diagnostics for the independent evaluation of the vertical transport rate and horizontal recirculation into the tropics between 16-32 km. These diagnostics are applied to two Global Modeling Initiative (GMI) chemistry and transport model (CTM) age tracer simulations to give new insights into the tropical transport characteristics of the meteorological fields from the GEOS4-GCM and the GEOS4-DAS. Both simulations are found to have modal ages that are in reasonable agreement with the empirically derived age (i.e ., transit times) over the entire altitude range. Both simulations show too little horizontal recirculation into the tropics above 22 km, with the GEOS4-DAS fields having greater recirculation. Using CH4 as a proxy for mean age, comparisons between HALOE and model CH4 in the Antarctic demonstrate how the strength of tropical recirculation affects polar composition in both CTM experiments. Better tropical recirculation tends to improve the CH4 simulation in the Antarctic. However, mean age in the Antarctic lower stratosphere can be compromised by poor representation of tropical ascent, tropical recirculation, or vortex barrier strength. The connection between polar and tropical composition shown in this study demonstrates the importance of diagnosing each of these processes separately in order to verify the adequate representation of the processes contributing to polar composition in models.

Strahan, S. E.↗
NASA NTRS2011

Carbon Dioxide Reduction Technology Trade Study

For long-term human missions, a closed-loop atmosphere revitalization system (ARS) is essential to minimize consumables. A carbon dioxide (CO2) reduction technology is used to reclaim oxygen (O2) from metabolic CO2 and is vital to reduce the delivery mass of metabolic O2. A key step in closing the loop for ARS will include a proper CO2 reduction subsystem that is reliable and with low equivalent system mass (ESM). Sabatier and Bosch CO2 reduction are two traditional CO2 reduction subsystems (CRS). Although a Sabatier CRS has been delivered to International Space Station (ISS) and is an important step toward closing the ISS ARS loop, it recovers only 50% of the available O2 in CO2. A Bosch CRS is able to reclaim all O2 in CO2. However, due to continuous carbon deposition on the catalyst surface, the penalties of replacing spent catalysts and reactors and crew time in a Bosch CRS are significant. Recently, technologies have been developed for recovering hydrogen (H2) from Sabatier-product methane (CH4). These include methane pyrolysis using a microwave plasma, catalytic thermal pyrolysis of CH4 and thermal pyrolysis of CH4. Further, development in Sabatier reactor designs based on microchannel and microlith technology could open up opportunities in reducing system mass and enhancing system control. Improvements in Bosch CRS conversion have also been reported. In addition, co-electrolysis of steam and CO2 is a new technology that integrates oxygen generation and CO2 reduction functions in a single system. A co-electrolysis unit followed by either a Sabatier or a carbon formation reactor based on Bosch chemistry could improve the overall competitiveness of an integrated O2 generation and CO2 reduction subsystem. This study evaluates all these CO2 reduction technologies, conducts water mass balances for required external supply of water for 1-, 5- and 10-yr missions, evaluates mass, volume, power, cooling and resupply requirements of various technologies. A system analysis and comparison among the technologies was made based on ESM, technology readiness level and reliability. Those technologies with potential were recommended for development.

Jeng, Frank F.↗
NASA NTRS2010

Can Vertical Profiles of Tropospheric Methane on Titan Be Derived from Radio-Occultation Soundings?

The intensity of the received signal at Earth in the radio occultations of Titan is attenuated both by refractive defocusing and pressure-induced absorption from N2-N2 and CH4-N2 pairs. Because the absorption strength is different for the two sets of pairs, matching the retrieved absorptivity profile can in principle yield the vertical variation in gaseous methane in the troposphere. There are two factors that make this difficult. The first is the propagation of noise in the phase and amplitude of the received signal in the absorption retrieval. The phase data is first inverted to retrieve vertical profiles of refractivity, from which the refractive defocusing is calculated. This is then subtracted from the observed. intensity attenuation of the received signal to generate a profile of atmospheric absorption. The second problem is the uncertainty in the pressure-induced absorption coefficients. Laboratory data at radio wavelengths is only available near room temperature (see, e.g., [1] for N2-N2), and the extrapolation to the low temperatures in Titan's troposphere is not well established. Ab initio calculations by Borysow et al. [2, 3] provide absorption coefficients at low temperatures and long wavelengths, but their accuracy has come into question. We present examples from Cassini radio occultations of Titan to illustrate the difficulties. For methane mole fractions in the lower troposphere comparable to that inferred from the Huygens probe (approximately 0.05), it will be difficult to separate the contributions of N2-N2 collisions from those of N2-CH4, collisions to the retrieved absorption. However, higher concentrations of CH4 and/or a higher signal-to-noise ratio from a future uplink experiment could result in a successful separation of the two components. However, key to this are highly accurate estimates of the absorption from a combination of laboratory measurements at love temperatures and long wavelengths, and possibly improved theoretical calculations.

