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At least 775 records · Page 43

Thioredoxins in evolutionarily primitive organisms

Thioredoxins are low molecular weight redox proteins, alternating between the S-S (oxidized) and SH (reduced) states, that function in a number of biochemical processes, including DNA synthesis, DNA replication, and enzyme regulation. Until recently, reduced ferredoxin was known to serve as the source of reducing power for the reduction of thioredoxins only in oxygenic photosynthetic cells. In all other organisms, the source of hydrogen (electrons) for thioredoxin reduction was considered to be NADPH. It was found that Clostridium pasteurianum, an anaerobic organism normally living in the soil unexposed to light, resembles photosynthetic cells in using ferredoxin for the reduction of thioredoxin. The results reveal the existence of a pathway in which ferredoxin, provides the reducing power for the reduction of thioredoxin via the flavoprotein enzyme, ferredoxinthioredoxin reductase. In related studies, it was found that Chromatium vinosum, an anaerobic photosynthetic purple sulfur bacterium, resembles evolutionarily more advanced micro-organisms in having an NADP-thioredoxin system composed of a single thioredoxin which is reduced by NADPH via NADP-thioredoxin reductase. The adoption of the NADP-thioredoxin system by Chromatium seems appropriate in view of evidence tha the organi sm utilizes ATP-driven reverse electron transport. Finally, results of research directed towards the identification of target enzymes of the ferredoxin/thioredoxin system in a cyanobacterium (Nostoc muscorum), show that thioredoxin-linked photosynthetic enzymes of cyanobateria are similar to those of chloroplasts. It now seems that the ferredoxin/thioredoxin system functions in regulating CO2 assimilation via the reductive pentose phosphate cycle in oxygenic but not anoxygenic photosynthetic cells.

Buchanan, B. B.↗

Thermal emission spectroscopy of the middle atmosphere

The general objective of this research is to obtain, via remote sensing, simultaneous measurements of the vertical distributions of stratospheric temperature, ozone, and trace constituents that participate in the catalytic destruction of ozone (NO(sub y): NO, NO2, NO3, HNO3, ClONO2, N2O5, HNO4; Cl(sub x): HOCl), and the source gases for the catalytic cycles (H2O, CH4, N2O, CF2Cl2, CFCl3, CCl4, CH3Cl, CHF2Cl, etc.). Data are collected during a complete diurnal cycle in order to test our present understanding of ozone chemistry and its associate catalytic cycles. The instrumentation employed is an emission-mode, balloon-borne, liquid-nitrogen-cooled Michelson interferometer-spectrometer (SIRIS), covering the mid-infrared range with a spectral resolution of 0.020 cm(exp -1). Cryogenic cooling combined with the use of extrinsic silicon photoconductor detectors allows the detection of weak emission features of stratospheric gaseous species. Vertical distributions of these species are inferred from scans of the thermal emission of the limb in a sequence of elevation angles. The fourth SIRIS balloon flight was carried out from Palestine, Texas on September 15-16, 1986 with 9 hours of nighttime data (40 km). High quality data with spectral resolution 0.022 cm(exp -1), were obtained for numerous limb sequences. Fifteen stratospheric species have been identified to date from this flight: five species from the NO(sub y) family (HNO3, NO2, NO, ClONO2, N2O5), plus CO2, O3, H2O, N2O, CH4, CCl3F, CCl2F2, CHF2Cl, CF4, and CCl4. The nighttime values of N2O5, ClONO2, and total odd nitrogen have been measured for the first time, and compared to model results. Analysis of the diurnal variation of N2O5 within the 1984 and 1986 data sets, and of the 1984 ClONO2 measurements, were presented in the literature. The demonstrated ability of SIRIS to measure all the major NO(sub y) species, and therefore to determine the partitioning of the nitrogen family over a continuous diurnal cycle, is a powerful tool in the verification and improvement of photochemical modeling.

Kunde, V. G.↗

Transport in the Subtropical Lowermost Stratosphere during the Cirrus Regional Study of Tropical Anvils and Cirrus Layers-Florida Area Cirrus Experiment

We use in situ measurements of water vapor (H2O), ozone (O3), carbon dioxide (CO2), carbon monoxide (CO), nitric oxide (NO), and total reactive nitrogen (NOy) obtained during the CRYSTAL-FACE campaign in July 2002 to study summertime transport in the subtropical lowermost stratosphere. We use an objective methodology to distinguish the latitudinal origin of the sampled air masses despite the influence of convection, and we calculate backward trajectories to elucidate their recent geographical history. The methodology consists of exploring the statistical behavior of the data by performing multivariate clustering and agglomerative hierarchical clustering calculations and projecting cluster groups onto principal component space to identify air masses of like composition and hence presumed origin. The statistically derived cluster groups are then examined in physical space using tracer-tracer correlation plots. Interpretation of the principal component analysis suggests that the variability in the data is accounted for primarily by the mean age of air in the stratosphere, followed by the age of the convective influence, and last by the extent of convective influence, potentially related to the latitude of convective injection (Dessler and Sherwood, 2004). We find that high-latitude stratospheric air is the dominant source region during the beginning of the campaign while tropical air is the dominant source region during the rest of the campaign. Influence of convection from both local and nonlocal events is frequently observed. The identification of air mass origin is confirmed with backward trajectories, and the behavior of the trajectories is associated with the North American monsoon circulation.

