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All sourcesNASA NTRSDOE OSTI
NASA NTRS2004

Halotolerant and Resistant to High pH Hydrogenase from Haloalkaliphilic Sulfate-Reducing Bacterium Desulfonatronum thiodismutans

Hydrogenase is the key enzyme of energetic metabolism in cells, it catalyzing the converse reaction of hydrogen oxidation and responsible for consumption and excretion of hydrogen in bacteria. Hydrogenases are proteins containing either Nickel and Iron, or the only Iron in theirs active center. Hydrogenases have been found in many microorganisms, such as Methanogenic, acetogenic, nitrogen-fixing, photosynthetic and sulfate-reducing bacteria that could utilize the hydrogen as energy source or use it as electron sink. Hydrogenases are subject for wide physiological, biochemical, physicochemical and genetic studies due to theirs abilities produce the molecular hydrogen as alternative source of pure energy. Notwithstanding on enough large quantity of works that deal with intracellular and extrasellular enzymes of halophilic bacteria, the data about hydrogenases and theirs functions of salts practically are absent. The study of hydrogenase in cell-free extracts of extremely halophilic eubacterium Acetohalobium mabaticum showed dramatic increasing activity of the enzyme at high concentrations of NaCl and KCI (close to saturated solution). Here we present the data of free-cells extracted hydrogenase from new haloalkaliphilic sulfate-reducing bacterium Desulfonatronum thiodismutans, which grow on highly miniralized carbonate-bicarbonate medium in salinity range 1 to 7 % and at pH 7.8 - 10.5. Studied enzyme was active in Concentration range from 0 to 4.3 M NaCl with optimum at 1.0 M NaCl. At 1.0 M NaCl the enzyme activity was increased on 20 %, but with changing concentration from 2.1 M to 3.4 M the activity decreased and was kept on constant level. NaHCO3 inhibited hydrogenase activity on more then 30 %. The maximum of enzyme activity was observed at pH 9.5 with limits 7.5 and 11.5 that practically equal to pH optimum of bacterial growth. Therefore the hydrogenase of Desulfanatronum thiodismutans is tolerant to high concentrations of sodium salts and it also resistant to high pH that make it the unique subject for different biochemical research and detects the possibility for biotechnological application.

Detkova, Ekaterina N.↗
NASA NTRSDate not supplied

NASA Lunabotics Robotic Mining Competition 10th Anniversary (2010-2019): Taxonomy and Technology Review

Space Mining for resources such as water ice, and regolith, which contain many elements in the form of metals, minerals, volatiles and other compounds, is a necessary step for In-Situ Space Resource Utilization (ISRU). One of the primary goals is to extract propellants from the regolith and water ice, such as oxygen and hydrogen which could then be used for in-space transportation. In addition, the space mining system can be used for various construction tasks that can benefit human and robotic exploration as well as scientific investigations based on excavated exposed topography, such as the side walls of trenches. The National Aeronautics & Space Administration (NASA) "Lunabotics" Robotic Mining Competition (RMC) is a university-level competition designed to engage and retain students in science, technology, engineering and mathematics (STEM). NASA has directly benefited from the competition by encouraging the development of innovative lunar excavation concepts from universities which has resulted in clever ideas and solutions which could be applied to an actual lunar excavation device or payload. The challenge is for students to design and build a remote controlled or autonomous excavator, called a "lunabot", which can collect and deposit a minimum of 10 kilograms of lunar simulant within 15 minutes. In recent years the goal has been changed to excavate a minimum of 1 kg of simulated icy regolith which is found under an overburden of regolith simulant. The complexities of the challenge include the abrasive characteristics of the lunar regolith simulant, the weight and size limitations of the lunabot, and the ability to control the lunabot from a remote-control center or operate it autonomously. This paper will present the results of the ten Lunabotics Robotic Mining Competitions held between May 2010 and May 2019. Each year over 50 university teams have attended, resulting in over 500 lunabot designs and subsequent prototypes. Over 6,000 university students have been part of the on-site competition at KSC. Even more students and the public were engaged via internet broadcasting and social networking media. The various designs have been cataloged and categorized here to provide information to future Lunabotics RMC mining robot designers and competitors. Categories will focus on both the mechanical design as well as the autonomy architecture/design. It is also expected to be of value for actual future space missions, as knowledge is gained from testing many innovative prototypes in simulated lunar regolith. A taxonomy of robotic excavator designs has been presented. In addition, the paper will discuss changes in learning paradigms occurring in the current generation of students, and how this competition leverages those changes to challenge students to develop skills in graduate level concepts and apply them. Examples of how this translates to hiring opportunities for commercial sponsors has also been discussed.

