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NASA NTRS2015

Aircraft Measurements of BrO, IO, Glyoxal, NO2, H2O, O2-O2 and Aerosol Extinction Profiles in the Tropics: Comparison with Aircraft-/Ship-Based in Situ and Lidar Measurements

Tropospheric chemistry of halogens and organic carbon over tropical oceans modifies ozone and atmospheric aerosols, yet atmospheric models remain largely untested for lack of vertically resolved measurements of bromine monoxide (BrO), iodine monoxide (IO) and small oxygenated hydrocarbons like glyoxal (CHOCHO) in the tropical troposphere. BrO, IO, glyoxal, nitrogen dioxide (NO2), water vapor (H2O) and O2-O2 collision complexes (O4/ were measured by the University of Colorado Airborne Multi-AXis Differential Optical Absorption Spectroscopy (CU AMAXDOAS) instrument, aerosol extinction by high spectral resolution lidar (HSRL), in situ aerosol size distributions by an ultra high sensitivity aerosol spectrometer (UHSAS) and in situ H2O by vertical-cavity surface-emitting laser (VCSEL) hygrometer. Data are presented from two research flights (RF12, RF17) aboard the National Science Foundation/ National Center for Atmospheric Research Gulfstream V aircraft over the tropical Eastern Pacific Ocean (tEPO) as part of the "Tropical Ocean tRoposphere Exchange of Reactive halogens and Oxygenated hydrocarbons" (TORERO) project (January/February 2012). We assess the accuracy of O4 slant column density (SCD) measurements in the presence and absence of aerosols. Our O4-inferred aerosol extinction profiles at 477 nm agree within 6% with HSRL in the boundary layer and closely resemble the renormalized profile shape of Mie calculations constrained by UHSAS at low (sub-Rayleigh) aerosol extinction in the free troposphere. CU AMAX-DOAS provides a flexible choice of geometry, which we exploit to minimize the SCD in the reference spectrum (SCDREF, maximize signal-to-noise ratio) and to test the robustness of BrO, IO and glyoxal differential SCDs. The RF12 case study was conducted in pristine marine and free tropospheric air. The RF17 case study was conducted above the NOAA RV Ka'imimoana (TORERO cruise, KA-12-01) and provides independent validation data from ship-based in situ cavity-enhanced DOAS and MAX-DOAS. Inside the marine boundary layer (MBL) no BrO was detected (smaller than 0.5 pptv), and 0.2-0.55 pptv IO and 32-36 pptv glyoxal were observed. The near-surface concentrations agree within 30% (IO) and 10% (glyoxal) between ship and air-craft. The BrO concentration strongly increased with altitude to 3.0 pptv at 14.5 km (RF12, 9.1 to 8.6 deg N; 101.2 to 97.4 deg W). At 14.5 km, 5-10 pptv NO2 agree with model predictions and demonstrate good control over separating tropospheric from stratospheric absorbers (NO2 and BrO). Our profile retrievals have 12-20 degrees of freedom (DoF) and up to 500m vertical resolution. The tropospheric BrO vertical column density (VCD) was 1.5 x 10(exp 13) molec cm(exp -2) (RF12) and at least 0.5 x 10(exp 13) molec cm(exp -2) (RF17, 0- 10 km, lower limit). Tropospheric IO VCDs correspond to 2.1 x 10(exp 12) molec cm(exp -2) (RF12) and 2.5 x 10(exp 12) molec cm(exp -2) (RF17) and glyoxal VCDs of 2.6 x 10(exp 14) molec cm(exp -2) (RF12) and 2.7 x 10(exp 14) molec cm(exp -2) (RF17). Surprisingly, essentially all BrO as well as the dominant IO and glyoxal VCD fraction was located above 2 km (IO: 58 plus or minus 5 %, 0.1-0.2 pptv; glyoxal: 52 plus or minus 5 %, 3-20 pptv). To our knowledge there are no previous vertically resolved measurements of BrO and glyoxal from aircraft in the tropical free troposphere. The atmospheric implications are briefly discussed. Future studies are necessary to better understand the sources and impacts of free tropospheric halogens and oxygenated hydrocarbons on tropospheric ozone, aerosols, mercury oxidation and the oxidation capacity of the atmosphere.

