Assessing TEMPO Level 2 NO2 and HCHO Products with Airborne Spectrometer Data
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Laura Judd↗
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Kinetics and Thermochemistry of the Br((sup 2)P3/2) + NO2 Association Reaction
A laser flash photolysis-resonance fluorescence technique has been employed to study the kinetics of the Br((sup 2)P3/2) + NO2 association reaction as a function of temperature (259-432 K) pressure (12.5 - 700 Torr), and buffer gas identity (He, Ar, H2, N2, CO2, CF4, SF6). The reaction is found to be in the falloff regime between third and second order over the entire range of conditions investigated. At temperatures below 350 K, the association reaction is found to be irreversible on the time scale of the experiment (approximately 30 ms). At higher temperatures reversible addition is observed, allowing equilibrium constants for BrNO2 formation and dissociation to be determined. Second- and third-law analyses of the equilibrium data are in only fair agreement and lead to the following thermochemical parameters for the association reaction: Delta-H(298) = 19.6 +/- 1.7 kcal/mol, Delta-H(0) = -18.6 +/- 2.0 kcal/mol, Delta-S(298) = 29.3 +/- 4.2 cal/mol/K, Delta-H(sub f)(sub 298)(BrNO2) = 17.0 +/-1.8 kcal/mol(uncertainties are 2 sigma estimates of absolute accuracy). The value for Delta-H(0) determined in this study has been employed to calculate k(sub 0)(sup SC), the low-pressure third-order rate coefficient in the strong collision limit, by using the method of Troe; calculated values of k(sub 0)(sup SC) are inconsistent with experimental results unless Delta-H(0) is assigned a value near the lower limit derived from analysis of the high-temperature approach to equilibrium data, i.e. delta-H(0) approximately equals -16.6 kcal/mol. A potential source of systematic error in the calculation of both k(sub 0)(sup SC) and the absolute entropy of BrNO2 results from the complete lack of knowledge of the energies and degeneracies of the electronic states of BrNO3. The procedure developed by Troe and co-workers has been employed to extrapolate experimental falloff curves to the low- and high-pressure limits. Derived values for k(sub 0)(M,298K) in units of 10(exp -31) cm(exp 6)/sq molecule/s range from 2.75 for M = He to 6.54 for M = CO2; 2 sigma uncertainties are estimated to be +/- 20%. Values for k(sub 0)(N2,T) in units of 10(exp -31) cm(exp 6)/sq molecule/s are 5.73 at 259 K, 4.61 at 298 K, and 3.21 at 346 K; the observed temperature dependence for k(sub 0)(N2,T) is consistent with the theoretical temperature dependence for Beta(sub c)k(sub 0)(sup SC). Values for k(sub infinity)(T) in units of 10(exp -11) cu cm/molecule/s are 2.86 at 259 K, 3.22 at 298 K, and 3.73 at 346 K; 2 sigma uncertainties are estimated to be a factor of 2. Approximate falloff parameters in a convenient format for atmospheric modeling are also derived.
Kreutter, K. D.↗
The rate coefficient for the reaction NO2 + NO3 yielding NO + NO2 + O2 from 273 to 313 K
The ratio of rate constants for the reaction NO3 + NO yielding 2 NO2 (k3) and the reaction NO2 + NO3 yielding NO + NO2 + O2 (k4) were determined by measuring of NO and NO2 concentrations of NO and NO2 in an N2O5/NO2/N2 mixture over the temperature range 273-313 K. The measured ratio was found to be expressed by the equation k3/k4 = 387 exp(-1375/T). The results are consistent with those of Hammer et al. (1986).
