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All sourcesNASA NTRSDOE OSTI
NASA NTRS2015

Results of a Long-Term Demonstration of an Optical Multi-Gas Monitor on ISS

Previously at SAMAP we reported on the development of tunable diode laser spectroscopy (TDLS) based instruments for measuring small gas molecules in real time. TDLS technology has matured rapidly over the last 5 years as a result of advances in low power diode lasers as well as better detection schemes. In collaboration with two small businesses Vista Photonics, Inc. and Nanoracks LLC, NASA developed a 4 gas TDLS based monitor for an experimental demonstration of the technology on the International Space Station (ISS). Vista invented and constructed the core TDLS sensor. Nanoracks designed and built the enclosure, and certified the integrated monitor as a payload. The device, which measures oxygen, carbon dioxide, ammonia and water vapor, is called the Multi-Gas Monitor (MGM). MGM measures the 4 gases every few seconds and records a 30 second moving average of the concentrations. The relatively small unit draws only 2.5W. MGM was calibrated at NASA-Johnson Space Center in July 2013 and launched to ISS on a Soyuz vehicle in November 2013. Installation and activation of MGM occurred in February 2014, and the unit has been operating nearly continuously ever since in the Japanese Experiment Module. Data is downlinked from ISS about once per week. Oxygen and carbon dioxide data is compared with that from the central Major Constituents Analyzer. Water vapor data is compared with dew point measurements made by sensors in the Columbus module. The ammonia channel was tested by the crew using a commercial ammonia inhalant. MGM is remarkably stable to date. Results of 18 months of operation are presented and future applications including combustion product monitoring are discussed.

Mudgett, Paul↗
NASA NTRS2018

Robotic External Leak Locator (RELL) Leak Plume Field Detection on the International Space Station (ISS)

The Robotic External Leak Locator (RELL) was deployed to the International Space Station (ISS) with the objective of demonstrating the ability to detect and locate small leaks. On-orbit operations began in late November 2016 and following scanning activities to characterize the natural and induced environment of the ISS, RELL focused on the United States External Active Thermal Control System (EATCS). RELL successfully detected ammonia related to a known small ammonia leak in the port-side EATCS, with the highest pressure values around the inboard Radiator Beam Valve Module 1 (RBVM 1). An additional day of scanning was subsequently performed in December 2017 to focus on RBVM 1. RELL was approved for additional external operations in February 2017 with the goal of fine tuning the location of the leak. Using grid scanning patterns, RELL detected ammonia around RBVM 1 and located the approximate source of the leak. The potential leak site was inspected by a crew member during an Extravehicular Activity (EVA) in March 2017, and the suspected radiator-side lines were isolated from the port-side EATCS coolant loop in April 2017. Subsequent monitoring of the system pressures showed that the leak has stopped, indicating RELL accurately located the source of the EATCS leak. These activities verify that RELL enhances the ISS Program's ability to not only locate small leaks, but isolate the source with minimal impact to the entire ISS system.