Volkamer, R.↗
NASA NTRS2016

Optical Breath Gas Extravehicular Activity Sensor for the Advanced Portable Life Support System

The function of the infrared gas transducer used during extravehicular activity (EVA) in the current space suit is to measure and report the concentration of carbon dioxide (CO2) in the ventilation loop. The next generation portable life support system (PLSS) requires highly accurate CO2 sensing technology with performance beyond that presently in use on the International Space Station extravehicular mobility unit (EMU). Further, that accuracy needs to be provided over the full operating pressure range of the suit (3 to 25 psia). Accommodation within space suits demands that optical sensors meet stringent size, weight, and power requirements. A laser diode (LD) sensor based on infrared absorption spectroscopy is being developed for this purpose by Vista Photonics, Inc. Version 1.0 prototype devices were delivered to NASA Johnson Space Center (JSC) in September 2011. The prototypes were upgraded with more sophisticated communications and faster response times to version 2.0 and delivered to JSC in July 2012. The sensors incorporate a laser diode based CO2 channel that also includes an incidental water vapor (humidity) measurement. The prototypes are controlled digitally with an field-programmable gate array microcontroller architecture. Based on the results of the iterative instrument development, further prototype development and testing of instruments were performed leveraging the lessons learned where feasible. The present development extends and upgrades the earlier hardware for the advanced PLSS 2.5 prototypes for testing at JSC. The prototypes provide significantly enhanced accuracy for water vapor measurement and eliminate wavelength drift affecting the earlier versions. Various improvements to the electronics and gas sampling are currently being advanced including the companion development of engineering development units that will ultimately be capable of radiation tolerance. The combination of low power electronics with the performance of a long wavelength laser spectrometer enables multi-gas sensors with significantly increased performance over that presently offered in the EMU.

Wood, William R.↗
NASA NTRS2015

Evaluating a New Homogeneous Total Ozone Climate Data Record from GOME/ERS-2, SCIAMACHY/Envisat, and GOME-2/MetOp-A

The European Space Agency's Ozone Climate Change Initiative (O3-CCI) project aims at producing and validating a number of high-quality ozone data products generated from different satellite sensors. For total ozone, the O3-CCI approach consists of minimizing sources of bias and systematic uncertainties by applying a common retrieval algorithm to all level 1 data sets, in order to enhance the consistency between the level 2 data sets from individual sensors. Here we present the evaluation of the total ozone products from the European sensors Global Ozone Monitoring Experiment (GOME)/ERS-2, SCIAMACHY/Envisat, and GOME-2/MetOp-A produced with the GOME-type Direct FITting (GODFIT) algorithm v3. Measurements from the three sensors span more than 16 years, from 1996 to 2012. In this work, we present the latest O3-CCI total ozone validation results using as reference ground-based measurements from Brewer and Dobson spectrophotometers archived at the World Ozone and UV Data Centre of the World Meteorological Organization as well as from UV-visible differential optical absorption spectroscopy (DOAS)/Système D′Analyse par Observations Zénithales (SAOZ) instruments from the Network for the Detection of Atmospheric Composition Change. In particular, we investigate possible dependencies in these new GODFIT v3 total ozone data sets with respect to latitude, season, solar zenith angle, and different cloud parameters, using the most adequate type of ground-based instrument. We show that these three O3-CCI total ozone data products behave very similarly and are less sensitive to instrumental degradation, mainly as a result of the new reflectance soft-calibration scheme. The mean bias to the ground-based observations is found to be within the 1 plus or minus 1 percent level for all three sensors while the near-zero decadal stability of the total ozone columns (TOCs) provided by the three European instruments falls well within the 1-3 percent requirement of the European Space Agency's Ozone Climate Change Initiative project.

Satellite sensors↗
NASA NTRS2017

Developing V-Xanes Oxybarometry for Probing Materials Formed in Reducing Environments in the Early Solar Disk

Vanadium exhibits four oxidation states (V(sup 2+), V(sup 3+), V(sup 4+) and V(sup 5+)) that have been shown to preferentially partition between melt phases dependent on redox conditions, spanning oxygen fugacity across more than 10 log units. We are developing synchrotron-based x-ray absorption spectroscopy of low-fugacity standards for the determination of V oxidation state in highly reducing conditions relevant to the early solar nebula.