Pittman, Jasna V.↗

Transport in the Subtropical Lowermost Stratosphere during CRYSTAL-FACE

We use in situ measurements of water vapor (H2O), ozone (O3), carbon dioxide (CO2), carbon monoxide (CO), nitric oxide (NO), and total reactive nitrogen (NO(y)) obtained during the CRYSTAL-FACE campaign in July 2002 to study summertime transport in the subtropical lowermost stratosphere. We use an objective methodology to distinguish the latitudinal origin of the sampled air masses despite the influence of convection, and we calculate backward trajectories to elucidate their recent geographical history. The methodology consists of exploring the statistical behavior of the data by performing multivariate clustering and agglomerative hierarchical clustering calculations, and projecting cluster groups onto principal component space to identify air masses of like composition and hence presumed origin. The statistically derived cluster groups are then examined in physical space using tracer-tracer correlation plots. Interpretation of the principal component analysis suggests that the variability in the data is accounted for primarily by the mean age of air in the stratosphere, followed by the age of the convective influence, and lastly by the extent of convective influence, potentially related to the latitude of convective injection [Dessler and Sherwuud, 2004]. We find that high-latitude stratospheric air is the dominant source region during the beginning of the campaign while tropical air is the dominant source region during the rest of the campaign. Influence of convection from both local and non-local events is frequently observed. The identification of air mass origin is confirmed with backward trajectories, and the behavior of the trajectories is associated with the North American monsoon circulation.

Pittman, Jasna V.↗

A Multi-Sensor, Low Volume, Automated Culture System for Space Biology Experiments

Optical density (absorbance) is commonly used in microbiology to measure cell concentration and other colorimetric indicators. It is the main type of bioscience data returned from the BioSentinel small spacecraft mission, which was recently launched as a secondary payload on Artemis I. The flight unit takes absorbance measurements of yeast cultures at 570 nm, 630 nm, and 850 nm to track cell concentration and oxidation-reduction (redox) state of the metabolic indicator dye alamarBlue over time [1]. Because the data returned from a small spacecraft mission is necessarily limited, BioSentinel uses a specialized ground-based experiment apparatus to map the absorbance data onto several other parameters. This culture apparatus is composed of a polycarbonate base and lid which contain ports for several commercial sensors, including a standard 12 mm dissolved oxygen probe, gaseous CO2, fluid pressure, and two micro-probes for measuring pH and redox potential. It also contains a pressure relief valve, a rubber membrane for culture interaction, and a 12mm port for the custom optical probe designed to match in-flight measurements. Modules in two corners expand the culture volume into narrow columns, enabling solid-state optical density measurement and dielectric spectroscopy. The apparatus can be fit to a plate for magnetic stirring. The apparatus’s optical probe allows mapping between the flight unit’s optical data and the additional parameters measured by the ground-based experiments. Within the probe, a linear actuator pulls a plunger, drawing culture volume into the optical path. The actuator then pushes out the plunger and culture volume, cleaning any stray yeast from the inside surface of the probe. The probe chassis is 3D-printed from biocompatible resin with the optoelectronics cured inside an optically clear conformal coat which functions as a lens. To optimize the probe’s dimensions, including optical path, a test harness was developed to manipulate and measure distance while the LED light sources and photodiode detector are in operation. The test harness was composed of two 3/64” thick polycarbonate plates mounted to a set of calipers. The LEDs and photodiode were mounted on the outside of each plate. A cuvette of sample fluid was then clamped between the plates in line between the LEDs and photodiode. The test harness generated a 78% signal change between water and a dye standard for the green (570 nm) LED, a 90% signal change for the red (630 nm) LED, and a 25% signal change between water and overgrown yeast for the infrared (850 nm) LED. The improvements to the ground experiment apparatus (culture volume reduction, inclusion of an optical probe to measure flight-like optical data, and magnetic stirring for culture homogeneity) allow for more flight-like measurements to be taken and more accurate mapping of these additional parameters to the optical data returned from the flight unit. This enhancement to mission science return will give insight into how deep space radiation may affect human biology for future long-term space exploration.

