Tunable Diode Lasers (TDL) for Spectroscopy and Environmental Monitoring
The current status of III-V tunable diode lasers (TDLs) emitting between 1-5 mue wavelengths for spectroscopy and chemical analysis is described.
Diode↗
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Results for “chemical analysis”
Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.
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Aboveground and Belowground Responses to Cyanobacterial Biofertilizer Supplement in a Semi-Arid, Perennial Bioenergy Cropping System
The need for sustainable agricultural practices to meet the food, feed, and fuel demands of a growing global population while reducing detrimental environmental impacts has driven research in multi-faceted approaches to agricultural sustainability. Perennial cropping systems and microbial biofertilizer supplements are two emerging strategies to increase agricultural sustainability that are studied in tandem for the first time in this study. During the establishment phase of a perennial switchgrass stand in SW Montana, USA, we supplemented synthetic fertilization with a nitrogen-fixing cyanobacterial biofertilizer (CBF) and were able to maintain aboveground crop productivity in comparison to a synthetic only (urea) fertilizer treatment. Soil chemical analysis conducted at the end of the growing season revealed that late-season nitrogen availability in CBF-supplemented field plots increased relative to urea-only plots. High-throughput sequencing of bacterial/archaeal and fungal communities suggested fine-scale responses of the microbial community and sensitivity to fertilization among arbuscular mycorrhizal fungi, Planctomycetes, Proteobacteria, and Actinobacteria. Given their critical role in plant productivity and soil nutrient cycling, soil microbiome monitoring is vital to understand the impacts of implementation of alternative agricultural practices on soil health.
biofertilizer↗
Simulating Meteor Ablation at the Hypersonic Materials Environmental Test System
The ablation mechanisms of stony meteorite material and a terrestrial analog were investigated at the Hypersonic Materials Environmental Test System (HyMETS) facility at NASA’s Langley Research Center. The primary analyte (Tamdakht-H5) and arc-jet test conditions were chosen to simulate the entry of an ordinary chondrite through the Earth’s mesosphere. Basalt was selected to compare the meteorite response against material with enhanced polymerization and an elevated concentration of volatile species. The initial ablation process for each material commences with the vaporization of volatile species and germination of a viscous melt layer on the stagnation surface. However, each material exhibited distinct mass loss mechanisms, with basalt recessing at twice the rate of Tamdakht. Inspection of high-speed video and chemical analysis of the post-test melt layer suggests the dominant mode of mass loss of Tamdakht is expressed through the vaporization of volatile compounds. Vaporization rates of Tamdakht are 18x higher than basalt under the most severe test conditions which provides enhanced thermal shielding. Furthermore, Tamdakht produces a relatively stable melt flow, as evidenced by perpetual growth at the sidewall and the exiguous detachment of molten material into the flow. The ablation mechanism of basalt is markedly different from Tamdakht and is governed by volatile species in the virgin material. The dominant mode of mass loss for basalt is attributed to the detachment of large sections of the stagnation surface near the edge radius. An additional but subordinate mode of mass loss is assigned to the removal of melt flow as it passes over the edge radius, where shear forces overcome the rheological properties of the molten matter. Finally, mechanistic details will be discussed in terms of designing future test campaigns, developing meteorite-based materials response models, and impacting the broader scope of the Asteroid Threat Assessment Project (ATAP).
Meteor Ablation↗
Ramdb: The NASA Raman Spectral Database (version 1.00).