Cantrell, Chris A.↗
Peroxy radical measurements with NCAR's chemical amplifier
The present NCAR instrument for HO2/RO2 measurements has been described previously. It is based on the reactions involving HO2, RO2, and HO radicals with CO and NO. Since (HO2) + (RO2) + (HO) is much greater than (HO) for most atmospheres, it is useful as a peroxy radical detector. Operation of the instrument depends on the creation of a chemical chain reaction which is initiated as HO2 and RO2 radicals in ambient air encounter added NO gas; this forms an NO2 molecule and an HO or RO radical: HO2(RO2) + NO yields HO(RO) + NO2. RO radicals react relatively efficiently with O2 to form an HO2 radical, and subsequently an HO-radical, by reaction with NO. CO gas added to the reaction chamber during part of the operating cycle, recycles the HO to HO2; HO + CO (+O2) yields HO2 + CO2. The reaction sequence may form several hundred NO2 molecules per HO2 (RO2) originally present, before chain termination occurs. The added CO is replaced by N2 addition periodically so that the chain reaction is suppressed, and a 'blank' signal resulting from NO2, O3 and possibly other NO2-forming species (non-chain processes) in ambient air is recorded. The difference between the signal with and without CO is proportional to the peroxy radical concentration. The NO2 produced is monitored using a sensitive luminol chemiluminescence detector system. In the NCAR instrument the length of the amplification chain is determined using a stable source of HO2 radicals (H2O2 thermal decomposition); the ratio of the signal seen with CO present to that with N2 present gives the sensitivity of the instrument to HO2 (molecules of NO2 formed/peroxy radical). The instrument is automated to carry out in hourly repeated cycles: (1) chain length determination; (2) NO2 calibration; and (3) linearity check on the response of signals. One minute averages of signals are normally recorded. The sensitivity of the instrument to detect peroxy radicals is in the pptv range. The present instrument has operated continuously (24 hr/day) in the field studies which extended over a period of several weeks. The major advantages of this instrument are as follows: (1) its relative simplicity; (2) low power requirements; and (3) its rapid response to all types of peroxy radicals--HO2, CH3O2 and the higher alkyl and acyl peroxy radicals; however not all RO2 species generate HO2 radicals with perfect efficiency and hence have somewhat lower response/molecule than HO2 radicals.
Cantrell, Christopher↗
Photo-sensitized ignition of hydrogen/oxygen mixtures for hypersonic flight vehicles
An approach toward improving supersonic ignition and combustion efficiency was investigated under a feasibility program with NASA-Ames. The idea is to selectively irradiate targetted species in the combustion zone. The ensuing photodissociation reactions produce highly reactive radicals which modify the gas phase kinetics. The overall objective of this research was to demonstrate photosensitized ignition of H2/O2 mixtures, and to gain a preliminary understanding of the ignition mechanism, especially as it pertains to the concept of supersonic combustion. To this end, a series of experiments were performed with a model sensitizer, NO2. At subatmospheric pressures and moderate temperatures (above 100 F), mixtures of H2/O2/NO2 are ignitable by a pulsed eximer laser at 308 nm, 115 to 200 mJ. Ignitability was found to be a function of NO2 pressure, temperature, laser energy per pulse, and laser lens focal length (fluence at focal volume). Mixtures could not be ignited in the absence of the sensitizer. While increasing temperature improved sensitized ignition in the lower temperature range, a retarding effect was observed at the highest temperatures. To more thoroughly understand these thermal effects, the UV-Vis and IR spectra of NO2 and H2/O2/NO2 mixtures were studied over the temperature range 70 to 900 F. Initially, increasing temperature shifts the N2O4 in a reversible reaction to 2 NO2 equilibrium toward NO2, favoring photochemical ignition. However, at still higher temperature, NO2 converts to non-absorbing NO + 1/2 O2, thus preventing photosensitized ignition.
Lavid, Moshe↗
Analysis of the physical state of one Arctic polar stratospheric cloud based on observations
During the Arctic Airborne Stratospheric Expedition (AASE) simultaneous measurements of aerosol size distribution and NO(y)(HN03 + NO + NO2 + 2(N205)) were made along ER-2 flight paths. The flow characteristics of the NO(y) instrument allow us to derive the condensed NO(y) amount (assumed to be HN03) present during polar stratospheric cloud (PSC) events. Analysis of the January 24th flight indicates that this condensed HN03 amount does not agree well with the aerosol volume if the observed PSCs are composed of solid nitric acid trihydrate (NAT), as is generally assumed. However, the composition agrees well with that predicted for liquid H2S04/HN03/H20 solution droplets using a new Aerosol Physical Chemistry Model (APCM). The agreement corresponds in detail to variations in temperature and humidity. The weight percentages of H2SO4, HN03, and H2O derived from the measurements all correspond to those predicted for ternary, liquid solutions.