Flasar, F. Michael↗
NASA NTRS2010

The Formation of Sulfate and Elemental Sulfur Aerosols Under Varying Laboratory Conditions: Implications for Early Earth

The presence of sulfur mass-independent fractionation (S-MIF) in sediments more than 2.45 x 10(exp 9) years old is thought to be evidence for an early anoxic atmosphere. Photolysis of sulfur dioxide (SO2) by UV light with lambda < 220 nm has been shown in models and some initial laboratory studies to create a S-MIF; however, sulfur must leave the atmosphere in at least two chemically different forms to preserve any S-MIF signature. Two commonly cited examples of chemically different sulfur species that could have exited the atmosphere are elemental sulfur (S8) and sulfuric acid (H2S04) aerosols. Here, we use real-time aerosol mass spectrometry to directly detect the sulfur-containing aerosols formed when SO2 either photolyzes at wavelengths from 115 to 400 nm, to simulate the UV solar spectrum, or interacts with high-energy electrons, to simulate lightning. We found that sulfur-containing aerosols form under all laboratory conditions. Further, the addition of a reducing gas, in our experiments hydrogen (H2) or methane (CH4), increased the formation of S8. With UV photolysis, formation of S8 aerosols is highly dependent on the initial SO2 pressure; and S8 is only formed at a 2% SO2 mixing ratio and greater in the absence of a reductant, and at a 0.2% SO2 mixing ratio and greater in the presence of 1000 ppmv CH4. We also found that organosulfur compounds are formed from the photolysis of CH4 and moderate amounts of SO2, The implications for sulfur aerosols on early Earth are discussed.

DeWitt, H. Langley↗
NASA NTRS2011

High-Frequency Measurements of Methane Ebullition Over a Growing Season at a Temperate Peatland Site

Bubbles can contribute a significant fraction of methane emissions fr om wetlands; however the range of reported fractions is very large an d accurate characterization of this pathway has proven difficult. Her e we show that continuous automated flux chambers combined with an in tegrated cavity output spectroscopy (ICOS) instrument allow us to qua ntify both CH4 ebullition rate and magnitude. For a temperate poor f en in 2009, ebullition rate varied on hourly to seasonal time scales. A diel pattern in ebullition was identified with peak release occurr ing between 20:00 and 06:00 local time, though steady fluxes (i.e., t hose with a linear increase in chamber headspace CH4 concentration) d id not exhibit diel variability. Seasonal mean ebullition rates peake d at 843.5 +/- 384.2 events m(exp -2)/d during the summer, with a me an magnitude of 0.19 mg CH4 released in each event.

Goodrich, Jordan P.↗
NASA NTRS2010

Lidar Measurements of Methane and Applications for Aircraft and Spacecraft

Atmospheric methane levels have remained relatively constant over the last decade around 1.78 parts per million (ppm) but observations since 2007 show that levels may be increasing. This trend may be caused by increased fossil fuel production, rice farming, livestock and landfills, but the underlying causes are quite uncertain. One hypothesis is that reservoirs of carbon trapped in the permafrost regions of northern Canada, Europe, and Siberia thaw as global temperatures rise and are releasing increasing amounts of methane. Another hypothesis points to increased production of methane by microbes as the permafrost warms. Currently most observations of greenhouse gases are limited to in-situ (surface and tower sites) and limited airborne in-situ measurements. Space column density measurements are starting to become available from the GOSAT mission. Although methane survives for a shorter time in the atmosphere than CO2, its impact on climate change per molecule is about 23 times than that of CO2. Accurate global observations of several greenhouse gases, including methane, are urgently needed in order to better understand climate change processes and to reduce the uncertainty in the carbon budget. Differential absorption lidar is a well-established technique to measure atmospheric gases, and methane has optical absorption bands near 1.65,2.2,3.4 and 7.8 micron. The near infrared overtones lines of CH4 near 1650 nm are relatively free of interference from other species. There are absorption lines near 1651 nm which are both temperature insensitive and have line strengths well suited for lidar measurements. We have developed a laser and demonstrated lidar measurements of CH4 using lines in this band. Our laser uses a narrow linewidth 1064 nm laser pulse passing through a nonlinear crystal. We generate the tunable laser signals near 1651 nm by using the optical parametric amplification (OPA) process. Inside the crystal the 1064 nm beam overlaps with an injection seed laser near 1651 nm from a wavelength tunable diode laser. Incident photons from the pump laser pulse are converted into two photons, with one at the wavelength of the injection seeder. The wavelength of the OPA output is tuned via the wavelength of diode laser. Our laser is tunable, operates near 1651 nm and generates approximately 4 uJ/pulse at 6 KHz. We vary the emission wavelengths within this band by tuning the diode laser's wavelength. We have used this OPA transmitter to make measurements of CH4 at various pressures in a gas cell and over open outdoor horizontal paths. We have measured the lineshape of methane in a 6 cm long cell at various energy levels with this transmitter, with excellent agreement with the lineshape calculated by HITRAN. We have also measured the absorption lineshape of atmospheric methane in an open 3 km outdoor path. The agreement between the measurements and HITRAN, for 1746 ppb and 760 Torr was quite good. We have also made pulsed two wavelength lidar measurements of methane line absorption in the column to a tower at 1.5 km range. These used on- and off-line wavelengths of 1650.957 nm, and 1651.072 nm, and a 20 cm diameter receiver telescope with an infrared PMT detector. The absorption of the on-line photons was 30%. The methane column absorption was estimated via HITRAN, and was in good agreement with the expected methane absorption for a concentration of 1750 ppm. Finally we have calculated the measurement performance of an airborne methane lidar using this transmitter, as well as the energy and telescope scaling needed for a lidar for space. These results, and more details of our experiments will be described in the presentation.