Multi-Sensor↗

Stability of Basalt plus Anhydrite plus Calcite at HP-HT: Implications for Venus, the Earth and Mars

"Canali" observed at Venus surface by Magellan are evidence for very long melt flows, but their composition and origin remain uncertain. The hypothesis of water-rich flow is not reasonable regarding the temperature at Venus surface. The length of these channels could not be explained by a silicate melt composition but more likely, by a carbonate-sulfate melt which has a much lower viscosity (Kargel et al 1994). One hypothesis is that calcite CaCO3 and anhydrite CaSO4 which are alteration products of basalts melted during meteorite impacts. A famous example recorded on the Earth (Chicxulub) produced melt and gas rich in carbon and sulfur. Calcite and sulfate evaporites are also present on Mars surface, associated with basalts. An impact on these materials might release C- and S-rich melt or fluid. Another type of planetary phenomenon (affecting only the Earth) might provoke a high pressure destabilization of basalt+anhydrite+calcite. Very high contents of C and S are measured in some Earth s magmas, either dissolved or in the form of crystals (Luhr 2008). As shown by the high H content and high fO2 of primary igneous anhydrite-bearing lavas, the high S content in their source may be explained by subduction of an anhydrite-bearing oceanic crust, either directly (by melting followed by eruption) or indirectly (by release of S-rich melt or fluid that metasomatize the mantle) . Calcite is a major product of oceanic sedimentation and alteration of the crust. Therefore, sulfate- and calcite-rich material may be subducted to high pressures and high temperatures (HP-HT) and release S- and C-rich melts or fluids which could influence the composition of subduction zone lavas or gases. Both phenomena - meteorite impact and subduction - imply HP-HT conditions - although the P-T-time paths are different. Some HP experimental/theoretical studies have been performed on basalt/eclogite, calcite and anhydrite separately or on a combination of two. In this study we performed piston-cylinder experiments at 1 GPa between 950 and 1700 C using a mixture of 70wt% tholeiitic basalt + 15wt% anhydrite + 15wt% calcite. Up to ~1440 C, an ultracalcic (CaO>13.5 wt%; CaO/Al2O3>1 wt%) picrobasaltic (SiO2~40-45 wt%; Na2O+K2O<2 wt%) melt containing up to 5 wt% SO3 and up to 5.3 wt% CO2+H2O (calculated by difference) is present in equilibrium with clinopyroxene, anhydrite, spinel-chromite, a CAS-phase and a gas composed mainly of CO and an aliphatic thiol (CH2)4SH. Hydrogen was incorporated either by contact between the starting material and air or by diffusion through the capsule during the experiments. The S content in the gas increases with temperature and run duration, implying that gases with various C/S ratios might be released during an impact or at subduction zones, depending on the P-T-t path and on the H content. Above approx.1440 C, a Ca-rich carbonate-sulfate melt forms (in equilibrium with the picrobasaltic melt) which contains a few percents of Na and K. Such melt is not expected to form at Earth s subduction temperatures. If it forms by meteorite impact, it might crystallize too fast to explain long flows like Venus canali. A different basalt/anhydrite/calcite ratio might, however, decrease its formation temperature.

Martin, A. M.↗

The Pascal Discovery Mission: A Mars Climate Network Mission

The climate of Mars is a major focus of Mars exploration. With the loss of MCO, however, it remains uncertain how it will be achieved. We argue that a truly dedicated climate mission to Mars should have both orbital and landed components, and that these should operate simultaneously for at least 1 Mars year if not longer. Pascal is a Discovery mission that emphasizes the landed component. Its principal goal is to establish a network of 24 small weather stations on the surface of Mars that will operate for 2 Mars years, with an extended mission option for an additional 8 Mars years bringing the total mission lifetime up to 10 Mars years. The stations will collect hourly measurements of pressure, temperature, and optical depth. After delivering the probes to Mars, Pascal's carrier spacecraft will go into an elliptical orbit which will serve as a relay for the landers, and a platform for synoptic imaging. These simultaneous measurements from the surface and from orbit will allow us to characterize the planet's general circulation and its interaction with the dust, water, and CO2 cycles. During entry, descent, and landing, each of Pascal's 24 probes will also measure the temperature structure of the atmosphere and acquire images of the surface. These data will allow us to determine the global structure of the atmosphere between 15 and 130 km, and characterize the local terrain to help interpret the landed data. The descent images are part of Pascal's outreach program, as the probe camera system will be developed by faculty-supervised student project. The intent is to generate enthusiasm for the Pascal mission by directly involving students. Pascal will be launched on a Delta II-7925 in August of 2005. A type I trajectory will deliver Pascal to Mars in January of 2006. On approach, the three-axis stabilized carrier spacecraft will spring deploy the Pascal probes in 4 separate salvo's of 6 each. Global coverage is achieved with small time-of-arrival adjustments in between each salvo. Pascal's probes utilize an aeroshell, parachute, and crushable material for entry, descent and landing. On the surface, their long life and global coverage is enabled by a Micro Thermal Power Source with demonstrated heritage. After all probes are released, the carrier spacecraft will execute a small burn for insertion into an elliptical orbit. The long lifetime of the Pascal network was chosen in part to maximize the chances that orbital sounding, like that planned with MCO, would occur at some point during the mission. If Pascal is selected for launch in '05, this could occur if MCO-like science is reflown in the '05 opportunity or, if it is reflown in '03, the mission is extended to overlap with Pascal. The combination of temperature sounding from orbit, and surface pressure mapping from the surface will allow a direct determination of the full 3-D wind field for the first time.