Drdla, K.↗
Lithium Dinitramide as an Additive in Lithium Power Cells
Lithium dinitramide, LiN(NO2)2 has shown promise as an additive to nonaqueous electrolytes in rechargeable and non-rechargeable lithium-ion-based electrochemical power cells. Such non-aqueous electrolytes consist of lithium salts dissolved in mixtures of organic ethers, esters, carbonates, or acetals. The benefits of adding lithium dinitramide (which is also a lithium salt) include lower irreversible loss of capacity on the first charge/discharge cycle, higher cycle life, lower self-discharge, greater flexibility in selection of electrolyte solvents, and greater charge capacity. The need for a suitable electrolyte additive arises as follows: The metallic lithium in the anode of a lithium-ion-based power cell is so highly reactive that in addition to the desired main electrochemical reaction, it engages in side reactions that cause formation of resistive films and dendrites, which degrade performance as quantified in terms of charge capacity, cycle life, shelf life, first-cycle irreversible capacity loss, specific power, and specific energy. The incidence of side reactions can be reduced through the formation of a solid-electrolyte interface (SEI) a thin film that prevents direct contact between the lithium anode material and the electrolyte. Ideally, an SEI should chemically protect the anode and the electrolyte from each other while exhibiting high conductivity for lithium ions and little or no conductivity for electrons. A suitable additive can act as an SEI promoter. Heretofore, most SEI promotion was thought to derive from organic molecules in electrolyte solutions. In contrast, lithium dinitramide is inorganic. Dinitramide compounds are known as oxidizers in rocket-fuel chemistry and until now, were not known as SEI promoters in battery chemistry. Although the exact reason for the improvement afforded by the addition of lithium dinitramide is not clear, it has been hypothesized that lithium dinitramide competes with other electrolyte constituents to react with lithium on the surface of the anode to form a beneficial SEI. Apparently, nitrides and oxides that result from reduction of lithium dinitramide on the anode produce a thin, robust SEI different from the SEIs formed from organic SEI promoters. The SEI formed from lithium dinitramide is more electronically insulating than is the film formed in the presence of an otherwise identical electrolyte that does not include lithium dinitramide. SEI promotion with lithium dinitramide is useful in batteries with metallic lithium and lithium alloy anodes.
Gorkovenko, Alexander A.↗
Highlights from 40 Years of Satellite UV Measurements
This year we are celebrating the 40th anniversary of the launch of the Backscatter Ultraviolet (BUV) instrument on NASA's Nimbus-4 satellite. The purpose of this instrument was to demonstrate the capability to measure total column ozone and its vertical distribution from space. The success of this instrument led to about a dozen instruments of this type on various NASA and NOAA satellites. These instruments used a single photomultiplier tube (PMT) that restricted the measurements to 6-12 discrete wavelengths in the 250-380 nm range. With the availability of solid-state detector arrays in the past decade it has been possible to make similar measurements but with hyperspectral (contiguous in wavelength) sampling and enhanced spectral resolution. This has allowed global mapping of several weakly-absorbing trace gases including S0 2, NO2, BrO, HCHO, and CIIOCHO. Since these measurements are affected by clouds and aerosols, a great deal of effort has gone into understanding their effect on ultraviolet radiation- both upwelling and downwelling. The downwelling UV radiation is chemically and biologically active and has both negative (genetic damage, air pollution) and positive (production of vitamin D and OH radical) environmental effects. I will discuss how the interaction of Rayleigh-scattered UV radiation with clouds and aerosols produce a variety of interesting effects that are leading to new methods of remote sensing of their properties. The UV measurements can greatly enhance the information that one derives from more traditional methods that use infrared and visible part of the solar spectrum.
Bhartia, Pawan K.↗
Planetary Aeronomy: NO2 In the Martian Atmosphere - 2
The transmission curve of the Martian atmosphere derived by Opik is compared with transmission curves of an atmosphere containing various amounts of nitrogen dioxide. It is found that the amount of 6 x l0(exp 18) sq cm column NO2 (or even less) given by Sinton as an upper limit for the Martian NO2 content could adequately explain the phenomenon of the blue haze. This finding made it worthwhile to investigate the effect of the temperature and pressure sensitive equilibrium 2 NO2 reversibly yields N204 upon the total NO2 content and the altitude-number density distributions of NO2 and N204. Computations were carried out for surface temperatures of 273 K, 243 K, 213 K, and 183 K and for three different temperature distributions. The discussion of the results leads to the suggestion of several important new experiments.
Warneck, P.↗
Reference NO2 calibration system for ground-based intercomparisons during NASA's GTE/CITE 2 mission
An NO2 calibration system, based on a permeation device and a two-stage dynamic dilution system, was designed, constructed, and characterized at the National Bureau of Standards. In this system, calibrant flow entering the second stage was controlled without contacting a metal flow controller, and permeation oven temperature and flow were continuously maintained, even during transport. The system performance and the permeation emission rate were characterized by extensive laboratory tests. This system was capable of accurately delivering known NO2 concentrations in the ppbv and sub-ppbv concentration range with a total uncertainty of approximately 10 percent. The calibration system was placed on board NASA research aircraft at both the Wallops Island and Ames research facilities. There it was employed as the reference standard in NASA's Global Tropospheric Experiment/Chemical Instrumental Test and Evaluation 2 mission in August 1986.