Riris, Haris↗
NASA NTRS2012

Miniaturized Laser Heterodyne Radiometer (LHR) for Measurements of Greenhouse Gases in the Atmospheric Column

This passive laser heterodyne radiometer (LHR) instrument simultaneously measures multiple trace gases in the atmospheric column including carbon dioxide (CO2) and methane (CH4), and resolves their concentrations at different altitudes. This instrument has been designed to operate in tandem with the passive aerosol sensor currently used in AERONET (an established network of more than 450 ground aerosol monitoring instruments worldwide). Because aerosols induce a radiative effect that influences terrestrial carbon exchange, simultaneous detection of aerosols with these key carbon cycle gases offers a uniquely comprehensive measurement approach. Laser heterodyne radiometry is a technique for detecting weak signals that was adapted from radio receiver technology. In a radio receiver, a weak input signal from a radio antenna is mixed with a stronger local oscillator signal. The mixed signal (beat note, or intermediate frequency) has a frequency equal to the difference between the input signal and the local oscillator. The intermediate frequency is amplified and sent to a detector that extracts the audio from the signal. In the LHR instrument described here, sunlight that has undergone absorption by the trace gas is mixed with laser light at a frequency matched to a trace gas absorption feature in the infrared (IR). Mixing results in a beat signal in the RF (radio frequency) region that can be related to the atmospheric concentration. For a one-second integration, the estimated column sensitivities are 0.1 ppmv for CO2, and <1 ppbv for CH4. In addition to producing a standalone ground measurement product, this instrument could be used to calibrate/validate four Earth observing missions: ASCENDS (Active Sensing of CO2 Emissions over Nights, Days, and Seasons), OCO-2 (Orbiting Carbon Observatory), OCO-3, and GOSAT (Greenhouse gases Observational SATellite). The only network that currently measures CO2 and CH4 in the atmospheric column is TCCON (Total Carbon Column Observing Network), and only two of its 16 operational sites are in the United States. TCCON data is used for validation of GOSAT data, and will be used for OCO-2 validation. While these Fourier-transform spectrometers (FTS) can measure the largest range of trace gases, the network is severely limited due to the high cost and extreme size of these instruments (these occupy small buildings and require personnel for operation). The LHR/AERONET instrument offers a significantly smaller (carry-on luggage size) autonomous instrument that can be incorporated into AERONET s much larger (450 instruments) global network.