Haberle, R. M.↗

The Pascal Discovery Mission: A Mars Climate Network Mission

The climate of Mars is a major focus of Mars exploration. With the loss of MCO, however, it remains uncertain how it will be achieved. We argue that a truly dedicated climate mission to Mars should have both orbital and landed components, and that these should operate simultaneously for at least I Mars year if not longer. Pascal is Discovery mission that emphasizes the landed component. Its principal goal is to establish a network of 24 small weather stations on the surface of Mars that will operate for 2 Mars years, with an extended mission option for an additional 8 Mars years bringing the total mission lifetime up to 10 Mars years. The stations will collect hourly measurements of pressure, temperature, and optical depth. After delivering the probes to Mars, Pascal's carrier spacecraft will go into an elliptical orbit which will serve as a relay for the landers, and a platform for synoptic imaging. These simultaneous measurements from the surface and from orbit will allow us to characterize the planet's general circulation and its interaction with the dust, water, and CO2 cycles. During entry, descent, and landing, each of Pascal's 24 probes will also measure the temperature structure of the atmosphere and acquire images of the surface. These data will allow us to determine the global structure of the atmosphere between 15 and 130 km, and characterize the local terrain to help interpret the landed data. The descent images are part of Pascal's outreach program, as the probe camera system will be developed by faculty-supervised student project. The intent is to generate enthusiasm for the Pascal mission by directly involving students. Pascal will be launched on a Delta 11-7925 in August of 2005. A type I trajectory will deliver Pascal to Mars in January of 2006. On approach, the three-axis stabilized carrier spacecraft will spring deploy the Pascal probes in 4 separate salvo's of 6 each. Global coverage is achieved with small time-of-arrival adjustments in between each salvo. Pascal's probes utilize an aeroshell, parachute, and crushable material for entry, descent and landing. On the surface, their long life and global coverage is enabled by a Micro Thermal Power Source with demonstrated heritage. After all probes are released, the carrier spacecraft will execute a small bum for insertion into an elliptical orbit. The long lifetime of the Pascal network was chosen in part to maximize the chances that orbital sounding, like that planned with MCO, would occur at some point during the mission. If Pascal is selected for launch in -05, this could occur if MCO-like science is reflown in the '05 opportunity or, if it is reflown in '03, the mission is extended to overlap with Pascal. The combination of temperature sounding from orbit, and surface pressure mapping from the surface will allow a direct determination of the full 3-D wind field for the first time.

Haberle, Robert M.↗

On the Ability of Space- Based Passive and Active Remote Sensing Observations of CO2 to Detect Flux Perturbations to the Carbon Cycle

Space-borne observations of CO2 are vital to gaining understanding of the carbon cycle in regions of the world that are difficult to measure directly, such as the tropical terrestrial biosphere, the high northern and southern latitudes, and in developing nations such as China. Measurements from passive instruments such as GOSAT (Greenhouse Gases Observing Satellite) and OCO-2 (Orbiting Carbon Observatory 2), however, are constrained by solar zenith angle limitations as well as sensitivity to the presence of clouds and aerosols. Active measurements such as those in development for the Active Sensing of CO2 Emissions over Nights, Days and Seasons (ASCENDS) mission show strong potential for making measurements in the high-latitude winter and in cloudy regions. In this work we examine the enhanced flux constraint provided by the improved coverage from an active measurement such as ASCENDS. The simulation studies presented here show that with sufficient precision, ASCENDS will detect permafrost thaw and fossil fuel emissions shifts at annual and seasonal time scales, even in the presence of transport errors, representativeness errors, and biogenic flux errors. While OCO-2 can detect some of these perturbations at the annual scale, the seasonal sampling provided by ASCENDS provides the stronger constraint. Plain Language Summary: Active and passive remote sensors show the potential to provide unprecedented information on the carbon cycle. With the all-season sampling, active remote sensors are more capable of constraining high-latitude emissions. The reduced sensitivity to cloud and aerosol also makes active sensors more capable of providing information in cloudy and polluted scenes with sufficient accuracy. These experiments account for errors that are fundamental to the top-down approach for constraining emissions, and even including these sources of error, we show that satellite remote sensors are critical for understanding the carbon cycle.