Robert P Mueller↗
NASA NTRSDate not supplied

NASA LUNABOTICS ROBOTIC MINING COMPETITION 10TH ANNIVERSARY (2010 – 2019): TAXONOMY AND TECHNOLOGY REVIEW

Space Mining for resources such as water ice, and regolith, which contain many elements in the form of metals, minerals, volatiles and other compounds, is a necessary step for In-Situ Space Resource Utilization (ISRU). One of the primary goals is to extract propellants from the regolith and water ice, such as oxygen and hydrogen which could then be used for in-space transportation. In addition, the space mining system can be used for various construction tasks that can benefit human and robotic exploration as well as scientific investigations based on excavated exposed topography, such as the side walls of trenches. The National Aeronautics & Space Ad-ministration (NASA) Lunabotics Robotic Mining Competition (RMC) is a university-level competition designed to engage and retain students in science, technology, engineering and mathematics (STEM). NASA has directly benefited from the competition by encouraging the development of innovative lunar excavation concepts from universities which has resulted in clever ideas and solutions which could be applied to an actual lunar excavation device or payload. The challenge is for students to design and build a remote controlled or autonomous excavator, called a lunabot, that can collect and deposit a minimum of 10 kilograms of lunar simulant within 15 minutes. In recent years the goal has been changed to excavate a minimum of 1 kg of simulated icy regolith which is found under an over-burden of regolith simulant. The complexities of the challenge include the abrasive characteristics of the lunar simulant, the weight and size limitations of the lunabot, and the ability to control the lunabot from a remote control center. This paper will present the results of the 10 Lunabotics Robotic Mining Competitions held between May 2010 and May 2019. Each year over 50 university teams have attended, resulting in over 500 lunabot designs and subsequent prototypes. Over 5,000 university students have been part of the competition on-site at KSC. More students and the public were en-gaged via internet broadcasting and social net-working media. The various designs will be cataloged and categorized to provide information to future Lunabotics mining robot designers and competitors. It is also expected to be of value for actual future space missions, as knowledge is gained from testing many innovative prototypes in simulated lunar regoith. A taxonomy of robotic excavator designs will be presented.

Competition↗
NASA NTRSDate not supplied

Lunabotics Robotic Mining Competition for Universities

Space Mining for resources such as water ice, and regolith, which contain many elements in the form of metals, minerals, volatiles and other compounds, is a necessary step for In-Situ Space Resource Utilization (ISRU). One of the primary goals is to extract propellants from the regolith and water ice, such as oxygen and hydrogen which could then be used for in-space transportation. In addition, the space mining system can be used for various construction tasks that can benefit human and robotic exploration as well as scientific investigations based on excavated exposed topography, such as the side walls of trenches. The National Aeronautics & Space Administration (NASA) “Lunabotics” Robotic Mining Competition (RMC) is a university-level competition designed to engage and retain students in science, technology, engineering and mathematics (STEM). NASA has directly benefited from the competition by encouraging the development of innovative lunar excavation concepts from universities which has resulted in clever ideas and solutions which could be applied to an actual lunar excavation device or payload. The challenge is for students to design and build a remote controlled or autonomous 80 kg mass lightweight excavator, called a “lunabot”, which can collect and deposit a minimum of 10 kilograms of lunar simulant within 15 minutes. In recent years the goal has been changed to excavate a minimum of 1 kg of simulated icy regolith which is found under an overburden of regolith simulant. The complexities of the challenge include the abrasive characteristics of the lunar regolith simulant, the weight and size limitations of the lunabot, and the ability to control the lunabot from a remote mission control center or operate it autonomously. This presentation will summarize the results of the Lunabotics Robotic Mining Competitions held in May 2022. Each year, since 2010, over 50 university teams have attended, resulting in over 500 lunabot designs and subsequent prototypes. Over 6,000 university students have been part of the on-site competition at KSC, and many are employed in the space sector today with thriving careers. Even more students and the public were engaged via internet broadcasting and social networking media. Examples of how this translates to hiring opportunities for commercial sponsors will also be discussed. Overall, this competition has proven to be popular with multi-disciplinary university senior design classes and a valuable tool for NASA and academia in educating and inspiring the next generation of space engineers.