Given that, in most instances, minimal sample preparation is required and due to its contactless instrument design, Raman spectroscopy is one of the most versatile vibrational spectroscopic techniques for the chemical analysis of environmental and biological specimens. The diversity of applications of Raman spectroscopy ranges anywhere from art [1] to planetary science missions [2]. The advancement in the use of Raman spectroscopy in Solar System missions, notably in post-mission sample return analysis, requires a spectral library holding the broad range of specimens that could be found in Solar System sources. For this purpose, we have initiated the development of a Raman spectral database (Ramdb) at NASA Ames Research Center. Currently, the database includes experimental and theoretical Raman spectra of PAHs [3, 4], as well as laboratory Raman spectra of amino acids, carbon allotropes, minerals, and analogs relevance to Earth Sciences [5], Exobiology [6], Planetary [7], and Astrochemistry [8] to name just a few examples. Ramdb can be found on the web at www.astrochemistry.org/ramdb, where raw and processed Raman spectra can be downloaded in CSV format. The laboratory Raman spectra are measured using a laser Raman spectrometer (JASCO NRS-5500-532QRI). The Raman instrument is equipped with three excitation lasers, with wavelengths of 405, 532, and 785 nm. A clean silicon substrate is used as the internal standard for wavenumber calibration. Powdered samples were prepared (microscopic >10 um, grounded microscopic < 10 um) on glass slides. Some raw data exhibited a background signal arising as a combination of laser-induced fluorescence from the sample. To correct this background, we developed a Python pipeline that uses open-source Python libraries. Ramdb provides both raw and processed (using Python pipeline) data, which includes tabulated Raman shift transitions and other measurement details. The theoretical Raman band positions of PAHs (pyrene monomers and tetramer clusters) were computed using density functional theory (DFT) with the help of the Gaussian 16 suite of programs [9]. In the near future, Ramdb will serve as a repository of Raman spectral data from Laboratory Astrophysics and Planetary Science experiments involving the irradiation of organic compounds under simulated space and planetary conditions. In addition, online and offline tools will be developed for utilising the database for comparison to the user’s sample.
N Punnakayathil↗
Lunar Impact Melt Crystallization Produces Reflectance Spectra Dominated By Clinopyroxene Signatures: Implications for the Origin of Pink Spinel Anorthosite
Magma-wallrock interaction and impact melt crystallization are the two leading hypotheses for the formation of orbitally detected lunar “pink” spinel anorthosite (PSA) [1-3]. Distinguishing among hypotheses is complicated because both require mixing of anorthositic crust and MgO-rich ultramafic components. Models for PSA formation need to account for either the thermodynamic hurdles of crustal assimilation, or the size of impactor and composition of target material needed to generate spinel during crater and basin formation. Determining whether the energy source is endogenic or exogenic is important for understanding the thermal and chemical evolution of the lunar crust. Here we test the impact melt hypothesis by performing controlled cooling experiments on two hypothetical impact melt compositions. The compositions represent mixing of ultramafic magma and anorthositic crust in molar ratios of approximately 50:50 and 25:75. Synthetic crystallized assemblages were prepared for chemical analysis and bidirectional reflectance spectroscopy in the visible to near-infrared wavelengths. All crystallization experiments contained plagioclase, olivine, and clinopyroxene, but trace amounts of spinel were only observed in the 50:50 mix. The experimental spinel is similar to the compositions inferred from remote observations. However, the high-Ca pyroxene in our experimental assemblages (9 – 18 wt.%) resulted in 1 and 2 µm absorption band center positions consistent with synthetic clinopyroxene. The clinopyroxene absorptions are present regardless of specific mineral modes and the presence of either olivine or spinel. These results suggest that impact melt crystallization will produce clinopyroxene-bearing lithologies, the presence of which masks spectral contributions from coexisting spinel and olivine. Assuming that the trace amounts of spinel observed in our experiments could be concentrated and isolated from the mafic silicates by convection or density settling in the impact melt sheet, the spinel-rich areas would still be proximally associated with the remaining silicate-dominated assemblage exhibiting strong clinopyroxene spectral signatures. We conclude that impact melting of the lunar crust can explain rare cases of PSA in association with clinopyroxene. Previous investigations of magma-wallrock interactions [2] demonstrate that small plagioclase-contaminated regions of an ultramafic intrusion can concentrate spinel whereas larger portions of the same intrusion remain relatively uncontaminated and yield olivine and orthopyroxene, consistent with the more common occurrence of PSAs in association with orthopyroxene ±olivine in the remote sensing database (e.g., Moscoviense Basin) [4].
petrology↗
Simulating Ordinary Chondrite (Tamdakht) Ablation at the Hypersonic Materials Environmental Test System (HyMETS) Facility.