Butterworth, A. L.↗
NASA NTRS2017

Molecular Composition Analysis of Distant Targets

This document is the Final Report for NASA Innovative Advanced Concepts (NIAC) Phase I Grant 15-NIAC16A-0145, titled Molecular Composition Analysis of Distant Targets. The research was focused on developing a system concept for probing the molecular composition of cold solar system targets, such as Asteroids, Comets, Planets and Moons from a distant vantage, for example from a spacecraft that is orbiting the target (Hughes et al., 2015). The orbiting spacecraft is equipped with a high-power laser, which is run by electricity from photovoltaic panels. The laser is directed at a spot on the target. Materials on the surface of the target are heated by the laser beam, and begin to melt and then evaporate, forming a plume of asteroid molecules in front of the heated spot. The heated spot glows, producing blackbody illumination that is visible from the spacecraft, via a path through the evaporated plume. As the blackbody radiation from the heated spot passes through the plume of evaporated material, molecules in the plume absorb radiation in a manner that is specific to the rotational and vibrational characteristics of the specific molecules. A spectrometer aboard the spacecraft is used to observe absorption lines in the blackbody signal. The pattern of absorption can be used to estimate the molecular composition of materials in the plume, which originated on the target. Focusing on a single spot produces a borehole, and shallow subsurface profiling of the targets bulk composition is possible. At the beginning of the Phase I research, the estimated Technology Readiness Level (TRL) of the system was TRL-1. During the Phase I research, an end-to-end theoretical model of the sensor system was developed from first principles. The model includes laser energy and optical propagation, target heating, melting and evaporation of target material, plume density, thermal radiation from the heated spot, molecular cross section of likely asteroid materials, and estimation of the absorption profile at a distant spectrometer. Results obtained by executing simulations based on the model provide compelling evidence that the concept of remote laser evaporative molecular absorption spectroscopy is feasible. In this document, technical details of the model are presented, and results of simulations are described that indicate the utility of the proposed sensor system. Additionally, an asteroid rendezvous mission is analyzed, with a survey of system requirements to accomplish molecular composition analysis of the asteroid. Based on positive theoretical results obtained during Phase I, the estimated TRL of the system is now TRL-2. This document also describes potential future research and experimentation that could push the system to TRL-4 within 2 years. Steps required for construction of a laboratory prototype are described. An experiment to test predictions of the theory is described, based on the laboratory prototype setup.

asteroid↗
NASA NTRS2017

Characterizing Nanophase Materials on Mars: Spectroscopic Studies of Allophane and Imogolite

Allophane is an amorphous or poorly crystalline hydrous aluminosilicate material. Allophane's chemical structure represents a hollow nanosphere, 5-6 nm in diameter with 4-7 large pores in the structure. Identification of allophane and other amorphous and nanophase minerals on Mars has provided clues about the aqueous geochemical environment there. These materials likely represent partially altered or leached basaltic ash and therefore, could represent a geologic marker for where water was present on the Martian surface; as well as indicate regions of climate change, where surface water was not present long enough or sufficiently warm to form clays. Characterization of these materials is important for increasing spectral recognition capabilities using visible/near-infrared (VNIR) and thermal infrared (TIR) spectra of Mars. A suite of synthetic allophane samples was created using a method that has been modified to produce allophane with Fe isomorphically substituted for Al in octahedral coordination. Compositions of the materials range from high-Si allophane (molar Al:Si = 1:2) to protoimogolite (Al:Si = 2:1), with Fe(3+) and Fe(2+) isomorphically substituted for Al from 0-10 mol% of total Al. These compositions span the range observed in natural terrestrial allophanes. Fe K-edge X-ray absorption spectroscopy provided information on the speciation and electrochemical and structural position of Fe in the framework. Fourier transform infrared spectroscopy confirmed syntheses and demonstrated changes in infrared spectroscopic signature with Fe substitution. VNIR reflectance spectra and TIR Thermal infrared emissivity spectra were also collected for direct comparison to Martian data. By increasing spectral recognition capacities of nanophase materials, more accurate estimates can be made on the aqueous geochemical environment of Mars.