Fried, Alan↗
Substitution Effects and Linear Free Energy Relationships During Reduction of 4- Benzoyl-n-(4-substituted Benzyl)pyridinium Cations
In analogy to 4-(para-substituted benzoyl)-N-methylpyridinium cations (1-X's), the title species (2-X's, -X = -OCH3, -CH3, -H, -Br, -COCH3, -NO2) undergo two reversible, well-separated (E(sub 1/2) greater than or equal to 650 mV) one-electron reductions. The effect of substitution on the reduction potentials of 2-X's is much weaker than the effect of the same substituents on 1-X's: the Hammett rho-values are 0.80 and 0.93 for the 1st- and 2nd-e reduction of 2-X's vs. 2.3 and 3.3 for the same reductions of 1-X's, respectively. Importantly, the nitro group of 2-NO2 undergoes reduction before the 2nd-e reduction of the 4-benzoylpyridinium system. These results suggest that the redox potentials of the 4-benzoylpyridinium system can be course-tuned via p-benzoyl substitution and fine-tuned via para-benzyl substitution. Introducing the recently derived substituent constant of the -NO2(sup)- group (sigma para-NO2(sup)- = -0.97) yields an excellent correlation for the 3rd-e reduction of 2- NO2 (corresponding to the reduction of the carbonyl group) with the 2nd-e reduction of the other 2-X's, and confirms the electron donating properties of -NO2(sup)-.
Leventis, Nicholas↗
Application of OMI Observations to a Space-Based Indicator of NOx and VOC Controls on Surface Ozone Formation
We investigated variations in the relative sensitivity of surface ozone formation in summer to precursor species concentrations of volatile organic compounds (VOCs) and nitrogen oxides (NOx) as inferred from the ratio of the tropospheric columns of formaldehyde to nitrogen dioxide (the "Ratio") from the Aura Ozone Monitoring Instrument (OMI). Our modeling study suggests that ozone formation decreases with reductions in VOCs at Ratios less than 1 and NOx at Ratios greater than 2; both NOx and VOC reductions may decrease ozone formation for Ratios between 1 and 2. Using this criteria. the OMI data indicate that ozone formation became: 1. more sensitive to NOx over most of the United States from 2005 to 2007 because of the substantial decrease in NOx emissions, primarily from stationary sources, and the concomitant decrease in the tropospheric column of NO2. and 2. more sensitive to NOx with increasing temperature, in part because emissions of highly reactive, biogenic isoprene increase with temperature, thus increasing the total VOC reactivity. In cities with relatively low isoprene emissions (e.g .. Chicago). the data clearly indicate that ozone formation became more sensitive to NOx from 2005 to 2007. In cities with relatively high isoprene emissions (e.g ., Atlanta), we found that the increase in the Ratio due to decreasing NOx emissions was not obvious as this signal was convolved with variations in the Ratio associated with the temperature dependence of isoprene emissions and, consequently, the formaldehyde concentration.
Duncan, Bryan N.↗
Updated assessment of TROPOMI NO2 and HCHO columns using airborne spectrometers during the MOOSE and TRACER-AQ field campaigns
Airborne spectrometer data offers the opportunity to evaluate satellite product performance without the impact of subpixel heterogeneity between the different satellite and ground-based measurement footprints. Previous measurements during the Long Island Sound Tropospheric Ozone Study were used to evaluate TROPOMI’s v1.3 NO2 product and found very strong relationships (r2=0.96) between the airborne spectrometer and TROPOMI with a systematic low bias mostly attributed to the coarse a priori profile assumption within the standard TROPOMI retrieval. This presentation will update that analysis using the most up-to-date version 2 TROPOMI NO2 product as well as expand analysis to the HCHO product. In summer 2021, NASA GeoCAPE Airborne Simulator (GCAS) collected measurements over southeast Michigan/western Ontario for the Michigan-Ontario Ozone Source Experiment (MOOSE) and Houston, Texas during the TRacking Aerosol Convection ExpeRiment – Air Quality (TRACER-AQ). Flight strategies for both deployments included repeated systematic sampling over common areas of interest coinciding with TROPOMI. During these flights, GCAS NO2 tropospheric columns are available at 250 m x 560 m resolution. Preliminary evaluation of GCAS NO2 retrievals with Pandora spectrometer data in Houston, Texas (3 sites) shows a median percent difference of 1.4% with an interquartile range of -15.5-14.9% (r2=0.72). Column HCHO was also retrieved at a slightly coarser resolution in Houston, Texas (750 m x 1680 m) showing distinct spatial patterns associated with secondary production through the oxidation of VOCs downwind of industrial facilities. Comparison to Pandora HCHO showed a low bias of ~25% (r2=0.29) with further investigation needed to identify the cause for this bias. This presentation will share how the GCAS/Pandora/TROPOMI NO2 and HCHO intercompare and will also extend analysis toward thinking about how these assets will contribute to the validation of future geostationary observations.