NASA’s Science Mission Directorate (SMD) created the Asteroid Threat Assessment Project (ATAP) to inform decision-makers of risks associated with Potentially Hazardous Objects (PHOs), which may pose an existential threat to human civilization. ATAP assesses risk, in part, by developing analytical physics-based damage models which draw upon data collected during material property characterization efforts, entry simulations, hazard simulations, and ground-based arc-jet testing. Therefore, a pathfinder test campaign was con-ducted at the Hypersonic Materials Environmental Test System (HyMETS) at the NASA Langley Re-search Center to investigate the ablation mechanisms of an ordinary chondrite (Tamdakht H5) and a terrestrial analog (basalt). The HyMETS facility is a 400 kW constricted arc heater used to screen material performance under simulated aerothermal conditions of hypersonic flow.1 Facility conditions were chosen to simulate Earth entry conditions be-tween the upper-mesosphere and the lower thermo-sphere. The ablation mechanisms of Tamdakht and bas-alt are illustrated with still images collected from high-speed video cameras (fig. 1, Tamdakht). Tamdakht produces a relatively stable melt flow, as evidenced by the perpetual growth of a flange at the sidewall and the exiguous detachment of molten material into the flow. Furthermore, an inspection of high-speed video and chemical analysis of the post-test melt layer suggests that the dominant mode of mass loss for Tamdakht, at these test conditions, is expressed through the vaporization of volatiles (e.g., iron, potassium, sodium, phosphorus, and sulfur). The vaporization rates of Tamdakht are greater than basalt under the most extreme test conditions, which leads to an enhanced blowing layer, in-creased thermal shielding, and reduced recession. The ablation mechanisms of basalt are markedly different from Tamdakht and are attributed to the presence of hydrated minerals dispersed at irregular intervals throughout the silicate matrix. Rapid de-composition of secondary minerals and the subsequent formation of water lead to the ejection of the subsurface and overlying melt layer. Furthermore, the presence of water is suspected of lowering the viscosity of the melt layer resulting in increased mass loss near the edge of the test article where drag forces overcome rheological properties (fig. 1, bas-alt). Finally, the results will be discussed in the broader context of meteorite-based material response model development and the potential impact on the Asteroid Threat Assessment Project (ATAP).
Brody K. Bessire↗
Role of Oxygen Fugacity on the Melting Properties of Enstatite Chondrites and Implications for Mercury’s Magmatic Evolution
Mercury, the innermost terrestrial planet, is the most reduced planet in our solar system. Insights from MESSENGER mission data revealed the presence of several distinct geochemical terranes, evidence of complex magmatic processes and collisional processes exposing subsurface materials. Surface chemical analysis indicated elevated S (~2-3 wt%) and low FeO (~1.5 wt%) concentrations. The high sulfur concentration indicates reduced conditions with an average of 5.4 log units below the Iron-Wüstite (IW) oxygen fugacity ( O 2 ) buffer (IW-5.4). Surface compositions also show a range in redox conditions during mantle melting and eruption, with inferred log f O 2 , ranging from IW-6.5 to IW-3.5. The effects of oxygen fugacity on magmatic differentiation are poorly constrained, despite their significance in our understanding of mantle-crust differentiation in the solar system. Enstatite High-Fe (EH) chondrites are very reduced undifferentiated meteorites with elevated concentrations of Fe and volatiles like S, Cl, Na, and K as compared to other chondrites. These characteristics suggest that EH chondrites are a potential analog for Mercury’s building blocks. However, the comparison of Mercury’s surface composition with melting products of EH chondrites is necessary to determine whether Mercury surface materials may be derived from EH chondrite- like materials. Here, we investigate the role of f O 2 on EH melting properties and its implications for Mercury’s accretion and differentiation.
