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NASA NTRS2013

Advanced Optical Diagnostics for Ice Crystal Cloud Measurements in the NASA Glenn Propulsion Systems Laboratory

A light extinction tomography technique has been developed to monitor ice water clouds upstream of a direct connected engine in the Propulsion Systems Laboratory (PSL) at NASA Glenn Research Center (GRC). The system consists of 60 laser diodes with sheet generating optics and 120 detectors mounted around a 36-inch diameter ring. The sources are pulsed sequentially while the detectors acquire line-of-sight extinction data for each laser pulse. Using computed tomography algorithms, the extinction data are analyzed to produce a plot of the relative water content in the measurement plane. To target the low-spatial-frequency nature of ice water clouds, unique tomography algorithms were developed using filtered back-projection methods and direct inversion methods that use Gaussian basis functions. With the availability of a priori knowledge of the mean droplet size and the total water content at some point in the measurement plane, the tomography system can provide near real-time in-situ quantitative full-field total water content data at a measurement plane approximately 5 feet upstream of the engine inlet. Results from ice crystal clouds in the PSL are presented. In addition to the optical tomography technique, laser sheet imaging has also been applied in the PSL to provide planar ice cloud uniformity and relative water content data during facility calibration before the tomography system was available and also as validation data for the tomography system. A comparison between the laser sheet system and light extinction tomography resulting data are also presented. Very good agreement of imaged intensity and water content is demonstrated for both techniques. Also, comparative studies between the two techniques show excellent agreement in calculation of bulk total water content averaged over the center of the pipe.

Bencic, Timothy J.↗

NASA NTRS2013

Direct Measurement of Dust Attenuation in z approx. 1.5 Star-Forming Galaxies from 3D-HST: Implications for Dust Geometry and Star Formation Rates

The nature of dust in distant galaxies is not well understood, and until recently few direct dust measurements have been possible. We investigate dust in distant star-forming galaxies using near-infrared grism spectra of the 3D-HST survey combined with archival multi-wavelength photometry. These data allow us to make a direct comparison between dust towards star-forming regions (measured using Balmer decrements) and the integrated dust properties (derived by comparing spectral energy distributions [SEDs] with stellar population and dust models) for a statistically significant sample of distant galaxies. We select a sample of 163 galaxies between 1.36< or = z< or = 1.5 with H(alpha) SNR > or = 5 and measure Balmer decrements from stacked spectra. First, we stack spectra in bins of integrated stellar dust attenuation, and find that there is extra dust extinction towards star-forming regions (AV,HII is 1.81 times the integrated AV, star), though slightly lower than found for low-redshift starburst galaxies. Next, we stack spectra in bins of specific star formation rate (log sSFR), star formation rate (log SFR), and stellar mass (logM∗). We find that on average AV,HII increases with SFR and mass, but decreases with increasing sSFR. The amount of extra extinction also decreases with increasing sSFR and decreasing stellar mass. Our results are consistent with the two-phase dust model - in which galaxies contain both a diffuse and a stellar birth cloud dust component - as the extra extinction will increase once older stars outside the star-forming regions become more dominant. Finally, using our Balmer decrements we derive dust-corrected H(alpha) SFRs, and find evidence that SED fitting produces incorrect SFRs if very rapidly declining SFHs are included in the explored parameter space. Subject headings: dust, extinction- galaxies: evolution- galaxies: high-redshift