tropical terrestrial biosphere↗

Climates of Warm Earth-Like Planets. I. 3D Model Simulations

We present a large ensemble of simulations of an Earth-like world with increasing insolation and rotation rate. Unlike previous work utilizing idealized aquaplanet congurations we focus our simulations on modern Earth-like topography. The orbital period is the same as modern Earth, but with zero obliquity and eccentricity. The atmosphere is 1 bar N2-dominated with CO2=400 ppmv and CH4=1 ppmv. The simulations include two types of oceans; one without ocean heat transport (OHT) between grid cells as has been commonly used in the exoplanet literature, while the other is a fully coupled dynamic bathtub type ocean. The dynamical regime transitions that occur as day length increases induce climate feedbacks producing cooler temperatures, rst via the reduction of water vapor with increasing rotation period despite decreasing shortwave cooling by clouds, and then via decreasing water vapor and increasing shortwave cloud cooling, except at the highest insolations. Simulations without OHT are more sensitive to insolation changes for fast rotations while slower rotations are relatively insensitive to ocean choice. OHT runs with faster rotations tend to be similar with gyres transporting heat poleward making them warmer than those without OHT. For slower rotations OHT is directed equator-ward and no high latitude gyres are apparent. Uncertainties in cloud parameterization preclude a precise determination of habitability but do not a affect robust aspects of exoplanet climate sensitivity. This is the first paper in a series that will investigate aspects of habitability in the simulations presented herein. The datasets from this study are open source and publicly available.

Planetary systems↗

In-Situ Reaction Monitoring for Lunar Applications Utilizing a Single Quadrupole Residual Gas Analyzer

With a revived focus to create a permeant presence on the moon and in preparation for future Mars exploration, it is imperative that all re-sources are utilized to their fullest potential. In-Situ Resource Utilization (ISRU) will be critical for future mission success as it would enable independent operation of missions while minimally relying on the complex supply chain created between the Earth, moon and Mars. One of the most critical resources that have been identified for ISRU is the creation of liquid oxygen (O2) for not only breathable air, but also for rocket fuel. On the moon and potentially Mars, one of the most O2 rich resources is in the presence of regolith. Although there are numerous minerals within regolith and various processes to extract O2, this is not the scope of this paper. Since the O2 extraction method can vary, a critical standardized analytical method is needed to verify O2 (or oxygenated precursor compounds) for extraction efficiency and purity. Our group utilizes a modified consumer off-the-shelf (COTS), Residual Gas Analyzer (RGA) Single Quadrupole Mass Spectrometer (QMS). Due to the current field mission requirements, the gas analysis module will need to rely only on mass-to-charge ratios (m/z) and peak intensities to differentiate and quantitate targeted gas-phase reactants or products, i.e. carbon monoxide (CO), carbon dioxide (CO2), methane (CH4) and hydrogen (H2). However, due to solar wind implanted volatiles and various other compounds present in lunar regolith, such as nitrogen (N2), helium (He), and deuterium (D2), deconvolution and quantification of isobaric compounds becomes quite difficult. Specifically, the presence of N2 makes quantification of CO, an oxygenated precursor, difficult due to both compounds having a peak at m/z 28. Approaches to differentiate isobaric components: Initially, the solution to overcome isobaric overlap was to use isotopic ratios, particularly be-tween carbon-13 and nitrogen-15. Although limited literature discuss isotopic composition and attempt to quantify the ratios, variation is particularly high and limited to a few lunar regolith samples. The following were identified as potential approaches to quantify isobaric species, N2 and CO, using our RGA. Threshold Ionization. CO and N2 both have peaks at m/z 28, but only N2 is capable of producing a peak at m/z 7. While a N2 peak at m/z 7 is generally rare, instrument parameters can be optimized in order to maximize the peak intensity. Typically a standard ionization energy of 70 eV is used to monitor a batch process and would produce reliable results for a majority of the reactants or products that we are interested in quantifying. However, to analyze the rare molecular fragment of N2 (N2+ at m/z 7), a different ionization energy may be beneficial. Threshold Ionization Mass Spectrometry (TIMS) will be explored to optimize the N2+ peak at m/z 7 by varying parameters such as ionization energy and pressure. Therefore, a quantitative value at m/z 7 will be used to determine the product gas concentration of N2, which will be subtracted from the total concentration determined at m/z 28 enabling us to approximate the amount of CO. Secondary Detector (infrared gas detector, IR). Another approach to quantitate and differentiate be-tween isobaric components is to leverage alternative modes of detection. Unlike mass spectrometry, which generally uses a separation step prior to analysis (i.e. gas chromatography), IR produces energy that is specifically absorbed depending on the bond and configuration of the molecule. This technique could be leveraged since it is generally only active on non-symmetric molecules, i.e. CO. Utilizing concentrations of CO determined from another detector could help correct concentrations of CO obtained from the QMS. However, the inclusion of another detector adds additional mission requirements, such as power, software changes and avionics updates that add additional cost and schedule requirements.

mass spectrometry↗

A Simulated High CO 2 Spaceflight Environment Increases Plant Preference for Ammonium as a Nitrogen Source.