Mercury↗
Surface Exposure History of Asteroid Bennu Based on Cosmogenic Radionuclides in OSIRIS-Rex Samples
The surface of asteroid Bennu changes over time because of impacts, mass movement, and particle ejections [1-4]. The OSIRIS-REx samples were collected from a 20-m-diameter crater on Bennu called Hokioi. One of the driving hypotheses of the mission is that Hokioi is part of a population of small (<25 m) craters that are less than 0.1 Myr old and contain relatively unweathered material [1,4]. Our goal is to understand the recent surface exposure history of Bennu, utilizing radionuclides (10Be, 26Al, 36Cl, 41Ca) produced by both galactic and solar cosmic rays. We received ~12 mg of aggregate sample OREX-803014-0. We picked five of the larger particles with masses ranging from 0.24 to 0.68 mg. We dissolved each particle, along with 0.15 mg Be and 1.0 mg Cl carrier, in HF/HNO3 mixture, and did the same for the remaining aggregate sample of 9.8 mg. After dissolution, we took a small aliquot for chemical analysis, added 0.7 mg of Al carrier, and separated Be, Al, and Cl for analysis of cosmogenic 10Be, 26Al, and 36Cl by accelerator mass spectrometry [5]. Preliminary 26Al results show concentrations of 21–27 dpm/kg for the Bennu samples, with an average of 22.5 ± 0.6 dpm/kg for the five particles and 21.1 ± 0.7 dpm/kg for the remaining aggregate. These values are close to the expected 26Al saturation values of 25–30 dpm/kg for the top 1 m of Bennu’s regolith, suggesting a minimum exposure age of 1.5–2.0 Myr near the surface. Our initial Bennu results also resemble those found for Ryugu samples [6,7]; thus, we can hypothesize that the two asteroids have had similar surface exposure histories.
K C Welten↗
Porous membrane enabled mass spectrometry characterization of microfluidic devices
A system for sampling a liquid includes a sample fluid conduit including a membrane having pores. The membrane prevents the passage of the sample liquid through the pores at a first pressure of the sample liquid in the sample fluid conduit. A surface sampling capture probe has a distal end. The capture probe includes a solvent supply conduit and a solvent exhaust conduit. A solvent composition flowing at the distal end of the capture probe establishes a liquid junction with the membrane and establishes a second pressure within the liquid junction at the membrane. The second pressure is lower than the first pressure. Sample liquid will be drawn through the pores of the membrane by the second pressure at the liquid junction. A method for sampling a liquid and for performing chemical analysis on a liquid are also disclosed.
Cahill, John F.↗
Accurate Prediction of Algal Biomass Lipid, Protein, and Carbohydrate Composition with Machine Learning Regression Modelling of Near-IR Spectra
During large scale algal biomass cultivation, it is difficult to reliably control relative composition to target levels. Rapid determination of chemical composition is feasible by using near infrared (NIR) spectral data. We sought to build and improve on reliable high-throughput screening prediction method based on partial least squares regression (PLSR) by the application of artificial neural networks (ANN) and associated optimization strategies. The algal biomass sample set was designed and created in an iterative process of culturing in physiologically diverse conditions at the GAI field site, followed by compositional analyses at NREL. The workflow allowed us to identify gaps in compositional space for informing the subsequent cultivation and sampling efforts and generated a high quality set of 210 unique samples with chemical analysis results, spectral scanning data, and cultivation metadata. We observed a significant improvement in the performance of carbohydrate content predictions using an optimized ANN model compared to PLSR, with > 16% reduction in mean absolute percent error (MAPE) when tested on the same set of reserved data. The optimized ANN models for FAME and protein prediction performed exceptionally well with 5.99% and 5.09% MAPE, respectively. Application of these methods to detection and quantification of minor biomass constituents that are relevant to certain product streams has shown positive preliminary results, opening the possibility for extensions to the outputs of this powerful data type. All models are accompanied by prediction uncertainties and unsupervised spectral outlier detection to alert an operator to unreliable spectral data. These tools can be deployed for rapid determination of algal culture status, and cultivation and biomass quality improvement.