Direct↗

NASA NTRS2011

TPSAS-NF1676L-13040-DND

We examine the feasibility of using airborne lidar data to: 1) infer CRC Convair-580 profiles of submicrometer fraction (SMF) over land (which is the fraction of aerosols with diameters less than 1 micrometer and is closely related to FMF) and 2) provide a proxy for CCN. If these initial Aerosol Extinction Aerosol Effective Radius feasibility studies prove successful, we will then apply these methodologies in subsequent studies to examine the feasibility of using CALIPSO data in a similar manner. We use data acquired by the NASA Langley Research Center airborne High Spectral Resolution Lidar (HSRL) during several recent field missions conducted by NASA, the Department of Energy, and NOAA. The airborne HSRL, which has acquired over 300 hours of data coincident with CALIPSO overpasses, measures aerosol extinction (532 nm), backscatter (532 and 1064 nm), and depolarization (532 and 1064 nm) profiles and thereby provides a dataset directly applicable to the CALIPSO measurements. During several of these field campaigns, airborne in situ measurements were acquired simultaneously within the HSRL “curtains” thereby facilitating direct correlations of the lidar observables to in situ measurements of particle size and composition, including SMF and CCN concentration. Previous studies have used simultaneous in situ measurements of SMF and Angström exponents derived from in situ scattering (Anderson et al., 2005) and remote sensing extinction (Redemann et al. 2009) measurements to build empirical relationships between these parameters. We adopt a similar approach and investigate relationships between the lidar observables, such as backscatter and extinction Angström exponents, with the coincident airborne in situ measurements of SMF and CCN concentration.

Richard Ferrare↗

NASA NTRSDate not supplied

TPSAS-NF1676L-23266-DND

Currently, near-surface air quality information (e.g. PM_2.5) must be inferred from column-integrated quantities (i.e. Aerosol Optical Thickness – AOT) obtained by passive remote sensing from downward-looking satellite instruments. Such retrievals must address the following questions: What do we use for the height of the aerosols? Mixed Layer (ML) height? Can we assume that near-surface aerosol extinction is about the same as the mean aerosol extinction in the ML? How well is near-surface extinction related to surface PM_2.5? How well can column AOT be used to infer near-surface aerosol extinction and PM_2.5?

Richard Ferrare↗

NASA NTRSDate not supplied

Distribution and Sources of Tropospheric Aerosols Over the Western North Atlantic During ACTIVATE (February-March 2020)

The Aerosol Cloud meTeorology Interactions oVer the western ATlantic Experiment (ACTIVATE) is a five-year (2019-2023) NASA Earth-Venture Suborbital-3 (EVS-3) mission to robustly characterize aerosol-cloud-meteorology interactions during February-June, with a focus on marine boundary layer clouds. This characterization requires understanding of aerosol composition, distribution, transport pathways, and sources. Here we use the GEOS-Chem chemical transport model driven by the MERRA-2 reanalysis to simulate tropospheric carbon monoxide (CO) and aerosols over the western North Atlantic Ocean (WNAO) during the first field deployment of ACTIVATE (February-March 2020). CO is used as a tracer to diagnose transport pathways for continental pollution outflow to the WNAO. The aerosol simulation represents all major aerosols including sulfate-nitrate-ammonium (SNA), mineral dust, sea salt, black and organic carbon aerosols. Model-simulated mixing ratios of SNA and organic carbon are compared with aircraft observations. We show that intensive aerosol mass measurements in the lower troposphere over the North American outflow region during ACTIVATE provide strong constraints on model aerosol wet scavenging. Comparisons of model aerosol extinctions with the airborne High Spectral Resolution Lidar-2 (HSRL-2) measurements indicate that the model generally captures continental outflow of aerosols and enhanced extinctions associated with sea salt. Simulated aerosol optical depths (AODs) and extinction vertical profiles are also compared with satellite retrievals from MODIS/Aqua and CALIOP/CALIPSO, respectively. CALIOP sometimes observes enhanced aerosol extinction at altitudes between ~1.5km and ~2.0km south of 32°N. The model reproduces this enhancement and attributes it to coarse-mode sea salt associated with high relative humidity. The relative contributions of continental and oceanic sources to the aerosol loading, AOD, and their distributions over the study domain will also be discussed.

aerosols↗

NASA NTRSDate not supplied

Effects of Ambient Inert Gas Properties on Cool-Flame Combustion of Normal-Alkane Droplets in Microgravity