Steel, Emily↗
NASA NTRS2012

Primary Volatile Abundances in Comets from Infrared Spectroscopy: Implications for Reactions on Grain Surfaces in the Interstellar/Nebular Environment

Comets retain relatively primitive icy material remaining from the epoch of Solar System formation, however the extent to which they are modified from their initial state remains a key question in cometary science. High-resolution lR spectroscopy has emerged as a powerful tool for measuring vibrational emissions from primary volatiles (i.e., those contained in the nuclei of comets). With modern instrumentation, most notably NIRSPEC at the Keck II 10-m telescope, we can quantify species of astrobiological importance (e.g., H20, C2H2, CH4, C2H6, CO, H2CO, CH30H, HCN, NH3). In space environments, compounds of keen interest to astrobiology could originate from HCN and NH3 (leading to amino acids), H2CO (leading to sugars), or C2H6 and CH4 (suggested precursors of ethyl- and methylamine). Measuring the abundances of these precursor molecules (and their variability among comets) is a feasible task that contributes to understanding their delivery to Earth's early biosphere and to the synthesis of more complex pre biotic compounds. Over 20 comets have now been measured with IR spectroscopy, and this sample reveals significant diversity in primary volatile compositions. From this, a taxonomic classification scheme is emerging, presumably reflecting the diverse conditions experienced by pre-cometary grains in interstellar and subsequent nebular environs. The importance of H-atom addition to C2H2 on the surfaces of interstellar grains to produce C2H6 was validated by the discovery of abundant ethane in comet C/1996 B2 (Hyakutake) with C2H6/CH4 well above that achievable by gas-phase chemistry , and then in irradiation experiments on laboratory ices at 10 - 50 K. The large abundance ratios C2H6/CH4 observed universally in comets establish H-atom addition as an important and likely ubiquitous process, and comparing C2H6/C2H2 among comets can provide information on its efficiency. The IR is uniquely capable since symmetric hydrocarbons (e.g., C2H2, CH4, C2H6) have no electric dipole moment and thus no allowed pure rotational transitions. CO should also be hydrogenated on grain surfaces. Irradiation experiments on interstellar ice analogs show this to require very low temperatures, the resulting yields of H2CO and CH30H being highly dependent on temperature in the range approx 10 - 25 K. The relative abundances of these chemically-related molecules in comets provide one measure of the efficiency of H-atom addition to CO Oxidation of CO is also important on grain mantles, as evidenced by the widespread presence of C02 ice towards interstellar sources observed with ISO and in a survey of 17 comets observed with AKARI. H-atom addition to C2H2 produces the vinyl radical, and through subsequent oxidation1reduction reactions can lead to vinyl alcohol, acetaldehyde, and ethanol This may have implications for interpreting observed abundance ratios CO/C2H2. We will discuss possible implications regarding formation conditions in the context of measured primary volatile compositions, emphasizing recently observed comets and published results. These are continually providing new insights regarding our taxonomic scheme and also delivery of pre-biological material to the young Earth.

DiSanti, M. A.↗
NASA NTRS2012

Titan's Stratospheric Condensibles at High Northern Latitudes During Northern Winter

The Infrared Interferometer Spectrometer (IRIS) instrument on board Voyager 1 caught the first glimpse of an unidentified particulate feature in Titan's stratosphere that spectrally peaks at 221 per centimeter. Until recently, this feature that we have termed 'the haystack,' has been seen persistently at high northern latitudes with the Composite Infrared Spectrometer (CIRS) instrument onboard Cassini, The strength of the haystack emission feature diminishes rapidly with season, becoming drastically reduced at high northern latitudes, as Titan transitions from northern winter into spring, In contrast to IRIS whose shortest wavenumber was 200 per centimeter, CIRS extends down to 10 per centimeter, thus revealing an entirely unexplored spectral region in which nitrile ices have numerous broad lattice vibration features, Unlike the haystack, which is only found at high northern latitudes during northern winter/early northern spring, this geometrically thin nitrile cloud pervades Titan's lower stratosphere, spectrally peaking at 160 per centimeter, and is almost global in extent spanning latitudes 85 N to 600 S, The inference of nitrile ices are consistent with the highly restricted altitude ranges over which these features are observed, and appear to be dominated by a mixture of HCN and HC3N, The narrow range in altitude over which the nitrile ices extend is unlike the haystack, whose vertical distribution is significantly broader, spanning roughly 70 kilometers in altitude in Titan's lower stratosphere, The nitrile clouds that CIRS observes are located in a dynamically stable region of Titan's atmosphere, whereas CH4 clouds, which ordinarily form in the troposphere, form in a more dynamically unstable region, where convective cloud systems tend to occur. In the unusual situation where Titan's tropopause cools significantly from the HASI 70.5K temperature minimum, CH4 should condense in Titan's lower stratosphere, just like the aforementioned nitrile clouds, although in significantly larger abundances. We will present the spectral and vertical distribution of Titan's stratospheric particulates during northern winter on Titan. The drastically changing abundance of the haystack over a small latitude range will be highlighted, specifically comparing the IRIS and CIRS epochs, Finally, we will discuss the situation in which CH4 condenses in Titan's lower stratosphere, forming an unexpected quasi steady-state stratospheric Ice cloud.