Lunabotics↗
NASA NTRS1995

Advanced Dependent Pressure Vessel (DPV) nickel-hydrogen spacecraft cell and battery design

The dependent pressure vessel (DPV) nickel-hydrogen (NiH2) battery is being developed as a potential spacecraft battery design for both military and commercial satellites. Individual pressure vessel (IPV) NiH2 batteries are currently flying on more than 70 Earth orbital satellites and have accumulated more than 140,000,000 cell-hours in actual spacecraft operation. The limitations of standard NiH2 IPV flight battery technology are primarily related to the internal cell design and the battery packaging issues associated with grouping multiple cylindrical cells. The DPV cell design offers higher specific energy and reduced cost, while retaining the established IPV NiH2 technology flight heritage and database. The advanced cell design offers a more efficient mechanical, electrical and thermal cell configuration and a reduced parts count. The internal electrode stack is a prismatic flat-plate arrangement. The flat individual cell pressure vessel provides a maximum direct thermal path for removing heat from the electrode stack. The cell geometry also minimizes multiple-cell battery packaging constraints by using an established end-plateltie-rod battery design. A major design advantage is that the battery support structure is efficiently required to restrain only the force applied to a portion of the end cell. As the cells are stacked in series to achieve the desired system voltage, this increment of the total battery weight becomes small. The geometry of the DPV cell promotes compact, minimum volume packaging and places all cell terminals along the length of the battery. The resulting ability to minimize intercell wiring offers additional design simplicity and significant weight savings. The DPV battery design offers significant cost and weight savings advantages while providing minimal design risks. Cell and battery level design issues will be addressed including mechanical, electrical and thermal design aspects. A design performance analysis will be presented at both the cell and battery level. The DPV is capable of delivering up to 76 Watt-hours per kilogram (Wh/kg) at the cell level and 70 Wh/kg at the full battery level. This represents a 40 percent increase in specific energy at the cell level and a 60 percent increase in specific energy at the battery level compared to current IPV NiH2 technology.

Coates, Dwaine↗
NASA NTRS2007

Technical Findings, Lessons Learned, and Recommendations Resulting from the Helios Prototype Vehicle Mishap

The Helios Prototype was originally planned to be two separate vehicles, but because of resource limitations only one vehicle was developed to demonstrate two missions. The vehicle consisted of two configurations, one for each mission. One configuration, designated HP01, was designed to operate at extremely high altitudes using batteries and high-efficiency solar cells spread across the upper surface of its 247-foot wingspan. On August 13, 2001, the HP01 configuration reached an altitude of 96,863 feet, a world record for sustained horizontal flight by a winged aircraft. The other configuration, designated HP03, was designed for long-duration flight. The plan was to use the solar cells to power the vehicle's electric motors and subsystems during the day and to use a modified commercial hydrogen-air fuel cell system for use during the night. The aircraft design used wing dihedral, engine power, elevator control surfaces, and a stability augmentation and control system to provide aerodynamic stability and control. At about 30 minutes into the second flight of HP03, the aircraft encountered a disturbance in the way of turbulence and morphed into an unexpected, persistent, high dihedral configuration. As a result of the persistent high dihedral, the aircraft became unstable in a very divergent pitch mode in which the airspeed excursions from the nominal flight speed about doubled every cycle of the oscillation. The aircraft s design airspeed was subsequently exceeded and the resulting high dynamic pressures caused the wing leading edge secondary structure on the outer wing panels to fail and the solar cells and skin on the upper surface of the wing to rip away. As a result, the vehicle lost its ability to maintain lift, fell into the Pacific Ocean within the confines of the U.S. Navy's Pacific Missile Range Facility, and was destroyed. This paper describes the mishap and its causes, and presents the technical recommendations and lessons learned for improving the design, analysis, and testing methods and techniques required for this class of vehicle.