Cool-flame-supported quasi-steady droplet combustion was first observed during droplet combustion experiments conducted onboard the International Space Station (ISS) in the Combustion Integrated Rack (CIR) with n-alkane fuels. These cool flames, not visible to the naked eye, result from the existence of the negative-temperature-coefficient (NTC) region during the combustion n-alkane fuels when the chemical-kinetic pathways experience a transition from the low-temperature chemistry to the normal, high-temperature-controlled chemistry. In this study, we present results for the cool-flame-supported droplet burning rates and extinction diameters for n-alkane fuels (n-heptane, n-octane, n-decane, and n-dodecane) in inert-diluent-substituted ambient environments. In these ISS experiments, some of the nitrogen in the ambient gas mixture is replaced by an inert gas, namely, carbon dioxide, helium, or xenon. Different diluents were observed to exert remarkably different influences on the cool-flame combustion of fuel droplets. The results show that the cool-flame extinction diameter is drastically increased with helium dilution compared to N2, CO2 or Xe, and Xe dilution leads to longer burning with a smaller extinction diameter. Unlike hot flames, the cool-flame burning rates are controlled by the cool-flame temperature established in the NTC region by the chemical kinetics, rather than by equilibrium thermodynamics, and the thermo-physical properties of the ambient gases, which control the heat feed back to the liquid droplet. The cool-flame extinction is triggered by the instability that occurs at the low-temperature end of the NTC region, below which cool diffusion flames become statically unstable. A quasi-steady theoretical model, presented earlier, which involves a six-step reduced-chemistry mechanism, valid around the lower end of the NTC region, is shown to explain the observed experimental trends qualitatively.

microgravity↗

NASA NTRS2021

Evidence for the predictability of changes in the stratosphericaerosol size following volcanic eruptions of diverse magnitudesusing space-based instruments

An analysis of multiwavelength stratospheric aerosol extinction coefficient data from the Stratospheric Aerosol and Gas Experiment II and III/ISS instruments is used to demonstrate a coherent relationship between the perturbation in extinction coefficient in an eruption’s main aerosol layer and the wavelength dependence of that perturbation. This relationship spans multiple orders of magnitude in the aerosol extinction coefficient of stratospheric impact of volcanic events. The relationship is measurement-based and does not rely on assumptions about the aerosol size distribution. We note limitations on this analysis including that the presence of significant amounts of ash in the main sulfuric acid aerosol layer and other factors may significantly modulate these results. Despite these limitations, the findings suggest an avenue for improving aerosol extinction coefficient measurements from single-channel observations such as the Optical Spectrograph and Infrared Imager System as they rely on a prior assumptions about particle size. They may also represent a distinct avenue for the comparison of observations with interactive aerosol models used in global climate models and Earth system models.

Larry W Thomason↗

NASA NTRSDate not supplied

Shortwave Broadband Irradiance Computations Using Cloud Properties Combined from CALIPSO, CloudSat, and MODIS

In this study, cloud properties measured from the CALIPSO, CloudSat, and MODIS (CCM) are used for top-of-atmosphere (TOA) shortwave (SW) broadband (BB) irradiance computations. The CALIPSO and CloudSat active sensors provide detailed cloud vertical profiles, but these occasionally miss parts of the cloud columns due to the full attenuation of sensor signals, surface clutter, or insensitivity to a certain range of cloud particle sizes. As a result, the CCM-merged cloud extinction coefficient profiles can be underestimated. Therefore, we compare the column-integrated visible scaled cloud optical depth (VSCOD) of the CCM-merged cloud extinction coefficient profile with the MODIS-estimated VSCOD and apply a scaling factor to the CCM-merged cloud extinction profile. The VSCOD is defined as a visible cloud optical depth multiplied by (1¬–asymmetry parameter). The SW irradiances are computed using the scaled CCM-merged cloud extinction coefficient and effective radius profiles. It is shown that the multi-sensor-combined cloud profiles significantly reduce positive TOA SW BB biases, compared to those with MODIS-derived cloud properties only. The improvement is more pronounced for optically thick clouds, where MODIS ice particle effective radius is largely underestimated.