Jeute, Thomas↗
NASA NTRS2018

The Network for the Detection of Atmospheric Composition Change (NDACC): History, Status and Perspectives

The Network for the Detection of Atmospheric Composition Change (NDACC) is an international global network of more than 90 stations making high-quality measurements of atmospheric composition that began official operations in 1991 after 5 years of planning. Apart from sonde measurements, all measurements in the network are performed by ground-based remote-sensing techniques. Originally named the Network for the Detection of Stratospheric Change (NDSC), the name of the network was changed to NDACC in 2005 to better reflect the expanded scope of its measurements. The primary goal of NDACC is to establish long-term databases for detecting changes and trends in the chemical and physical state of the atmosphere (mesosphere, stratosphere, and troposphere) and to assess the coupling of such changes with climate and air quality. NDACC's origins, station locations, organizational structure, and data archiving are described. NDACC is structured around categories of ground-based observational techniques (sonde, lidar, microwave radiometers, Fourier-transform infrared, UV-visible DOAS (differential optical absorption spectroscopy)-type, and Dobson-Brewer spectrometers, as well as spectral UV radiometers), timely cross-cutting themes (ozone, water vapour, measurement strategies, cross-network data integration), satellite measurement systems, and theory and analyses. Participation in NDACC requires compliance with strict measurement and data protocols to ensure that the network data are of high and consistent quality. To widen its scope, NDACC has established formal collaborative agreements with eight other cooperating networks and Global Atmosphere Watch (GAW). A brief history is provided, major accomplishments of NDACC during its first 25 years of operation are reviewed, and a forward-looking perspective is presented.

lidar↗
NASA NTRS2017

High-Resolution NO2 Observations from the Airborne Compact Atmospheric Mapper: Retrieval and Validation

Nitrogen dioxide (NO2) is a short-lived atmospheric pollutant that serves as an air quality indicator and is itself a health concern. The Airborne Compact Atmospheric Mapper (ACAM) was flown on board the NASA UC-12 aircraft during the Deriving Information on Surface Conditions from Column and Vertically Resolved Observations Relevant to Air Quality Maryland field campaign in July 2011. The instrument collected hyperspectral remote sensing measurements in the 304-910 nm range, allowing daytime observations of several tropospheric pollutants, including nitrogen dioxide (NO2), at an unprecedented spatial resolution of 1.5 × 1.1 sq. km. Retrievals of slant column abundance are based on the differential optical absorption spectroscopy method. For the air mass factor computations needed to convert these retrievals to vertical column abundance, we include high-resolution information for the surface reflectivity by using bidirectional reflectance distribution function data from the Moderate Resolution Imaging Spectroradiometer. We use high-resolution simulated vertical distributions of NO2 from the Community Multiscale Air Quality and Global Modeling Initiative models to account for the temporal variation in atmospheric NO2 to retrieve middle and lower tropospheric NO2 columns (NO2 below the aircraft). We compare NO2 derived from ACAM measurements with in situ observations from NASA's P-3B research aircraft, total column observations from the ground-based Pandora spectrometers, and tropospheric column observations from the space-based Ozone Monitoring Instrument. The high-resolution ACAM measurements not only give new insights into our understanding of atmospheric composition and chemistry through observation of subsampling variability in typical satellite and model resolutions, but they also provide opportunities for testing algorithm improvements for forthcoming geostationary air quality missions.

Lamsal, L. N.↗
NASA NTRS2020

Evaluation of the Stratospheric and Tropospheric Bromine Burden over Fairbanks, Alaska Based on Column Retrievals of Bromine Monoxide

In spring 2011, columns of bromine monoxide (BrO) were retrieved over Fairbanks, Alaska using a ground-based multifunction differential optical absorption spectroscopy (MFDOAS) instrument. MFDOAS vertical column BrO is consistently lower than retrievals from the satellite-based Ozone Monitoring Instrument (OMI), with a relative bias of 20 ± 14%. Numerous tropical-based studies suggest that 5 ± 2 ppt of bromine from very short-lived substances (VSLS) reaches the stratosphere. We evaluate upper limits on the contribution of VSLS to stratospheric bromine by treating the column retrievals of BrO as purely stratospheric and modeling the ratio of BrO to total inorganic bromine. The OMI and MFDOAS retrievals respectively present 8 and 5 ppt upper limits on the stratospheric injection of VSLS, and kinetic uncertainties in the daytime partitioning of bromine species decrease both values by ~1.6 ppt. The OMI-based estimate is in agreement with the 5 ppt tropical-based value for stratospheric injection of VSLS if the tropospheric column of BrO is 1.5 × 10(exp 13) molecules/cu. cm over Fairbanks, which is within the range of uncertainty of a second ground-based instrument that monitored tropospheric BrO during the campaign. Because our ground-based instruments detected no BrO near the surface, this value for tropospheric BrO would originate from the free troposphere and is in agreement with previous retrievals of background tropospheric BrO. Our calculations of tropospheric BrO over Fairbanks are most sensitive to uncertainties in the stratospheric loading of VSLS, followed by the difference between the OMI and MFDOAS retrievals of BrO.