External Active Thermal Control System↗
NASA NTRSDate not supplied

Organic-rich fluids in Pluto’s interior—A source of cryovolcanic activity

The highly variegated surface of Pluto revealed by the New Horizons spacecraft is composed of both volatile ices (N2, CH4, CO) and H2O ice, all of which are intrinsically colorless. The colors on Pluto reveal a non-ice component generally acknowledged to be a refractory complex organic material (tholins) produced by photolysis in the planet’s atmosphere [1], and by photolysis and radiolysis of the surface ices [2-4]. These processes have produced a range of colors from pale yellow to red to brown, and result in a variation of a factor of 10in albedo across the surface. Tholins are disordered polymer-like materials made of repeating chains of linked subunits and complex combinations of functional groups containing carbon. Nitrogen, oxygen, and other elements can be substituted in both the aliphatic and aromatic subunits. The detection of the spectral absorption of an ammoniated compound associated with surface exposures of red-colored H2O ice (herein, RAW) in the LEISA spectral mapping data from New Horizons suggests that a third source of a colored material is ejected from Pluto’s interior as a water-rich fluid(cryomagma) that rapidly freezes at the low temperature (~40K) of the surface [5,6]. The ammoniated compound is thought to be an ammonia hydrate or an ammoniated salt; the spectral data cover a limited wavelength range, resulting in ambiguity in the identification of the form of the ammonia. The distribution of RAW in the vicinity of tectonically stressed and deformed geological structures, particularly graben (fossae), is seen as the result of both fluid effusion and fountaining ejection of cryoclastic materials in Pluto’s Virgil Fossae region [5,6]. RAW is seen elsewhere on Pluto, both in association with graben complexes and on broad expanses of old surface, but primarily in zones of tectonic stress. The nature of the putative subsurface fluid is unknown, but it must have existed at relatively shallow depths such that the graben faulting could reach it. Geochemical modeling of fluids in the interiors of small planetary bodies in the outer Solar System[7] shows that ammonia-bearing H2O in contact with rock and metal components produce a rich chemical soup, including gases that can, in principle, help propel the fluid from shallow reservoirs through crustal fractures to reach the surface. An organic component of the fluid cryomagma is predicted to originate from thermal processing of the components [ref] and may be an example of one-pot synthesis of such complexes as amino acid precursors [ref].

Dale P Cruikshank↗
NASA NTRS2021

Cryovolcanic flooding in Viking Terra on Pluto

A prominent fossa trough (Uncama Fossa) and adjacent 28-km diameter impact crater (Hardie) in Pluto's Viking Terra, as seen in the high-resolution images from the New Horizons spacecraft, show morphological evidence of in-filling with a material of uniform texture and red-brown color. A linear fissure parallel to the trough may be the source of a fountaining event yielding a cryoclastic deposit having the same composition and color properties as is found in the trough and crater. Spectral maps of this region with the New Horizons LEISA instrument reveal the spectral signature of H2O ice in these structures and in distributed patches in the adjacent terrain in Viking Terra. A detailed statistical analysis of the spectral maps shows that the colored H2O ice filling material also carries the 2.2-μm signature of an ammoniated component that may be an ammonia hydrate (NH3·nH2O) or an ammoniated salt. This paper advances the view that the crater and fossa trough have been flooded by a cryolava debouched from Pluto's interior along fault lines in the trough and in the floor of the impact crater. The now frozen cryolava consisted of liquid H2O infused with the red-brown pigment presumed to be a tholin, and one or more ammoniated compounds. Although the abundances of the pigment and ammoniated compounds entrained in, or possibly covering, the H2O ice are unknown, the strong spectral bands of the H2O ice are clearly visible. In consideration of the factors in Pluto's space environment that are known to destroy ammonia and ammonia-water mixtures, the age of the exposure is of order ≤109 years. Ammoniated salts may be more robust, and laboratory investigations of these compounds are needed.

Pluto↗
NASA NTRS2024

The Thermal Structure and Composition of Jupiter's Great Red Spot From JWST/MIRI

Jupiter's Great Red Spot (GRS) was mapped by the James Webb Space Telescope (JWST)/Mid-Infrared Instrument (4.9–27.9 μm) in July and August 2022. These observations took place alongside a suite of visual and infrared observations from; Hubble, JWST/NIRCam, Very Large Telescope/VISIR and amateur observers which provided both spatial and temporal context across the jovian disc. The stratospheric temperature structure retrieved using the NEMESIS software revealed a series of hot-spots above the GRS. These could be the consequence of GRS-induced wave activity. In the troposphere, the temperature structure was used to derive the thermal wind structure of the GRS vortex. These winds were only consistent with the independently determined wind field by JWST/NIRCam at 240 mbar if the altitude of the Hubble-derived winds were located around 1,200 mbar, considerably deeper than previously assumed. No enhancement in ammonia was found within the GRS but a link between elevated aerosol and phosphine abundances was observed within this region. North-south asymmetries were observed in the retrieved temperature, ammonia, phosphine and aerosol structure, consistent with the GRS tilting in the north-south direction. Finally, a small storm was captured north-west of the GRS that displayed a considerable excess in retrieved phosphine abundance, suggestive of vigorous convection. Despite this, no ammonia ice was detected in this region. The novelty of JWST required us to develop custom-made software to resolve challenges in calibration of the data. This involved the derivation of the “FLT-5” wavelength calibration solution that has subsequently been integrated into the standard calibration pipeline.