Cloud↗

NASA NTRSDate not supplied

Evaluation of GEOS Aerosols Using CAMP2Ex Observations

Biomass burning aerosol impacts aspects of the atmosphere and Earth system through direct and semi-direct effects, as well as influencing air quality. Despite its importance, the representation of biomass burning aerosol is not always accurate in numerical weather prediction and climate models or reanalysis products. Using observations collected as part of the Cloud, Aerosol and Monsoon Processes Philippines Experiment (CAMP2Ex) in August through October of 2019, aerosol concentration and optical properties are evaluated within the Goddard Earth Observing System (GEOS) and its underlying aerosol module, GOCART. In the operational configuration, GEOS assimilates aerosol optical depth observations at 550 nm from AERONET and MODIS to constrain aerosol fields. Particularly for biomass burning aerosol, without the assimilation of aerosol optical depth, aerosol extinction is underestimated compared to observations collected in the Philippines region during the CAMP2Ex campaign. The assimilation process adds excessive amounts of carbon to account for the underestimated extinction, resulting in positive biases in the mass of black and organic carbon, especially within the boundary layer, relative to in situ observations from the Langley Aerosol Research Group Experiment. Counteracting this, GEOS is deficient in sulfate and nitrate aerosol just above the boundary layer. Aerosol extinction within GEOS is a function of the mass of different aerosol species, the ambient relative humidity, the assumed spectral optical properties, and particle size distribution per species. The relationship between dry and ambient extinction in GEOS reveals that hygroscopic growth is too high within the model for biomass burning aerosol. An additional concern lies in the assumed particle size distribution for GEOS, which has a single mode radius that is too small for organic carbon. Variability in the observed particle size distribution for biomass burning aerosol within a single flight also illuminates the fact that a single assumed particle size distribution is not sufficient and that for a proper representation, a more advanced aerosol module within GEOS may be necessary.

Allison Collow↗

NASA NTRS2024

CREST: a Climate Data Record of Stratospheric Aerosols

Climate-related studies need information about the distribution of stratospheric aerosols, which influence the energy balance of the Earth’s atmosphere. In this work, we present a merged dataset of vertically resolved stratospheric aerosol extinction coefficients, which is derived using data from six limb and occultation satellite instruments: SAGE (Stratospheric Aerosol and Gas Experiment) II on ERBS (Earth Radiation Budget Satellite), GOMOS (Global Ozone Monitoring by Occultation of Stars) and SCIAMACHY (Scanning Imaging Spectrometer for Atmospheric Chartography) on Envisat, OSIRIS (Optical Spectrograph and InfraRed Imaging System) on Odin, OMPS (Ozone Monitor Profiling Suite Limb Profiler) on Suomi NPP, and SAGE III on the ISS (International Space Station). The merging of aerosol profiles is performed via the transformation of the aerosol datasets from individual satellite instruments to the same wavelength (750 nm) and their de-biasing and homogenization by adjusting the seasonal cycles. After such homogenization, the data from individual satellite instruments are in good agreement. The merged aerosol extinction coefficient is computed as the median of the adjusted data from the individual instruments. The merged time series of vertically resolved monthly mean aerosol extinction coefficients at 750 nm is provided in 10° latitudinal bins from 90° S to 90° N, in the altitude range from 8.5 to 39.5 km. The time series of the stratospheric aerosol optical depth (SAOD) is created via the integration of aerosol extinction profiles from the tropopause to 39.5 km; it is also provided as monthly mean data in 10° latitudinal bins. The created aerosol climate record covers the period from October 1984 until December 2023, and it is intended to be extended in the future. The merged CREST aerosol dataset (v2) is available at https://doi.org/10.57707/fmib2share.dfe14351fd8548bcaca3c2956b17f665 (Sofieva et al., 2024a). It can be used in various climate-related studies.