The growth of crops to sustain astronauts will be critical to long-duration spaceflight missions. Carbon dioxide (CO 2 ) concentrations are very high in spaceflight cabin environments, often 5-10X the CO 2 concentration on Earth 1 . It is therefore crucial to understand how plants respond to elevated CO 2 (eCO 2 ). Nitrogen (N) is important for plant survival, though the effects of eCO 2 on plant uptake of different N forms remain poorly understood. Shoot nitrate assimilation may be reduced at eCO 2 due to a decrease in available reducing power through increased carbon fixation and inhibition of photorespiration 2 , suggesting that eCO 2 may increase plant ammonium preference (Figure 1). A deeper understanding of changes in plant nitrogen form preference in response to eCO 2 will inform nutrient optimization for future space crop production and wastewater processing system design requirements 3 in addition to developing future eCO 2 climate-ready crops.

nitrogen↗

Ground and Airborne Methane Measurements using Optical Parametric Amplifiers

We report on an initial airborne demonstration of atmospheric methane column measurements at 1.65 micrometers using a widely tunable, seeded optical parametric amplifier (OPA) lidar and a photon counting detector. Methane is an important greenhouse gas and accurate knowledge of its sources and sinks is needed for climate modeling. Our lidar system uses 20 pulses at increasing wavelengths and integrated path differential absorption (IPDA) to map a methane line at 1650.9 nanometers. The wavelengths are generated by using a Nd:YAG pump laser at 1064.5 nanometers and distributed feedback diode laser at 1650.9 nanometers and a periodically-poled lithium niobate (PPLN) crystal. The pulse width was 3 nanoseconds and the pulse repetition rate was 6.28 KHz. The outgoing energy was approximately 13 microJoules/pulse. A commercial 20 nanometer diameter fiber-coupled telescope with a photon counting detector operated in analog mode with a 0.8 nanometer bandpass filter was used as the lidar receiver. The lidar system was integrated on NASA's DC-8 flying laboratory, based at Dryden Airborne operations Facility (DAOF) in Palmdale CA. Three flights were performed in the central valley of California. Each flight lasted about 2.5 hours and it consisted of several flight segments at constant altitudes at approximately 3, 4.5, 6, 7.6, 9.1, 10.6 km (l0, 15, 20, 25, 30, 35 kft). An in-situ cavity ring down spectrometer made by Picarro Inc. was flown along with the lidar instrument provided us with the "truth" i.e. the local CH4, CO2 and H2O concentrations at the constant flight altitude segments. Using the aircraft's altitude, GPS, and meteorological data we calculated the theoretical differential optical depth of the methane absorption at increasing altitudes. Our results showed good agreement between the experimentally derived optical depth measurements from the lidar instrument and theoretical calculations as the flight altitude was increased from 3 to 10.6 kilometers, assuming a constant methane mixing ratio of 1.8 parts per million. The in-situ spectrometer did not show any significant deviations from the ambient concentrations. Further analysis using meteorological data from the Global Modeling and Assimilation Office (http://gmao.gsfc.nasa.gov/) to derive the theoretical optical depth also showed good agreement with the experimentally derived values. The OPA lidar system with slight modifications has also been used to measure CO2, water vapor, and CO in the near and mid-infrared spectral regions on the ground.

Riris, Haris↗

Ice-Covered Lakes in Gale Crater Mars: The Cold and Wet Hypothesis

Recent geological discoveries from the Mars Science Laboratory provide evidence that Gale crater may have intermittently hosted a fluvio-lacustine environment during the Hesperian, with individual lakes lasting for a period of tens to hundreds of thousands of years. (Grotzinger et al., Science, 350 (6257), 2015). Estimates of the CO2 content of the atmosphere at the time the Gale sediments formed are far less than needed by any climate model to warm early Mars (Bristow et al., Geology, submitted), given the low solar energy input available at Mars 3.5 Gya. We have therefore explored the possibility that the lakes in Gale during the Hesperian were perennially covered with ice using the Antarctic Lakes as an analog. Using our best estimate for the annual mean surface temperature at Gale at this time (approx. 230K) we computed the thickness of an ice-covered lake. These thickness range from 10-30 meters depending on the ablation rate and ice transparency and would likely inhibit sediments from entering the lake. Thus, a first conclusion is that the ice must not be too cold. Raising the mean temperature to 245K is challenging, but not quite as hard as reaching 273K. We found that a mean annual temperature of 245K ice thicknesses range from 3-10 meters. These values are comparable to the range of those for the Antarctic lakes (3-6 m), and are not implausible. And they are not so thick that sediments cannot penetrate the ice. For the ice-covered lake hypothesis to work, however, a melt water source is needed. This could come from subaqueous melting of a glacial dam in contact with the lakes (as is the case for Lake Untersee) or from seasonal melt water from nearby glaciers (as is the case for the Dry Valley lakes). More work is needed to better assess these possibilities. However, the main advantage of the ice-covered lake model (and the main reason we pursued it) is that it relaxes the requirement for a long-lived active hydrological cycle involving rainfall and runoff, which no climate model is able to produce given known constraints on the early Mars environment.