Pamela A. Wales↗
NASA NTRS2020

High-Precision Determination of Oxygen-Kalpha Transition Energy Excludes Incongruent Motion of Interstellar Oxygen

We demonstrate a widely applicable technique to absolutely calibrate the energy scale of x-ray spectra with experimentally well-known and accurately calculable transitions of highly charged ions, allowing us to measure the K-shell Rydberg spectrum of molecular O2 with 8 meV-uncertainty. We reveal a systematic ~450meV shift from previous literature values, and settle an extraordinary discrepancy between astrophysical and laboratory measurements of neutral atomic oxygen, the latter being calibrated against the aforementioned O2 literature values. Because of the widespread use of such, now deprecated, references, our method impacts on many branches of x-ray absorption spectroscopy. Moreover, it potentially reduces absolute uncertainties there to below the meV level.

M A Leutenegger↗
NASA NTRSDate not supplied

Additional Trials & Tribulations in Synthesizing a Sulfide Standard

Well-characterized sulfide reference materials that can serve as matrix-matched calibrants for in-situ trace element analyses via laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) remain elusive. Here, we describe the creation an in-house sulfide standard at NASA JSC that will be used to measure siderophile and chalcophile trace elements in low pressure experimental products, specifically pentlandite ([FeNi]9S8) and pyrrhotite ([FeNi]1-xS), as well as natural sulfides in terrestrial and meteoritic mineral assemblages. Recent methods in creating a homogenous sulfide standard include pressed pellets, synthesized chips, or fused glass [e.g. 1-3]. Other studies, however, have had success in forming homogenous FeS standards via synthesization methods [e.g. 4-6]. We present a variation of the method described in [4], in which we create a pyrrhotite standard doped with a variety of trace elements (Zn, As, Se, Mo, Ru, Rh, Pd, Sn, Sb, Te, W, Os, Ir, Pt, Au) at ~10-40 ppm and Cu at ~200 ppm. Sulfide compositions were constructed using Fe and Ni metal and elemental sulfur powders. Trace elements were added to elemental sulfur from Atomic Absorption Spectroscopy (AAS) elemental standards as either nitrate or chloride solutions to prevent oxidation of the metal powders. The dried sulfur mixture was mixed with Fe and Ni powders and mechanically mixed before two aliquots were placed in separate SiO2 tubes. Each tube was held under vacuum for ~30 minutes, sealed under vacuum, and then heated at 800C for 48 hours. Like [4], the synthesis products were composed of pourous sulfide crystals. Major element analyses of both experimental aliquots, collected using an Electron Probe Microanalyser (EPMA), yield indistinguishable major element compositions (uncertainties in 2SE & 2RSE[%]), with an average of 57.90  0.09 (0.16 %), 4.95  0.03 (0.55 %), and 39.70  0.14 (0.34 %), for Fe, Ni, and S, respectively. Trace element data were measured using a Photon Machines 193nm laser ablation system coupled to a Thermo-Scientific Element-XR ICP-MS. Spot sizes were limited to 50 μm due to the porous nature of the sulfide target material. Trace element abundances, normalized to Fe as an internal standard, were also found to be homogenous between the two aliquots, with weighted mean 2RSE (%) values of <3.0 for all trace elements. Synthesized products were re-powdered and absolute concentrations measured via solution ICP-MS. Although the sulfide appears to be homogenous, sintering experiments will be performed to more closely match the standard density to natural sulfides and minimize differences in ablation behavior. Improved density also allows for higher sensitivity (i.e. more compact target material) and larger spot sizes or traverses, as void space is eliminated. Additional major and trace element analyses on the products of the sintering experiments will be undertaken.

Jacob B Setera↗
NASA NTRS2022

A Sub-THz CMOS Molecular Clock with 20 ppt Stability at 10,000 s Based on A Dual-Loop Spectroscopic Detection and Digital Frequency Error Integration

This paper presents a dual-loop chip-scale molecular clock (CSMC), which enhances the Allan Deviation performance by combining high signal-to-noise ratio of using fundamental mode and long-term stability of using higher order modes in derivative molecular absorption spectroscopy. In addition, digital frequency-error integration is adopted in the frequency-locked loop to provide an infinite open-loop DC gain, which fully suppresses any frequency drift caused by the temperature-sensitive crystal oscillator. This new generation CSMC is implemented in 65-nm CMOS, and achieves 20 ppt (part-per-trillion) Allan Deviation at 10,000 s averaging time with 71-mW power consumption.