Viktoria F Sofieva↗

DOE OSTI2025

Megahertz Rate Optical Diagnostics of Explosively Generated Soot

Detonation of a solid explosive produces a turbulent and luminous post‐detonation fireball containing condensed carbon soot. Diagnostics of soot dynamics are needed for model validation and to interpret emission signals. Diffuse back‐illumination extinction imaging (DBI‐EI) and laser‐induced incandescence (LII) are two common optical diagnostics for flame soot. This work extends both to measure time‐resolved soot dynamics from a 12 mm HMX hemisphere. DBI‐EI measured line‐of‐sight optical extinction exceeds 99% in some regions. Results are tomographically inverted to obtain a signal proportional to the soot volume fraction. Pulse‐burst LII measures are presented at 1 MHz. For the first time, LII results are combined with DBI‐EI extinction measurements to quantify and correct for signal trapping. Following this, spatially and temporally resolved DBI‐EI and LII measures are shown to be in reasonable agreement. Finally, experimental results are compared against recently developed simulations. Quantitative differences in the soot mixing dynamics are resolved. These findings motivate future model improvements and demonstrate ongoing needs for diagnostic advancements for heavily sooting environments.

diffuse back-illumination extinction imaging↗

DOE OSTI2022

Aerosols consistently suppress the convective boundary layer development

Aerosols with different vertical distribution and various optical properties induce diverse heating rates and thereby affecting convective boundary layer (CBL) development. Our results showed consistent CBL-suppression of aerosols during daytime with numerical experiments, in which aerosols were specified at different heights with synthesized single scattering albedo from 64 studies and asymmetry factor from 20 studies globally. Absorbing aerosols concentrated below but close to the CBL top had the strongest suppression effect on CBL development relative to that concentrated near surface or above CBL. Aerosol cooling effect by attenuating incident solar radiation and surface heat flux exceeded its warming effect by reheating the atmosphere layer with absorbed shortwave radiation, and eventually declined net heating rate, which inhibited CBL development, lowered mixed-layer potential temperature and stabilized atmospheric stratification. Stove effect of absorbing aerosols (CBL enhancement) under a zero background aerosol extinction coefficient is negligible for dominant dome effect (CBL suppression) which consistently suppresses CBL development regardless of aerosol vertical height and background aerosol extinction coefficient. Our study also highlighted the importance of specifying background aerosol extinction coefficient in numerical experiments for accurate assessment of aerosol radiative forcing and CBL-aerosol interactions.

54 ENVIRONMENTAL SCIENCES↗

DOE OSTI2022

The 2175 Å bump features in FeLoBAL quasars: One indicator of MW-like dust in the nuclear region of quasars

To investigate the properties of dust in the nuclear region of quasars, we explored the extinction curves of the iron low-ionisation broad absorption line (FeLoBAL) quasar SDSS J163004.29+311957.6 and its two analogues. The parametrised extinction curves indicated the Milky Way-like 2175 Å bump features in underlying extinction, which are similar to those seen in the Local Group and in a subset of high-redshift star-forming galaxies. Compared to the bump features in the Large Magellanic Cloud (LMC), the detections in this work are much closer to those in the Milky Way (MW). These bump features, as well as those in the high- and low-ionisation broad absorption line (BAL) quasars with 2175 Å bumps, are probably the counterpart of the 2175 Å bump features in the quasar environment. This type of dust grain is generally small, easily disrupted by high-energy photons, and has difficulty surviving in the radiation field of the active galactic nucleus. However, due to the presence of absorption-line outflows, the 2175 Å bump feature in quasars, which should be rare, is seen many times in BAL quasars. The shielding effect of outflow clouds allows the MW-like dust grains to be assembled or extends the survival period in the quasar nuclear region. The process and physical and chemical conditions deserve further observational study and investigation.