Jake Harkett↗
NASA NTRSDate not supplied

Artemis II Mission Performance of the Orion Active Thermal Control System

The Orion spacecraft has recently completed Artemis II, the first crewed mission around the moon in 54 years. This test flight demonstrated vehicle capability as the foundation for all future missions under the Artemis program. As a major system of Orion, the Active Thermal Control System (ATCS) successfully managed crew and vehicle heat loads to provide adequate cooling and thermal comfort for the duration of the Artemis II mission. Thermal control on the Orion vehicle is managed through two redundant cooling loops in the Crew Module (CM) that absorb heat loads from the cabin and Air Revitalization System (ARS) heat exchangers, the Liquid Cooling Garment (LCG) heat exchanger, and the avionics cold plates, and then transfer those heat loads to the Service Module (SM) radiator loops and/or the Phase Change Material (PCM) and ammonia boilers when required through thermal configuration or mission phase. During Artemis II, Orion did not necessitate any supplemental cooling from ammonia boilers until service module separation, allowing the maximum availability of ammonia cooling prior to entry. This presentation will provide an overview of the Orion ATCS major subsystems, highlight the performance during key mission phases, and comment on the applicability of the observed thermal response to future Artemis missions.

Ellie Thurston↗
DOE OSTI2013

LABORATORY TESTING TO SIMULATE VAPOR SPACE CORROSION IN RADIOACTIVE WASTE STORAGE TANKS

Radioactive liquid waste has been stored in underground carbon steel tanks for nearly 70 years at the Hanford nuclear facility. Vapor space corrosion of the tank walls has emerged as an ongoing challenge to overcome in maintaining the structural integrity of these tanks. The interaction between corrosive and inhibitor species in condensates/supernates on the tank wall above the liquid level, and their interaction with vapor phase constituents as the liquid evaporates from the tank wall influences the formation of corrosion products and the corrosion of the carbon steel. An effort is underway to gain an understanding of the mechanism of vapor space corrosion. Localized corrosion, in the form of pitting, is of particular interest in the vapor space. CPP testing was utilized to determine the susceptibility of the steel in a simulated vapor space environment. The tests also investigated the impact of ammonia gas in the vapor space area on the corrosion of the steel. Vapor space coupon tests were also performed to investigate the evolution of the corrosion products during longer term exposures. These tests were also conducted at vapor space ammonia levels of 50 and 550 ppm NH{sub 3} (0.005, and 0.055 vol.%) in air. Ammonia was shown to mitigate vapor space corrosion.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2015

Extraction of solubles from plant biomass for use as microbial growth stimulant and methods related thereto

A method for producing a microbial growth stimulant (MGS) from a plant biomass is described. In one embodiment, an ammonium hydroxide solution is used to extract a solution of proteins and ammonia from the biomass. Some of the proteins and ammonia are separated from the extracted solution to provide the MGS solution. The removed ammonia can be recycled and the proteins are useful as animal feeds. In one embodiment, the method comprises extracting solubles from pretreated lignocellulosic biomass with a cellulase enzyme-producing growth medium (such T. reesei) in the presence of water and an aqueous extract.

09 BIOMASS FUELS↗
DOE OSTI2016

Regional Climate Zone Modeling of a Commercial Absorption Heat Pump Hot Water Heater Part 1: Southern and South Central Climate Zones

Commercial hot water heating accounts for approximately 0.78 Quads of primary energy use with 0.44 Quads of this amount from natural gas fired heaters. An ammonia-water based commercial absorption system, if fully deployed, could achieve a high level of savings, much higher than would be possible by conversion to the high efficiency nonheat-pump gas fired alternatives. In comparison with air source electric heat pumps, the absorption system is able to maintain higher coefficients of performance in colder climates. The ammonia-water system also has the advantage of zero Ozone Depletion Potential and low Global Warming Potential. A thermodynamic model of a single effect ammonia-water absorption system for commercial space and water heating was developed, and its performance was investigated for a range of ambient and return water temperatures. This allowed for the development of a performance map which was then used in a building energy modeling software. Modeling of two commercial water heating systems was performed; one using an absorption heat pump and another using a condensing gas storage system. The energy and financial savings were investigated for a range of locations and climate zones in the southern and south central United States. A follow up paper will analyze northern and north/central regions. Results showed that the system using an absorption heat pump offers significant savings.