Anderson, Carrie↗
NASA NTRS2010

Regolith Volatile Characterization (RVC) in RESOLVE

Resource investigation in the lunar poles is of importance to the potential impact of in-situ resource utilization (ISRU). The RESOLVE project developed a payload to investigate the permanently shadowed areas of the lunar poles and demonstrate ISRU technology. As a part of the RESOLVE project, the regolith volatile characterization (RVC) subsystem was designed to examine the release of volatiles from sample cores. The test sample was heated in the reactor to release the volatiles where they were analyzed with gas chromatography. Subsequently, the volatile sample was introduced into the lunar water resource demonstration (LWRD) subsystem where the released hydrogen and water were selectively captured. The objective of the Regolith Volatile Characterization (RVC) subsystem was to heat the crushed core sample and determine the desorption of volatile species of interest. The RVC subsystem encompasses the reactor and the system for volatile analysis. The system was designed to analyze H2, He, CO, CO2, N2, 02, CH4, H2S and H2O. The GC chosen for this work is a Siemens MicroSAM process GC with 3 columns and 8 TCD detectors. Neon was chosen as the carrier gas to enhance the analysis of hydrogen and helium.The limit of detection for the gases is approx.1000ppm for H2, CO. CO2 , N2, O2 and H2 S. The limit of detection for CH4 is approx.4000ppm and the water limit of detection is -10000 ppm with a sample analysis time of 2-3 minutes. These values (with the exception of water and H2S) were determined by dilution of a six gas mixture from Scott Gas (5% CO2, CO, O2, N2, 4% CH4 and H2) using mass flow controllers (MFC5). Water was calibrated at low levels using an in house relative humidity (RH) generator. H 2S and high concentrations of H2 were calibrated by diluting a pure stream of gas with MFCs. Higher concentrations of N2 and 02 were calibrated using Air again diluting with MFCs. There were three modification goals for the GC in EBU2 that would allow this process GC to be used in the field demo for RESOLVE. The first modification was to decrease the weight associated with the GC, this included eliminating the explosion proof case (Figure 1) and replacing it with a lightweight case as well as using an on board COPV tank for the neon carrier gas. The next goal was to add a second oven for the molecular sieve column to allow for dual temperature control during GC operation; the separation of hydrogen and helium is optimum at lower temperatures while the water analysis required higher temperatures creating a competing design requirement. The second oven also allows a lower limit of detection for water quantification and avoids the possibility of water condensing in the GC which could ruin the column characteristics. The final goal was to modify the column arrangement to optimize the system for our specific application. Figure 2 shows the internal details of the module optimized optimized for our field application. The modifications and performance of the gas analysis system will be discussed in detail.

Captain, Janine↗
NASA NTRS2014

The Atmospheres of Directly Imaged Planets: Where Has All the Methane Gone?

Methane and ammonia both first appear at lower effective temperatures in brown dwarf atmospheres than equilibrium chemistry models would suggest. This has traditionally been understood as a consequence of vertical mixing timescales being shorter than chemical equilibration timescales in brown dwarf photospheres. Indeed the eddy diffusivity, a variable accounting for the vigor of vertical mixing, has become a standard part of the description of brown dwarf atmosphere models, along with Teff and log g. While some models have suggested that methane is less favored at lower gravity, the almost complete absence of methane in the atmospheres of directly imaged planets, such as those orbiting HR 8799, even at effective temperatures where methane is readily apparent in brown dwarf spectra, has been puzzling. To better understand the paucity of methane in low gravity atmospheres we have revisited the problem of methane chemistry and mixing. We employed a 1-D atmospheric chemistry code augmented with an updated and complete network of the chemical reactions that link CO to CH4. We find the methane abundance at altitudes at or above the effective photosphere is a strong function of surface gravity because higher g shifts the p-T structure to higher pressures (i.e., a given optical depth is proportional to p/g, a relation mitigated somewhat by pressure broadening). Thus quenching in more massive brown dwarfs occurs at a lower temperature and higher pressure, both favoring CH4. We predict that in the lowest mass young giant planets, methane will appear very late, at effective temperatures as low as 600 K rather than the 1200 K seen among field brown dwarfs. This methane deficiency has important implications for the interpretation of spectra as well as methane-based planetary companion searches, such as the NICI survey. The GPI and SPHERE surveys will test these ideas and probe atmospheric chemistry and composition in an entire new range of parameter space. A caveat is that these calculations presume that the C to O ratio is comfortably less than one; the behavior is quite different if C and O are equally abundant, and of course CH4 is always present if C exceeds O.

young giant planets↗