79 ASTRONOMY AND ASTROPHYSICS↗

DOE OSTI2023

A sample of dust attenuation laws for Dark Energy Survey supernova host galaxies

Type Ia supernovae (SNe Ia) are useful distance indicators in cosmology, provided their luminosity is standardized by applying empirical corrections based on light-curve properties. One factor behind these corrections is dust extinction, which is accounted for in the color–luminosity relation of the standardization. This relation is usually assumed to be universal, which can potentially introduce systematics into the standardization. The “mass step” observed for SN Ia Hubble residuals has been suggested as one such systematic. We seek to obtain a more complete view of dust attenuation properties for a sample of 162 SN Ia host galaxies and to probe their link to the mass step. We inferred attenuation laws toward hosts from both global and local (4 kpc) Dark Energy Survey photometry and composite stellar population model fits. We recovered a relation between the optical depth and the attenuation slope, best explained by differing star-to-dust geometry for different galaxy orientations, which is significantly different from the optical depth and extinction slope relation observed directly for SNe. We obtain a large variation of attenuation slopes and confirm these change with host properties, such as the stellar mass and age, meaning a universal SN Ia correction should ideally not be assumed. Analyzing the cosmological standardization, we find evidence for a mass step and a two-dimensional “dust step”, both more pronounced for red SNe. Although comparable, the two steps are not found to be completely analogous. We conclude that host galaxy dust data cannot fully account for the mass step, using either an alternative SN standardization with extinction proxied by host attenuation or a dust-step approach.

79 ASTRONOMY AND ASTROPHYSICS↗

DOE OSTI2024

Modelling the impact of host galaxy dust on type Ia supernova distance measurements

Type Ia Supernovae (SNe Ia) are a critical tool in measuring the accelerating expansion of the universe. Recent efforts to improve these standard candles have focused on incorporating the effects of dust on distance measurements with SNe Ia. In this paper, we use the state-of-the-art Dark Energy Survey 5 year sample to evaluate two different families of dust models: empirical extinction models derived from SNe Ia data and physical attenuation models from the spectra of galaxies. In this work, we use realistic simulations of SNe Ia to forward-model different models of dust and compare summary statistics in order to test different assumptions and impacts on SNe Ia data. Among the SNe Ia-derived models, we find that a logistic function of the total-to-selective extinction R V best recreates the correlations between supernova distance measurements and host galaxy properties, though an additional 0.02 mag of grey scatter is needed to fully explain the scatter in SNIa brightness in all cases. These empirically derived extinction distributions are highly incompatible with the physical attenuation models from galactic spectral measurements. From these results, we conclude that SNe Ia must either preferentially select extreme ends of galactic dust distributions, or that the characterization of dust along the SNe Ia line-of-sight is incompatible with that of galactic dust distributions.

79 ASTRONOMY AND ASTROPHYSICS↗

DOE OSTI2026

Integration of ultra-low coverage whole-genome sequences for reconstructing the evolutionary history of Galapagos giant tortoises

Genomic data from contemporary and historical samples often need to be coupled for evolutionary reconstructions of multitaxon complexes. However, the genetic data recovered from historical samples may result only in ultra-low coverage whole-genome sequences (ulcWGS; <0.15× depth), leading to inaccurate evolutionary inferences given a preponderance of missing data. Using the Galapagos giant tortoise radiation as a study system (Chelonoidis spp., composed of 13 extant and four extinct lineages), we assembled a novel methodological pipeline that removes potential noise introduced by the missing data and enhances the evolutionary signal from ulcWGS samples. We leveraged existing tools for phylogenomic placement (EPA-ng), population genomic structure (smartsnp) and admixture (Admixfrog, NGSadmix) to demonstrate that the evolutionary history of samples can be uncovered with sequencing depths as low as 0.008–0.139×. Importantly, these approaches do not use genotype imputation of the ulcWGS samples, which would require extensive reference datasets. Our application to two cases of extinct lineages of Galapagos giant tortoises, with and without references from the same lineage, demonstrates the general value of the approach. We confirm where the extinct lineages from San Cristóbal and Santa Fe islands fit into the Galapagos giant tortoise radiation, and that these lineages were evolutionarily distinct entities.