Geoghegan, Patrick J↗
DOE OSTI2017

Methods for pretreating biomass

A method for pretreating biomass is provided, which includes, in a reactor, allowing gaseous ammonia to condense on the biomass and react with water present in the biomass to produce pretreated biomass, wherein reactivity of polysaccharides in the biomass is increased during subsequent biological conversion as compared to the reactivity of polysaccharides in biomass which has not been pretreated. A method for pretreating biomass with a liquid ammonia and recovering the liquid ammonia is also provided. Related systems which include a biochemical or biofuel production facility are also disclosed.

09 BIOMASS FUELS↗
DOE OSTI2018

Nanostructured metal amides and nitrides for hydrogen storage

Nanostructured metal amides and nitrides are incorporated into nanoporous templates, such as carbon, using liquid ammonia as a solvent/reagent. This leads to unexpected improvements in metal amide nanoconfined hydrogen storage materials. The resulting nanostructured materials may reversibly absorb and desorb large capacities of hydrogen under conditions that are much milder compared to what has been achieved with bulk materials. In addition, the nanoconfined materials may reduce the amounts of ammonia released upon dehydriding, which may make the released hydrogen gas purer and may limit the capacity loss. In addition, nanoconfinement may simplify the reaction mechanism, eliminating undesired metal imide intermediates and promote hydrogen cycling under mild conditions. The liquid ammonia method also allows the simultaneous introduction of catalytic additives along with the parent hydrogen storage material.

Stavila, Vitalie↗
DOE OSTI2021

Catalytic membrane reactor, methods of making the same and methods of using the same for dehydrogenation reactions

A catalytic membrane reactor and methods of operating and producing the same are provided that efficiently produces highly pure hydrogen (H2) from ammonia (NH3) as well as operates according to other chemical conversion processes. In one embodiment, a tubular ceramic support made from porous yttria-stabilized zirconia has an outer surface that is impregnated with a metal catalyst such as ruthenium and then plated with a hydrogen permeable membrane such as palladium. An inner surface of the ceramic support is impregnated with cesium to promote conversion of ammonia to hydrogen and nitrogen (N2). The resulting catalytic membrane reactor produces highly pure hydrogen at low temperatures and with less catalytic loading. Therefore, ammonia can be used to effectively transport hydrogen for use in, for example, fuel cells in a vehicle.

Way, James Douglas↗
DOE OSTI2019

Multiscale Computational Model for Particle Size Evolution during Coprecipitation of Li-Ion Battery Cathode Precursors

Next generation lithium ion batteries require higher energy and power density, which can be achieved by tailoring the cathode particle morphology, such as particle size, size distribution, and internal porosity. All these morphological features are determined during the cathode synthesis process, which consists of two steps, (i) coprecipitation and (ii) calcination. Transition metal hydroxide precursors are synthesized during the coprecipitation process, whereas their oxidation and lithiation occur during calcination. The size and size distribution of crystalline primary and aggregated secondary particles and their internal porosity are determined during coprecipitation. Operating conditions of the chemical reactor, such as solution pH, ammonia concentration, and stirring speed control the final morphological features. Here, a multiscale computational model has been developed to capture the nucleation and growth of crystalline primary particles and their aggregation into secondary transition metal hydroxide precursor particles. The simulations indicate that increasing solution pH and decreasing ammonia concentration lead to smaller sizes of the secondary particles. Finally, a phase map has been developed that can help identify the synthesis conditions needed for a specified particle size and size distribution.