Han, Ruonan↗
NASA NTRSDate not supplied

Lunar Payloads to Constrain Exospheric Water through the NASA M-STAR program

Our understanding of water cycles on the Moon has significantly enhanced recent observations by Chang E-5, Lunar Prospector, and Chandrayaan-1 missions indicating the existence of an active water cycle on the Moon. In a new partnership between Delaware State University (DSU) and NASA Goddard Space Flight Center, enabled through the NASA’s M-STAR (MUREP Space Technology Artemis Research) program, we are developing low mass and power lunar rover payloads to enable long-duration human exploration missions. Payload technologies include wavelength modulation absorption spectroscopy to simultaneously detect water (H16OH) and isotopes (H16OD) in the (6700 nm) mid-infrared region using a closed path in compact Herriot cell optical design and wavelength modulation spectroscopy, and (2) Laser-induced breakdown spectroscopy (LIBS) to simultaneously detect and correlate water isotopes with characteristics elemental composition of lunar regolith. Due to the airless atmosphere of the Moon, we will utilize Artificial intelligence (AI) and Machine learning (ML) approaches to discriminate spectral interference with instrument drifts and correlate mid-IR trace gas profile with LIBS spectral information. This partnership will initiate a STEM engagement space program, e.g., Lander and CubeSat payload technology development for students and the next-generation NASA workforce for future lunar and Mars missions. DSU, a Historically Black University, prides itself in its proven excellence in teaching and research. It enrolls a diverse population of students (~5000) traditionally underrepresented in STEM disciplines. DSU has established itself at the forefront of optics and photonics research that transcends multidisciplinary fields of earth sciences, environmental, defense, and biomedical sensing applications.

water cycles↗
NASA NTRSDate not supplied

Evaluating Diurnal Ozone Emissions: A Comparative Analysis of DSCOVR EPIC, PANDORA, and TOLNet Data for Space-Based Monitoring Assessment: A Case Study by ASDC

Stratospheric ozone occurs naturally in the upper atmosphere, forming a protective layer that shields us from the sun's harmful ultraviolet rays. Tropospheric ozone is not emitted directly into the air but is created by chemical reactions between nitrogen oxides (NOx) and volatile organic compounds (VOC). This reaction happens when pollutants emitted by cars, power plants, industrial boilers, refineries, chemical plants, and other sources chemically react in sunlight [1]. Therefore, increased levels of tropospheric ozone indicate the presence of pollutants in the air. While daily anthropogenic activity causes an increase of ground-level ozone, variation of stratospheric ozone changes happens much slower, so that variation of the total ozone column reflects the variation of the tropospheric column due to natural, e.g., wildfires and anthropogenic air pollution. Both total and tropospheric ozone column products are used in this study. The reflectance spectra measured by the Earth Polychromatic Imaging Camera (EPIC) instrument aboard the Deep Space Climate Observatory (DSCOVR) spacecraft are compared with a set of radiative transfer-derived lookup tables for the EPIC filter transmission functions and a wide range of ozone values to retrieve ozone with a maximum resolution of 18 km at the sub-satellite point [2]. EPIC provides total column ozone in level 2 and level 4 products and tropospheric column ozone in level 4 products. Both EPIC Ozone products [2] are available at the Atmospheric Science Data Center (ASDC) at NASA Langley Research Center [3, 4]. Pandora spectrometer instrument measures columnar amounts of trace gases in the atmosphere. These gases (O3, NO2, CH2O) absorb light from the sun at specific wavelengths in the ultraviolet-visible spectrum [5]. Using the theoretical solar spectrum as a reference, Pandora determines trace gas amounts using differential optical absorption spectroscopy (DOAS). Pandora ozone retrievals are available from the Pandonia Global Network [6]. Pandora data from North American major metropolitan areas, New York, NY, Washington DC, Los Angeles, CA, and Mexico City. Tropospheric Ozone Lidar Network (TOLNet) was established in 2012 to provide high spatiotemporal observations of tropospheric ozone to (1) better understand physical processes driving the ozone budget in various meteorological and environmental conditions and (2) validate the tropospheric ozone measurements of space-borne missions [7]. TOLNet data are available at ASDC [8]. While EPIC provides global coverage of ozone retrievals several times daily, temporal resolution may miss some features in daily ozone variations. Ground-based sensors such as Pandora spectrometers and TOLNet lidars provide better temporal resolution while missing continuous spatial coverage. The forthcoming ozone retrieval from the TEMPO mission [9] will provide better spatial and temporal coverage of air quality (including ozone) over North America. This study investigates whether EPIC ozone products can detect diurnal air quality variations and compare ozone temporal development with retrieval by ground-based instruments.