ancient DNA↗

DOE OSTI2026

Flame dynamics and kinetic coupling of ammonia and dimethyl-ether in non-premixed cool and warm flames at elevated pressure

Developing advanced low-temperature combustion engines with ammonia-biofuel blends requires a comprehensive understanding of low-temperature flame dynamics and kinetic interactions between ammonia and oxygenated fuels at elevated pressures. This work aims to study the dynamics and kinetics of non-premixed Dimethyl Ether (DME)/Ammonia (NH 3 ) cool and warm flames, and their reignition to hot flames. A counterflow burner is employed to establish DME/NH 3 cool/warm flames at pressures up to 5 atm. The extinction limits of cool flame and the reignition limits of warm flame to hot flame are measured by varying NH 3 concentrations and compared to simulations to quantitatively examine the effects on DME/NH 3 flames. It is found that NH 3 inhibits low-temperature DME oxidation and results in lower cool flame extinction limits. Warm flames in the presence of NH 3 are observed for the first time, revealing a non-monotonic effect of NH 3 addition: a small amount of NH 3 presence enhances warm flame chemistry and promotes reignition to hot flames, while a high NH 3 concentration weakens the warm flame. This trend is further explained by 0-D PSR kinetic simulations and 1-D S-curve flame dynamic calculations. Three flame transition regimes between cool flames (CF), warm flames (WF), and hot flames (HF) by different levels of NH 3 additions at a specific strain rate are identified, namely WFHF reignition, WF-CF transition, and WF extinction. Reaction sensitivity analyses of OH at low temperatures show that NH3 inhibits DME oxidation through OH consumption via H-abstraction and the kinetic couplings of RO 2 /NH 2 , RO 2 /NO x , R/NO x , and O 2 QOOH/NO x further suppress the low-temperature branching. At intermediate-temperatures, NH 2 /NO x /HO 2 coupling promotes warm flames via the pathway NH 2 → H 2 NO → HNO → NO by converting O 2 → HO 2 → OH. At even higher NH₃ concentrations, radical termination reactions of NH 2 + NO/NO 2 and excessive OH consumption via H-abstraction inhibit the flame. The insights into the kinetic coupling between NH 3 and low-temperature chemistry at elevated pressure and its impact on the dynamics of cool-warm-hot flame transitions will contribute to advancing combustion technologies with reduced emissions and improved energy-efficiency.

42 ENGINEERING↗

DOE OSTI2021

Carbonyl Identification and Quantification Uncertainties for Oxidative Polymer Degradation

The most revealing indicator for oxidative processes or state of degraded plastics is usually carbonyl formation, a key step in materials degradation as part of the carbon cycle for man-made materials. Hence, the identification and quantification of carbonyl species with infrared spectroscopy have been the method of choice for generations, thanks to their strong absorbance and being an essential intermediate in carbon oxidation pathways. Despite their importance, precise identification and quantification can be challenging and rigorous fully traceable data are surprisingly rare in the existing literature. An overview of the complexity of carbonyl quantification is presented by the screening of reference compounds in solution with transmission and polymer films with ATR IR spectroscopy, and systematic data analyses. Significant variances in existing data and their past use have been recognized. Guidance is offered how better measurements and data reporting could be accomplished. Experimental variances depend on the combination of uncertainty in exact carbonyl species, extinction coefficient, contributions from neighboring convoluting peaks, matrix interaction phenomena and instrumental variations in primary IR spectral acquisition (refractive index and penetration depth for ATR measurements). In addition, diverging sources for relevant extinction coefficients may exist, based on original spectral acquisition. For common polymer degradation challenges, a relative comparison of carbonyl yields for a material is easily accessible, but quantification for other purposes, such as degradation rates and spatially dependent interpretation, requires thorough experimental validation. All variables featured in this overview demonstrate the significant error margins in carbonyl quantification, with exact carbonyl species and extinction coefficients already being major contributors on their own.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