25 ENERGY STORAGE↗
DOE OSTI2022

Recent Progress in Electrochemical Nitrogen Reduction on Transition Metal Nitrides

Distributed electrochemical nitrogen reduction reaction (ENRR) powered by renewable energy for the on-site production of ammonia is an attractive alternative to the industrial Haber–Bosch process, which is responsible for roughly 2 % of global energy consumption. Here, in this Review, we summarize recent progress in the ENRR catalyzed by transition metal nitrides (TMNs). The unique electronic structures of TMNs make them promising ENRR catalysts for active and selective ammonia production, which have been predicted theoretically and demonstrated experimentally. Reaction pathways and deactivation mechanisms of the ENRR on different TMNs are surveyed, and current understanding of structure-activity relations is discussed. To develop highly active, selective, and stable TMN catalysts for industrial-scale ENRR, membrane electrode assembly configuration is recommended in catalyst evaluation. Furthermore, we highlight the importance of developing mechanistic understanding on ENRR with different operando spectroscopic techniques.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2019

Autotrophic, Heterotrophic, and Mixotrophic Nitrogen Assimilation for Single-Cell Protein Production by Two Hydrogen-Oxidizing Bacterial Strains

To recover a nitrogen resource from high-ammonia-nitrogen wastewater, two amphitrophic hydrogen-oxidizing bacteria (HOB), Paracoccus denitrificans Y5 and P. versutus D6, capable of nitrogen assimilation for single-cell protein (SCP) production were isolated. These two HOB strains could grow autotrophically with H{sub 2} as an electron donor, O{sub 2} as an electron acceptor, CO{sub 2} as a carbon source, and ammonia nitrogen (NH{sub 4}{sup +}-N) as a nitrogen source. The cell molecular formulas of strains Y5 and D6 determined by autotrophic cultivation were C{sub 3.33}H{sub 6.83}O{sub 2.58}N{sub 0.77} and C{sub 2.87}H{sub 5.34}O{sub 3.17}N{sub 0.57}, respectively. The isolated strains could synchronously remove NH{sub 4}{sup +}-N and organic carbon and produce SCP via heterotrophic cultivation. The rates of removal of NH{sub 4}{sup +}-N and soluble chemical oxygen demand reached 35.47 and 49.04%, respectively, for Y5 under mixotrophic cultivation conditions with biogas slurry as a substrate. SCP content of strains Y5 and D6 was 67.34–73.73% based on cell dry weight. Compared with soybean meal, the SCP of Y5 contained a variety of amino acids.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2018

Assessment of calcium addition on the removal of U(VI) in the alkaline conditions created by NH3 gas

Remediation of uranium (U) contamination in the deep vadose zone (VZ) sediments abundant in calcite mineral is a challenging task considering the formation of highly stable and mobile uranyl complexes with carbonate and calcium in pore water composition. There is a concern that uranium contamination in the VZ can serve as a continued source for groundwater pollution, creating a risk to human health and the environment through the groundwater pathway. This requires in-situ remediation of the radionuclide-contaminated VZ to convert soluble U species to low solubility precipitates that are stable in the natural environment. Injection of reactive gasses (e.g., NH3) is a promising technology to decrease U mobility in the unsaturated zone without the addition of liquid amendments. The NH3 injection creates alkaline conditions that can alter the sediment pore water composition due to a release of elements from minerals (via desorption and dissolution) that are present in the sediment. However, it is not known how VZ pore water constituents (Si, Al3+, HCO3 -, and Ca2 +) would affect U(VI) removal/precipitation in alkaline conditions. This study quantified the role of major pore water constituents typically present in the arid and semi-arid environments of the western regions of the U.S and identified solid uranium-bearing phases that could potentially precipitate from solutions approximating pore water compositions after pH manipulations via ammonia gas injections. Triplicate samples were prepared using six Si (5, 50 100, 150, 200, and 250 mM), six HCO3 - (0, 3, 25, 50, 75, and 100 mM), and two Ca2+ (5 and 10 mM) concentrations. The concentration of aluminum and uranium was kept constant at 5mM and 0.0084 mM, respectively, in all synthetic formulations tested. Results showed that the percentage of U(VI) removal was controlled by the Si/Al molar ratios and Ca2+ concentrations. Regardless of the bicarbonate concentration tested, the percentage of U(VI) removed increased as the Si/Al ratios were increased. However, higher Ca concentrations correlated with higher U(VI) removal, ranging between 96% and 99%, at low Si/Al ratios. The SEM images of dried precipitates displayed dense amorphous regions high in silica content, where EDS elemental analysis unveiled higher U atomic percentages. The formation of uranyl silicate and carbonate minerals was also predicted by the speciation modeling. XRD analysis revealed the presence of uranyl carbonate mineral phases (andersonite, grimselite); however, uranyl silicates predicted (Naboltwoodite) were not identified experimentally, possibly due to the amorphous nature of the silica solid phases observed in our experiments.