algal biofuels↗
Porous membrane enabled mass spectrometry characterization of microfluidic devices
A system for sampling a liquid includes a sample fluid conduit including a membrane having pores. The membrane prevents the passage of the sample liquid through the pores at a first pressure of the sample liquid in the sample fluid conduit. A surface sampling capture probe has a distal end. The capture probe includes a solvent supply conduit and a solvent exhaust conduit. A solvent composition flowing at the distal end of the capture probe establishes a liquid junction with the membrane and establishes a second pressure within the liquid junction at the membrane. The second pressure is lower than the first pressure. Sample liquid will be drawn through the pores of the membrane by the second pressure at the liquid junction. A method for sampling a liquid and for performing chemical analysis on a liquid are also disclosed.
Cahill, John F.↗
Numerical Methods of Solution of Chemical Kinetics Equations
Numerical analysis of chemical kinetics in reacting gas equations applied to rocket nozzle and plume flows
ROCKET NOZZLE↗
Grid resolution requirement of chemical explosive mode analysis for large eddy simulations of premixed turbulent combustion
Full Article Figures & data References Citations Metrics Reprints & Permissions Read this article Abstract The grid resolution requirement for trustworthy Chemical Explosive Mode Analysis (CEMA) in Large Eddy Simulation (LES) of premixed turbulent combustion is proposed. Explicit filtering, to emulate the effect of the LES filter, is applied to one-dimensional laminar flame and three-dimensional planar turbulent flames across a wide range of Karlovitz numbers (5 - 239). The identification of the flame front by CEMA is found relatively insensitive to the cell size (Δ), while the combustion mode identification shows more significant sensitivity. Specifically, increasing Δ falsely enhances the auto-ignition and local extinction modes and suppresses the diffusion-assisted mode. Limited dependence of the CEMA performance on the turbulent combustion regime (Karlovitz number) is observed. A simple grid size criterion for reliable CEMA mode identification in LES is proposed as Δ ≲ δ L /2; The criterion can be relaxed to Δ ≲ δ L in the laminar flame limit. Furthermore, theoretical analysis is conducted on an idealised chemistry-diffusion system. The effects of the filtering process and turbulence on the local combustion mode are demonstrated, which is consistent with the numerical observations. Further, by incorporating turbulent combustion models in CEMA, potential improvement in identifying local combustion modes can be expected.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
A numerical study of ignition and flame development characteristics in GCI combustion using large eddy simulations and chemical explosive mode analysis
Here, this work investigates the ignition and flame development processes of low reactivity fuel combustion under compression ignition conditions based on the large eddy simulation approach. The chemical explosive mode analysis (CEMA) is employed to characterize the local combustion features, including gas-liquid fuel zone, auto-ignition, diffusion-assisted, extinction, cool flame and post-ignition zone, among which auto-ignition and post-ignition are found to play a key role in the overall heat release process. The local flame propagation modes in gasoline compression ignition (GCI) are determined by quantifying the relative magnitude of diffusion/chemistry at a representative progress variable in the pre-ignition zone. The results show that autoignition fronts and deflagration waves exist simultaneously in the ignition and intense high temperature heat release (HTHR) stages, but autoignition fronts dominate. In addition, the chemical kinetic processes of four heat release periods are analyzed. The heat release during the ignition period is found to be dominated by the reactions CH 3 + H (+M) <=> CH 4 (+M) and CH 3 CHO + H <=> CH 2 CHO + H 2 . The reaction CH 2 OH + OH <=> CH 2 O + H 2 O always plays an important role in the heat releases during the other three combustion stages including intense HTHR, moderate HTHR and post-combustion.