Antarctic lakes↗

Chemical Characteristics of Continental Outflow from Asia to the Troposphere over the Western Pacific Ocean during September - October 1991: Results from PEM-West A

An important objective of the Pacific Exploratory Mission-West A (PEM-West A) was the chemical characterization of the outflow of tropospheric trace gases and aerosol particles from the Asian continent over the western Pacific Ocean. This paper summarizes the chemistry of this outflow during the period September - October 1991. The vertical distributions of CO, C2H6, and NO(x), showed regions of outflow at altitudes below 2 km and from 8 to 12 km. Mixing ratios of CO were approx. equals 130 parts per billion by volume (ppbv), approx. equals 1OOO parts per trillion by volume (pptv) for C2H6, and approx. equals 100 pptv for NO(x) in both of these regions. Direct outflow of Asian industrial materials was clearly evident at altitudes below 2 km, where halocarbon tracer compounds such as CH3CCl3 and C2Cl4 were enhanced about threefold compared to aged Pacific air. The source attribution of species outflowing from Asia to the Pacific at 8-12 km altitude was not straightforward. Above 10 km altitude there were substantial enhancements of NO(y), O3, CO, CH4, SO2, C2H6, C3H8, C2H2, and aerosol Pb-210 but not halocarbon industrial tracers. These air masses were rich in nitrogen relative to sulfur and contained ratios of C2H2/CO and C3H8/C2H6 (approx. equals l.5 and 0.1 respectively) indicative of several- day-old combustion emissions. It is unclear if these emissions were of Asian origin, or if they were rapidly transported to this region from Europe by the high wind speeds in this tropospheric region (60 - 70 m/s). The significant cyclonic activity over Asia at this time could have transported to the upper troposphere emissions from biomass burning in Southeast Asia or emissions from the extensive use of various biomass materials for cooking and space heating. Apparently, the emissions in the upper troposphere were brought there by wet convective systems since water-soluble gases and aerosols were depleted in these air masses. Near 9 km altitude there was a distinct regional outflow that appeared to be heavily influenced by biogenic processes on the Asian continent, especially from the southeastern area. These air masses contained CH4 in excess of 1800 ppbv, while CO2 and OCS were significantly depleted (349 - 352 ppmv and 450 - 500 pptv, respectively). This signature seemingly reflected CH4 emissions from wetlands and rice paddies with coincident biospheric uptake of tropospheric CO2 and OCS.

Talbot, R. W.↗

Biogenic Methane and the Rise of Oxygen

Oxygenic photosynthesis does not make the rise of oxygen inevitable. What is required is that reductant and oxygen be separated and permanently segregated. The usual picture for Earth is that oxygenic photosynthesis split CO2 into carbon and oxygen, with the carbon buried in sediments and the oxygen mostly taken up by oxides of iron and sulfur. The relatively small atmospheric reservoir of O2 is regulated by the carbon burial rate, reaction with volcanic and metamorphic gases, and oxidation of reduced carbon released as old sediments weather. Absent from this picture is a distinction between the Archean and modern times: on average, carbon burial fluxes would have been matched by oxygen losses then as now. Separation of reductant from oxidant is only provisional. No net oxidation of the continents occurs, and so no change of diagenetic, metamorphic, or volcanic gases is expected. Nor would any change in oxidative weathering be expected. Something more than carbon burial is required to make the Archean different. The escape of hydrogen to space permanently separates the reductant from the oxidant. Hydrogen escape is widely believed to have led to the present highly oxidized states of Mars and Venus. Hydrogen escape has usually been thought small for Archaean Earth, because water vapor is cold-trapped at the troposphere and thus held to levels of a few ppmv in the stratosphere. This cold trapping renders hydrogen escape negligible. However, methane is not cold trapped, and its expected abundance in the Archaean, given low oxygen levels and a biogenic source, would have been high, probably more than 100 times present. At such levels methane would have driven geologically significant levels of hydrogen escape. Additional information is contained in the original extended abstract.