Noll, Thomas E.↗
NASA NTRS1994

Ways to Increase Launch Velocities of 2-Stage Gas Guns

The amount of space debris is rapidly increasing and the debris is distributed over a wide variety of orbits. Satellites, manned space vehicles and space stations will have to pay increasing attention to the dangers of impacts with space debris. Various armoring techniques (i.e., double or triple layer armor) will have to tested extensively to determine the most effective armor per unit weight. Intersecting near-earth orbits can lead to impact velocities up to 15 km/sec. Conventional two-stage light gas guns can launch intact, controlled-shape projectiles with a density of 1.2 gm/cc and length- to-diameter ratios of 0.5-1.0 at velocities up to 8-9 km/sec. Higher velocities (10-11 km/sec) can be obtained' for very light projectiles. The higher launch velocities tend to be very severe on the high pressure coupling and barrel of the gun and lead to short component lifetimes. Clearly, the ability to raise the launch velocity of a gun (for reasonably massive projectile shapes) from 8-9 km/sec to 11-13 km/sec (or higher), without reduction of component lifetimes, would have significant benefits. This would allow much better simulation of the higher velocity debris impacts as well as better simulation of high speed re-entry into planetary atmospheres. Several techniques for increasing the launcher muzzle velocity above 8-9 km/sec have been studied using CFD simulations and appear to offer the potential for significant gains. The first technique is to use multiple compressions, instead of a single compression, in the pump tube of the light gas gun. In a sense, this is a kind of pre-heating of the gas in the pump tube; other types of pre-heating have yielded disappointing results in the past. The dynamics of the multiple compression pump tube is very different, however, from the earlier techniques, where the pump tube was typically heated ohmically before the gun 2 cycle was started. In this paper, we present CFD calculations that show that significant increases in muzzle velocity can be obtained with multiple compressions in the pump tube. With a conventional two-stage gun, an important limitation to obtaining higher velocities is friction and heat transfer to the barrel, which typically has a length- to- diameter ratio of 200-400. These viscous losses greatly reduce the effectiveness of the regions of the barrel far removed from the second stage breech. We have studied computationally the effect of adding an additional breech (or breeches) along the barrel to reduce these viscous losses. Velocity increases from 6.5 to 7.2 km/sec have been obtained using the main breech and one additional breech. In these results, both breeches were operated with hydrogen, heated electrothermally. We have also studied a gun geometry where the main breech is operated in the conventional manner, using piston compression. The additional breech is operated either with electrothermal heating or heating by using a high explosive charge in a novel geometry. The latter option provides very effective compression, heating and acceleration of the hydrogen working gas and is fully reusable. Calculations are presented which show that very substantial increases in muzzle velocity can be obtained this way, without overstressing the projectile or the 'gun. The third technique studied is to add a section of ram accelerator tube after the barrel to further accelerate the projectile. The ram accelerator used here is not the conventional premixed gas ram accelerator, but a new technique using high explosive as the energy source and pure hydrogen as the working gas in a geometry which can be made fully reusable. Preliminary results with this new rain accelerator geometry were presented and showed that stable ram accelerator drive can be established. Herein, detailed calculations axe presented which show that substantial velocity increases can be obtained using this ram accelerator technique in tandem with a conventional light gas gun.