Katsenovich, Yelena↗
DOE OSTI2025

C3MechLite: An integrated component library of compact kinetic mechanisms for low-carbon, carbon neutral and zero-carbon fuels

Based on our latest detailed chemical reaction mechanism, C3MechV4.0, we have developed two reduced reaction mechanisms—C3MechLite and C3MechCore—targeting C 0 –C 3 chemical species including NH 3 . C3MechLite (61 species), contains a number of species comparable to GRI-Mech (53 species), that can accurately predict the combustion characteristics of hydrogen, carbon monoxide, ammonia, methane, natural gas, nitrogen oxides, and their mixtures for a wide range of conditions. C3MechCore (118 species) targets a more comprehensive range of C 0 –C 3 fuels, including ammonia, methanol, ethanol, and dimethyl ether. Both mechanisms demonstrate predictive accuracy comparable to C3MechV4.0 for the combustion characteristics of the target fuels. C3MechLite is designed with a component library structure, enabling further reduction in mechanism size depending on the fuel(s) of interest for 2D/3D numerical simulations. Various combinations of component libraries were validated, and the average prediction error remains within 1 % compared to C3MechLite. Furthermore, the mechanism was applied to 3D LES simulations of H 2 lifted flames and was confirmed to reproduce flame characteristics with high accuracy. C3MechLite and its component library structure enable high-fidelity and computationally efficient chemical kinetic mechanisms, paving the way for application in more complex combustion simulations.

Ammonia↗
DOE OSTI2018

Evaluation of NOx emissions of a retrofitted Euro 5 passenger car for the Horizon prize “Engine retrofit”

Highlights: • Many studies report diesel vehicles emitting more than 4 times the type approval NO{sub x} in real driving conditions. • One solution is retrofitting them, but there is no legislative background for passenger cars. • The Horizon 2020 prize for the “Engine Retrofit for Clean Air” aims at reducing the pollution in cities. • A Euro 5 retrofitted vehicle showed significant reductions over test cycles, but small at the cold start phases. • In some high speed conditions NH{sub 3} and N{sub 2}O were measured. The Horizon 2020 prize for the “Engine Retrofit for Clean Air” aims at reducing the pollution in cities by spurring the development of retrofit technology for diesel engines. A Euro 5 passenger car was retrofitted with an under-floor SCR (Selective Catalytic Reduction) for NO{sub x} catalyst in combination with a solid ammonia based dosing system as the NO{sub x} reductant. The vehicle was tested both on the road and on the chassis dynamometer under various test cycles and ambient temperatures. The NO{sub x} emissions were reduced by 350–1100 mg/km (60–85%) in the laboratory depending on the test cycle and engine conditions (cold or hot start), except at type approval conditions. The reduction for cold start urban cycles was < 75 mg/km (< 15%). The on road and laboratory tests were inline. In some high speed conditions significant increase of ammonia (NH{sub 3}) and nitrous oxide (N{sub 2}O) were measured. No effect was seen on other pollutants (hydrocarbons, carbon monoxide and particles). The results of the present study show that retrofitting high emitting vehicles can significantly reduce vehicle NO{sub x} emissions and ultimately pollution in cities.

54 ENVIRONMENTAL SCIENCES↗