diurnal ozone emissions, DSCOVR EPIC, PANDORA, spa↗
NASA NTRSDate not supplied

Shock Tube Characterization of Laser Absorption Sensors for Combustion Measurements of Green Propellants

Chemical kinetic models for green spacecraft propulsion systems are needed to calculate efficiency, estimate toxic products, and mitigate plume impingement risks. Laser absorption spectroscopy (LAS) is a common technique used to measure time-resolved mole fraction for model validation. LAS was used to measure species-time history nitrous oxide (N2O) and carbon monoxide (CO) behind reflected shock waves. The diagnostics were implemented at the University of Central Florida high-pressure shock tube facility. A mixture of ethylene (0.002) and N2O (0.008) was diluted with argon gas (0.99) and shock heated 12 bar and temperatures from 1400 to 1600 K.

Marley A. Albright↗
NASA NTRS2024

Fundamental Experimental Tests and Modeling of LOX/CH4 Engines at High Pressures

In recent years, the space travel industry has grown exponentially, resulting in the need for a low-cost, efficient rocket engine fuel. As such, there has been renewed interest in utilizing liquid natural gas (LNG) as it is less likely to soot than kerosene-based fuels and has widespread availability and low cost of use as compared to the traditional RP-X and even liquid methane (LCH4) fuels due to the reduced need for refinement. However, current literature does not fully cover varying blends of natural gas and the effects that impurities have on natural gas/methane fuels, with most studies being confined to low-pressure applications. Therefore, new experimental ignition delay time measurements at rocket engine relevant pressures are essential to ensure current chemical kinetic models capture the ignition behavior at these elevated conditions and to determine the optimal purity levels for a reliable, cost-efficient, aerospace-grade LCH4/LNG fuel. The current work explores various blends of natural gas/methane fuel with various impurities, including higher hydrocarbons as well as nitrogen-carriers. A shock tube study was carried out to study the ignition delay times and carbon monoxide time histories of these natural gas blends utilizing chemiluminescence and laser absorption spectroscopy at 20, 50 and 100 atm over temperatures ranging from 1400-1700K and at an equivalence ratio of 1. The experimental data was then compared to two different chemical kinetic mechanisms: the industry-standard GRI 3.0 and the in-house UCF 2022. The data is used to improve chemical kinetic mechanisms and modeling of LNG fuels for rocket engine applications.

Methane↗
NASA NTRS2008

Surface Analysis of 4-Aminothiophenol Adsorption at Polycrystalline Platinum Electrodes

Formation of self-assembled monolayer (SAM) of 4-aminothiophenol (4-ATP) on polycrystalline platinum electrodes has been studied by surface analysis and electrochemistry techniques. The 4-ATP monolayer was characterized by cyclic voltammetry (CV), Raman spectroscopy, reflection absorption infrared (RAIR) spectroscopy, and X-ray photoelectron spectroscopy (XPS). Cyclic voltammetry (CV) experiments give an idea about the packing quality of the monolayer. RAIR and Raman spectra for 4-ATP modified platinum electrodes showed the characteristic adsorption bands for neat 4-ATP indicating the adsorption of 4-ATP molecules on platinum surface. The adsorption on platinum was also evidenced by the presence of sulfur and nitrogen peaks by XPS survey spectra of the modified platinum electrodes. High resolution XPS studies and RAIR spectrum for platinum electrodes modified with 4-ATP indicate that molecules are sulfur-bonded to the platinum surface. The formation of S-Pt bond suggests that ATP adsorption gives up an amino terminated SAM. Thickness of the monolayer was evaluated via angle-resolved XPS (AR-XPS) analyses. Derivatization of 4-ATP SAM was performed using 16-Br hexadecanoic acid.

Rosario-Castro, Belinda I.↗