Bogdanoff, David W.↗
NASA NTRS2010

Potential Lunar In-Situ Resource Utilization Experiments and Mission Scenarios

The extraction and use of resources on the Moon, known as In-Situ Resource Utilization (ISRU), can potentially reduce the cost and risk of human lunar exploration while also increasing science achieved. By not having to bring all of the shielding and mission consumables from Earth and being able to make products on the Moon, missions may require less mass to accomplish the same objectives, carry more science equipment, go to more sites of exploration, and/or provide options to recover from failures not possible with delivery of spares and consumables from Earth alone. The concept of lunar ISRU has been considered and studied for decades, and scientists and engineers were theorizing and even testing concepts for how to extract oxygen from lunar soil even before the Apollo 11 mission to the Moon. There are four main areas where ISRU can significantly impact how human missions to the Moon will be performed: mission consumable production, civil engineering and construction, energy production, storage, and transfer, and manufacturing and repair. The area that has the greatest impact on mission mass, hardware design and selection, and mission architecture is mission consumable production, in particular, the ability to make propellants, life support consumables, and fuel cell reagents. Mission consumable production allows for refueling and reuse of spacecraft, increasing power production and storage, and increased capabilities and failure tolerance for crew life support. The other three areas allow for decreased mission risk due to radiation and plume damage, alternative power systems, and failure recover capabilities while also enabling infrastructure growth over Earth delivered assets. However, while lunar ISRU has significant potential for mass, cost, and risk reduction for human lunar missions, it has never been demonstrated before in space. To demonstrate that ISRU can meet mission needs and to increase confidence in incorporating ISRU capabilities into mission architectures, terrestrial laboratory and analog field testing along with robotic precursor missions are required. A stepwise approach with international collaboration is recommended. The first step is to understand the resources available through orbital and surface exploration missions. Resources of particular interest are hydrogen, hydroxyl, water, and other polar volatile resources recently measured by Chandrayaan, Lunar Reconnaissance Orbiter (LRO), and the Lunar Crater Observation and Sensing Satellite (LCROSS). The second step is to demonstrate critical aspects of ISRU systems to prove ISRU is feasible under lunar environmental and resource conditions (ex. subscale oxygen extraction from regolith). The third step is to perform integrated missions with ISRU and other connected systems, such as power, consumable storage, surface mobility, and life support at a relevant mission scale to demonstrate ISRU capabilities as well as the critical interfaces with other exploration systems. If possible, the mission should demonstrate the use of ISRU products (ex. in a rocket engine or fuel cell). This dress rehearsal mission would be the final step before full implementation of ISRU into human missions, and may be performed during human lunar exploration activities. This stepwise approach is the most conservative approach, and may only be possible with international cooperation due to the limited number of robotic missions each nation/space agency can perform within their budget.

Sanders, Gerald B.↗
NASA NTRS1993

Pigs in cyberspace

Exploration and colonization of the universe awaits, but Earth-adapted biological humans are ill-equipped to respond to the challenge. Machines have gone farther and seen more, limited though they presently are by insect-like behavior inflexibility. As they become smarter over the coming decades, space will be theirs. Organizations of robots of ever increasing intelligence and sensory and motor ability will expand and transform what they occupy, working with matter, space and time. As they grow, a smaller and smaller fraction of their territory will be undeveloped frontier. Competitive success will depend more and more on using already available matter and space in ever more refined and useful forms. The process, analogous to the miniaturization that makes today's computers a trillion times more powerful than the mechanical calculators of the past, will gradually transform all activity from grossly physical homesteading of raw nature, to minimum-energy quantum transactions of computation. The final frontier will be urbanized, ultimately into an arena where every bit of activity is a meaningful computation: the inhabited portion of the universe will be transformed into a cyberspace. Because it will use resources more efficiently, a mature cyberspace of the distant future will be effectively much bigger than the present physical universe. While only an infinitesimal fraction of existing matter and space is doing interesting work, in a well developed cyberspace every bit will be part of a relevant computation or storing a useful datum. Over time, more compact and faster ways of using space and matter will be invented, and used to restructure the cyberspace, effectively increasing the amount of computational spacetime per unit of physical spacetime. Computational speed-ups will affect the subjective experience of entities in the cyberspace in a paradoxical way. At first glimpse, there is no subjective effect, because everything, inside and outside the individual, speeds up equally. But, more subtly, speed-up produces an expansion of the cyber universe, because, as thought accelerates, more subjective time passes during the fixed (probably lightspeed) physical transit time of a message between a given pair of locations - so those fixed locations seem to grow farther apart. Also, as information storage is made continually more efficient through both denser utilization of matter and more efficient encodings, there will be increasingly more cyber-stuff between any two points. The effect may somewhat resemble the continuous-creation process in the old steady-state theory of the physical universe of Hoyle, Bondi and Gold, where hydrogen atoms appear just fast enough throughout the expanding cosmos to maintain a constant density.