Catling, David↗

A Primordial Atmospheric Origin of Hydrospheric Deuterium Enrichment on Mars

The deuterium-to-hydrogen (D/H or 2H/1H) ratio of Martian atmospheric water (~6× standard mean ocean water, SMOW) is higher than that of known sources, requiring planetary enrichment. A recent measurement by NASA’s Mars Science Laboratory rover Curiosity of Hesperian-era (>3 Ga) clays yields a D/H ratio ~3×SMOW, demonstrating that most of the enrichment occurs early in Mars’s history, reinforcing the conclusions of Martian meteorite studies. As on Venus, Mars’s D/H enrichment is widely thought to reflect preferential loss to space of 1H (protium) relative to 2H (deuterium), but both the cause and the global environmental context of large and early hydrogen losses remain to be determined. Here, we apply a recent model of primordial atmosphere evolution to Mars, link the magma ocean of the accretion epoch with a subsequent water-ocean epoch, and calculate the behavior of deuterium for comparison with the observed record. In contrast to earlier works that consider Martian D/H fractionation in atmospheres in which hydrogen reservoirs are present exclusively as H2O or H2, here we consider 2-component (H2O-H2) outgassed atmospheres in which both condensed (H2O) and escaping (H2) components – and their interaction – are explicitly calculated. We find that a a ≈2-3× hydrospheric deuterium-enrichment is produced rapidly if the Martian magma ocean is chemically reducing at last equilibration with the primordial atmosphere, making H2 and CO the initially dominant species, with minor abundances of H2O and CO2. Reducing gases – in particular H2 – can cause substantial greenhouse warming and prevent a water ocean from freezing immediately after the magma ocean epoch. We find that greenhouse warming due to plausible H2 inventories (pH2=1-102 bars) yields surface temperatures high enough (Ts=290-560 K) to stabilize a water ocean and produce an early hydrological cycle through which surface water can be circulated. Moreover, the pressure-temperature conditions are high enough to produce ocean-atmosphere H2O-H2 isotopic equilibrium through gas-phase deuterium exchange such that surface H2O strongly concentrates deuterium relative to H2, which preferentially takes up protium and escapes from the primordial atmosphere. The efficient physical separation of deuterium-rich (H2O) and deuterium-poor (H2) species via condensation permits equilibrium isotopic partitioning and early atmospheric escape to be recorded in modern crustal reservoirs. The proposed scenario of primordial H2-CO-rich outgassing and escape suggests significant durations (>Myr) of chemical conditions on the Martian surface conducive to prebiotic chemistry immediately following magma ocean crystallization.

Mars↗

Fiber-Optic Determination of N2, O2, and Fuel Vapor in the Ullage of Liquid-Fuel Tanks

A fiber-optic sensor system has been developed that can remotely measure the concentration of molecular oxygen (O2), nitrogen (N2), hydrocarbon vapor, and other gases (CO2, CO, H2O, chlorofluorocarbons, etc.) in the ullage of a liquid-fuel tank. The system provides an accurate and quantitative identification of the above gases with an accuracy of better than 1 percent by volume (for O2 or N2) in real-time (5 seconds). In an effort to prevent aircraft fuel tank fires or explosions similar to the tragic TWA Flight 800 explosion in 1996, OBIGGS are currently being developed for large commercial aircraft to prevent dangerous conditions from forming inside fuel tanks by providing an inerting gas blanket that is low in oxygen, thus preventing the ignition of the fuel/air mixture in the ullage. OBIGGS have been used in military aircraft for many years and are now standard equipment on some newer large commercial aircraft (such as the Boeing 787). Currently, OBIGGS are being developed for retrofitting to existing commercial aircraft fleets in response to pending mandates from the FAA. Most OBIGGS use an air separation module (ASM) that separates O2 from N2 to make nitrogen-enriched air from compressed air flow diverted from the engine (bleed air). Current OBIGGS systems do not have a closed-loop feedback control, in part, due to the lack of suitable process sensors that can reliably measure N2 or O2 and at the same time, do not constitute an inherent source of ignition. Thus, current OBIGGS operate with a high factor-of-safety dictated by process protocol to ensure adequate fuel-tank inerting. This approach is inherently inefficient as it consumes more engine bleed air than is necessary compared to a closed-loop controlled approach. The reduction of bleed air usage is important as it reduces fuel consumption, which translates to both increased flight range and lower operational costs. Numerous approaches to developing OBIGGS feedback-control sensors have been under development by many research groups and companies. However, the direct measurement of nitrogen (N2) is a challenge to most OBIGGS ullage sensors (such as tunable diode laser absorption) as they cannot measure N2 directly but depend on the measurement of oxygen (O2). The problem with a singular measure of O2, is that as the concentration (number density) of O2 decreases due to the inerting process or due to lower pressures from high altitudes, the precision and accuracy of the O2 measurement decreases. However, measuring O2 density in combination with N2 density (which is more abundant in air and in a N2-inerted fuel tank) can provide a much more accurate and reliable determination of the OBIGGS efficacy.

Nguyen, Quang-Viet↗