33 ADVANCED PROPULSION SYSTEMS↗
The Advanced Spectral Library (ASTRAL): Abundance Analysis of the Chemically Peculiar Star HR 465
This paper presents the results of the spectrum analysis of the B-type magnetic chemically peculiar star HR 465. HR 465 shows unusual abundance patterns that vary with a period of 21.5 yr. Our observations are recorded at ϕ = 0.45, 0.68, and 0.85 of the spectroscopic period, where ϕ = 0 represents the phase of maximum flux in the photometric y-band. Synthetic spectra, computed using an LTE atmosphere model, are fit to high-resolution ultraviolet Hubble Space Telescope (ϕ = 0.45) spectra obtained as part of the Advanced Spectral Library Project: Hot Stars program. The ultraviolet data are supplemented by high-resolution optical spectra (ϕ = 0.68 and 0.85) recorded at the Nordic Optical Telescope with the SOFIN spectrograph. The optical data are used as a complement to the high line-density ultraviolet spectrum to derive accurate abundances for elements without spectral lines in the ultraviolet and to improve the abundance phase coverage for many atoms/ions. This analysis presents abundance results for more than 70 atoms/ions and confirms parts of the abundance characteristics previously reported where elements with high mass numbers show significant abundance enhancements compared with solar values while some of the lighter elements show abundance deficiencies. In addition, our measured abundances are consistent with the periodic variability for chromium and rare-earth elements. Our results are compared with earlier investigations of this peculiar object to constrain stellar abundance and diffusion.
Krister E. Nielsen↗
Chemical Processing and Analysis of 'JACEE' Circumpolar Flight 13 & 14
This informal presentation will address the chemical processing status, the current locations and state of data analysis (including mapping and densitometry of x-ray films, event lists and tracing of events in nuclear emulsions, etc.) of the 12 cosmic ray chambers comprising the JACEE-13 and JACEE-14 South Pole circumnavigational long duration balloon flights.
Fountain, Walter↗
Chemical and Thermal Analysis
Work has included significant research in several areas aimed at further clarification of the aging and chemical failure mechanism of thermoplastics (PVDF or Tefzel) for pipes. Among the areas investigated were the crystallinity changes associated with both the Coflon and Tefzel after various simulated environmental exposures using X-Ray diffraction analysis. We have found that significant changes in polymer crystallinity levels occur as a function of the exposures. These crystallinity changes may have important consequences on the fracture, fatigue, tensile, and chemical resistance of the materials. We have also noted changes in the molecular weight distribution of the Coflon material using a dual detector Gel Permeation Analysis. Again these changes may result in variation in the mechanical and chemical properties in the material. We conducted numerous analytical studies with methods including X-Ray Diffraction, Gel Permeation Chromatography, Fourier Transform Infrared Spectroscopy, Thermogravimetric Analysis, and Differential Scanning Calorimetry. We investigated a number of aged samples of both Tefzel and Coflon that were forwarded from MERL. Pressurized tests were performed in a modified Fluid G, which we will call G2. In this case the ethylene diamine concentration was increased to 3 percent in methanol. Coflon pipe sections and powdered Coflon were exposed in pressure cells at 1700 psi at three separate test temperatures, 70 C, 110 C, and 130 C. The primary purpose of the pressure tests in Fluid G2 was to further elucidate the aging mechanism of PVDF degradation.
Bulluck, J. W.↗
An Interactive Spectral Analysis Tool for Chemical Identification and Quantification of Gas-Phase Species in Complex Spectra
A spectral analysis tool has been developed to interactively identify and quantify individual gas-phase species from complex infrared absorbance spectra obtained from laboratory or field data. The SpecQuant program has an intuitive graphical interface that accommodates both reference and experimental data with varying resolution and instrumental lineshape, as well as algorithms to readily align the wavenumber axis of a sample spectrum with the raster of a reference spectrum. Using a classical least squares model in conjunction with reference spectra such as those from the Pacific Northwest National Laboratory (PNNL) gas-phase infrared database or simulated spectra derived from the HITRAN line-by-line database, the mixing ratio of each identified species is determined along with its associated estimation error. After correcting the wavelength and intensity of the field data, SpecQuant displays the calculated mixing ratio versus the experimental data for each analyte along with the residual spectrum with any or all analyte fits subtracted for visual inspection of the fit and residuals. The software performance for multianalyte quantification was demonstrated using moderate resolution (0.5 cm –1 ) infrared spectra that were collected during the time-resolved infrared photolysis of methyl iodide.
Thompson, Christopher J.↗