Moravec, Hans↗
NASA NTRS2001

Chemical Engineering in Space

The aerospace industry has long been perceived as the domain of both physicists and mechanical engineers. This perception has endured even though the primary method of providing the thrust necessary to launch a rocket into space is chemical in nature. The chemical engineering and chemistry personnel behind the systems that provide access to space have labored in the shadows of the physicists and mechanical engineers. As exploration into the cosmos moves farther away from Earth, there is a very distinct need for new chemical processes to help provide the means for advanced space exploration. The state of the art in launch systems uses chemical propulsion systems, primarily liquid hydrogen and liquid oxygen, to provide the energy necessary to achieve orbit. As we move away from Earth, there are additional options for propulsion. Unfortunately, few of these options can compare to the speed or ease of use provided by the chemical propulsion agents. It is with great care and significant cost that gaseous compounds such as hydrogen and oxygen are liquefied and become dense enough to use for rocket fuel. These low-temperature liquids fall within a specialty area known as cryogenics. Cryogenics, the science and art of producing cold operating conditions for use on Earth, in orbit, or on some other nonterrestrial body, has become increasingly important to our ability to travel within our solar system. The production of cryogenic fuels and the long-term storage of these fluids are necessary for travel. As our explorations move farther away from Earth, we need to address how to produce the necessary fuels to make a round-trip. The cost and the size of these expeditions are extreme at best. If we take everything necessary for our survival for the round-trip, we invalidate any chance of travel in the near future. As with the early explorers on Earth, we need to harvest much of our energy and our life support from the celestial bodies. The in situ production of these energy sources is paramount to success. We are currently working on several processes to produce the propellants that would allow us to visit and explore the surface of Mars. The capabilities currently at our disposal for launching and delivering equipment to another planet or satellite dictate that the size and scale of any hardware must be extremely small. The miniaturization of the processes needed to prepare the in situ propellants and life support commodities is a real challenge. Chemical engineers are faced with the prospect of reproducing an entire production facility in miniature so the complex can be lifted into space and delivered to our destination. Another area that does not normally concern chemical engineers is the extreme physical aspects payloads are subjected to with the launch of a spacecraft. Extreme accelerations followed by the sudden loss of nearly all gravitational forces are well outside normal equipment design conditions. If the equipment cannot survive the overall trip, then it obviously will not be able to yield the needed products upon arrival. These launch constraints must be taken into account. Finally, we must consider both the effectiveness and efficiencies of the processes. A facility located on the Moon or Mars will not have an unlimited supply of power or other ancillary utilities. For a Mars expedition, the available electric power is severely limited. The design of both the processes and the equipment must be considered. With these constraints in mind, only the most efficient designs will be viable. Cryogenics, in situ resource utilization, miniaturization, launchability, and power/process efficiencies are only a few of the areas that chemical engineers provide support and expertise for the exploration of space.

Lobmeyer, Dennis A.↗
NASA NTRS1999

Instrumentation Working Group Summary

The Instrumentation Working Group compiled a summary of measurement techniques applicable to gas turbine engine aerosol precursors and particulates. An assessment was made of the limits, accuracy, applicability, and technology readiness of the various techniques. Despite advances made in emissions characterization of aircraft engines, uncertainties still exist in the mechanisms by which aerosols and particulates are produced in the near-field engine exhaust. To adequately assess current understanding of the formation of sulfuric acid aerosols in the exhaust plumes of gas turbine engines, measurements are required to determine the degree and importance of sulfur oxidation in the turbine and at the engine exit. Ideally, concentrations of all sulfur species would be acquired, with emphasis on SO2 and SO3. Numerous options exist for extractive and non-extractive measurement of SO2 at the engine exit, most of which are well developed. SO2 measurements should be performed first to place an upper bound on the percentage of SO2 oxidation. If extractive and non-extractive techniques indicate that a large amount of the fuel sulfur is not detected as SO2, then efforts are needed to improve techniques for SO3 measurements. Additional work will be required to account for the fuel sulfur in the engine exhaust. Chemical Ionization Mass Spectrometry (CI-MS) measurements need to be pursued, although a careful assessment needs to be made of the sampling line impact on the extracted sample composition. Efforts should also be placed on implementing non-intrusive techniques and extending their capabilities by maximizing exhaust coverage for line-of-sight measurements, as well as development of 2-D techniques, where feasible. Recommendations were made to continue engine exit and combustor measurements of particulates. Particulate measurements should include particle size distribution, mass fraction, hydration properties, and volatile fraction. However, methods to ensure that unaltered samples are obtained need to be developed. Particulate speciation was also assigned a high priority for quantifying the fractions of carbon soot, PAH, refractory materials, metals, sulfates, and nitrates. High priority was also placed on performing a comparison of particle sizing instruments. Concern was expressed by the workshop attendees who routinely make particulate measurements about the variation in number density measured during in-flight tests by different instruments. In some cases, measurements performed by different groups of researchers during the same flight tests showed an order of magnitude variation. Second priority was assigned to measuring concentrations of odd hydrogen and oxidizing species. Since OH, HO2, H2O2, and O are extremely reactive, non-extractive measurements are recommended. A combination of absorption and fluorescence is anticipated to be effective for OH measurements in the combustor and at the engine exit. Extractive measurements of HO2 have been made in the stratosphere, where the ambient level of OH is relatively low. Use of techniques that convert HO2 to OH for combustor and engine exit measurements needs to be evaluated, since the ratio of HO2/OH may be 1% or less at both the combustor and engine exit. CI-MS might be a viable option for H2O2, subject to sampling line conversion issues. However, H2O2 is a low priority oxidizing species in the combustor and at the engine exit. Two candidates for atomic oxygen measurements are Resonance Enhanced Multi-Photon Ionization (REMPI) and Laser-Induced Fluorescence (LIF). Particulate measurement by simultaneous extractive and non-extractive techniques was given equal priority to the oxidizer measurements. Concern was expressed over the ability of typical ground test sampling lines to deliver an unaltered sample to a remotely located instrument. It was suggested that the sampling probe and line losses be checked out by attempting measurements using an optical or non-extractive technique immediately upstream of the sampling probe. This is a possible application for Laser Induced Incandescence (LII) as a check on the volume fraction of soot. Optical measurements of size distribution are not well developed for ultrafine particles less than about 20 nm in diameter, so a non-extractive technique for particulate size distribution cannot be recommended without further development. Carbon dioxide measurements need to be made to complement other extractive measurement techniques. CO2 measurements enable conversion of other species concentrations to emission indices. Carbon monoxide, which acts as a sink for oxidizing species, should be measured using non-extractive techniques. CO can be rapidly converted to CO2 in extractive probes, and a comparison between extractive and non-extractive measurements should be performed. Development of non-extractive techniques would help to assess the degree of CO conversion, and might be needed to improve the concentration measurement accuracy. Measurements of NO(x) will continue to be critical due to the role of NO and NO2 in atmospheric chemistry, and their influence on atmospheric ozone. Time-resolved measurements of temperature, velocity, and species concentrations were included on the list of desired measurement. Thermocouples are typically adequate for engine exit measurements. PIV and LDV are well established for obtaining velocity profiles. The techniques are listed in the accompanying table; are divided into extractive and non-extractive techniques. Efforts were made to include a measurement uncertainty for each technique. An assessment of the technology readiness was included.

Zaller, Michelle↗
NASA NTRSDate not supplied

Effect of salinity on the preservation of biomarkers in hypersaline microbial mat kerogens

Kerogen is the residue that remains after the minerals and organic compounds have been extracted from a rock using acid and organic solvents, respectively [1]. It is not only the largest organic carbon sink in the geological record but the best-preserved fraction due to its recalcitrance and ability to retain syngenetic source information during deposition [2]. Due to the complex, macromolecular, cross-linked polymeric structure of kerogen, it is difficult to analyse intact, often requiring breakdown into smaller subunits through thermal (pyrolysis) or chemical treatment (chemolysis) [3]. Saline and hypersaline environments host diverse microbial communities, which can trap and bind organic matrices such as cellular components (e.g., extracellular polymeric substances, cell wall, peptidoglycan, sheath material, etc.) with sediments, forming layered, laminated structures called microbial mats. Here we present depth profiles of two hypersaline cores through a microbial mat with differing total salinities. We looked at the composition of organic compounds released from kerogen during high temperature, hydrogen-assisted, pyrolysis to understand the effect of salinity on the composition and timing of their incorporation [4]. Field Site: The Exportadora del Sal S. A. (ESSA) saltern of Guerrero Negro (Baja California Sur, Mexico) lies within a typical sabhka environment adjacent to Laguna Ojo de Liebre. Note the spatial extent of the 13 major ponds of the ESSA system. The GN ponds thrive under well-monitored and stable conditions with steady state accretion and degradation of mat layers (around 0.5–1.4 cm per year). Organic mats typically attain up to 10 cm in thickness, depending on the location, which represents about 60 years of growth since these ponds were established. Sedimentation rate is rapid in these non-lithifying and non-mineralising mats, 1–1.5 cm per year. This environment is ideal for investigating in situ lipid preservation and diagenesis without the influence of constantly changing physical parameters. Methods: P4n5 and P5AB cores were collected as ~9 cm and 6.5 cm fresh cores, respectively, in June 2001 and September 2010, respectively from the ESSA saltern. The P4n5 core (9-9.1% salinity) was taken from Pond 4 near 5 and sub-divided into 10 layers. The P5AB core (11.2% salinity) was taken from Pond 5A near 5B and sub-divided into 8 layers. Lyophilised microbial mat powders were solvent-extracted using a modified Bligh-Dyer method and analysed by gas chromatography-mass spectrometry (GC-MS). Additionally, a subset of layers—layer 4 and layer 7—which represented active biomass and sediment-processed, respectively, were subjected to mild-acid methanolysis. The respective residues from conventional solvent extraction and acid methanolysis were loaded with a molybdenum sulfide catalyst and placed into a stainless-steel reactor. Samples were run on the hydropyrolysis set up (heated to 500 °C with 13-15 MPa of H2 pressure), extracted, and analysed by GC-MS. Results: Molecular profiles from the two ponds were significantly different and reflect the contributions of different photosynthetic and respiratory microbial communities to preserved organic matter. For example, the higher salinity P5AB core showed evidence of greater archaeal inputs (similarly observed in lab culture experiments [5]) as well as potential kerogen-bound carotenoids/carotenoid rearranged products or fragments. A hydrophobic emulsion formed during the acid methanolysis processing of layer 4 from both P4n5 and P5AB and layer 7 of P5AB. Hydropyrolysis of this hydrophobic residues released a greater abundance of polycyclic lipids relative to the pre-extracted control. Implications and Future Work: Catalytic hydropyrolysis of kerogen can rapidly generate abundant saturated pyrolysate products from the bound biomarker pool without altering the structures or stereochemistries of the products [6]. Chemical processing of solvent-extractable residues indicated that cellular matrices such as extracellular polymeric substances (EPS) may play a role in the sequestration of polycyclic lipid biomarkers such as steranes and hopanes. Their higher relative abundance compared to the pre-extracted control in the higher salinity layers and cores preliminarily aligns with this hypothesis, although further experiments are required to confirm this. It has been well-documented that EPS plays an important role in mineralisation, specifically carbonate formation, in microbial ecosystems. EPS can enhance calcium carbonate precipitation by providing diffusion-limited sites that create alkalinity gradients in response to microbial processes [7]. It has been experimentally demonstrated that salinity influences the total amount of EPS (both loosely- and tightly-bound) which increases with increasing salinity [8]. The higher salinity at Guerrero Negro switches the microbial population from filamentous Microcoleus to being dominated by Phormidium, Oscillatoria, and unicellular cyanobacteria. We demonstrated that lipid binding into kerogen via strong covalent linkages occurs at the very earliest stages of sedimentary diagenesis. We are currently investigating the influence of salinity on organic preservation through experimental and modelling approaches. Understanding how key biomarkers transform into preserved organic matter (i.e., from precursor biolipids to bound geolipids) in brine ecosystems will aid the search for organic biosignatures on other planetary bodies, especially Icy Moons and modern Mars.

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