Laura Judd↗
Ammonia on the prebiotic Earth: Iron(II) reduction of nitrite
Theories for the origin of life require the availability of reduced nitrogen. In the non-reducing atmosphere suggested by geochemical evidence, production in the atmosphere and survival of NH3 against photochemical destruction are problematic. Electric discharges and impact shocks would produce NO rather than HCN or NH3. Conversion of NO to nitrous and nitric acid (by way of HNO) and precipitation in acid rain would provide a source of fixed nitrogen to the early ocean. One solution to the NH3 problem may have been the reduction of nitrite/nitrate in the ocean with aqueous ferrous iron, Fe(2+): 6Fe(+2) + 7 H2O + NO2(-) yields 3Fe2O3 + 11 H(+) + NH3. We have measured the kinetics of this reaction as a function of temperature, pH, and concentrations of salts, Fe(+2), and NO2(-). Cations (Na(+), Mg(2+), K(+)) and anions (Cl(-), Br(-), SO4(2-)) increase the rate by factors of 4 to 8. Although a competing pathway yields N2, the efficiency of the conversion of nitrite to ammonia ranges from 25% to 85%. Nitrate reduction was not consistently reproducible; however, when it was observed, its rate was slower by at least 8X than that of nitrite reduction. If the prebiotic atmosphere contained 0.2 to 10 atmospheres CO2 as suggested by Walker (1985), the Fe(+2) concentration and the rate would have been limited by siderite (FeCO3) solubility.
Summers, David P.↗
A study for hypergolic vapor sensor development
In summary, the following tasks were completed within the scope of this work: (1) a portable Monomethylhydrazine analyzer was developed, designed, fabricated and tested. (2) A portable NO2 analyzer was developed, designed, fabricated and tested. (3) Sampling probes and accessories were designed and fabricated for this instrumentation. (4) Improvements and modifications were made to the model 7630 Ecolyzer in preparation for field testing. (5) Instrument calibration procedures and hydrazine handling techniques necessary to the successful application of this hardware were developed.
Stetter, J. R.↗
Particulate emissions from a mid-latitude prescribed chaparral fire
Particulate emission from a 400-acre prescribed chaparral fire in the San Dimas Experimental Forest was investigated by collecting smoke aerosol on Teflon and glass-fiber filters from a helicopter, and using SEM and EDAX to study the features of the particles. Aerosol particles ranged in size from about 0.1 to 100 microns, with carbon, oxygen, magnesium, aluminum, silicon, calcium, and iron as the primary elements. The results of ion chromatographic analysis of aerosol-particle extracts (in water-methanol) revealed the presence of significant levels of NO2(-), NO3(-), SO4(2-), Cl(-), PO4(3-), C2O4(2-), Na(+), NH4(+), and K(+). The soluble ionic portion of the aerosol was estimated to be about 2 percent by weight.
Cofer, Wesley R., III↗
Nitrification in a zeoponic substrate
Clinoptilolite is a zeolite mineral with high cation exchange capacity used in zeoponic substrates that have been proposed as a solid medium for growing plants or as a fertilizer material. The kinetics of nitrification has not been measured for NH4+ saturated zeoponic substrate. Experiments were conducted to evaluate the production of NO2- and NO3-, and nitrifier populations in zeoponic substrates. Small columns were filled with zeoponic substrate inoculated with a commercial inoculum or soil enrichment culture of nitrifying bacteria. In addition to column studies, a growth chamber study was conducted to evaluate the kinetics of nitrification in zeoponic substrates used to grow radishes (Raphanus sativus L.). The zeoponic substrate provided a readily available source of NH4+, and nitrifying bacteria were active in the substrate. Ammonium oxidation rates in column studies ranged from 5 to 10 micrograms N g-1 substrate h-1, and NO2- oxidation rates were 2 to 9.5 micrograms N g-1 substrate h-1. Rates determined from the growth chamber study were approximately 1.2 micrograms N g-1 substrate h-1. Quantities of NH4+ oxidized to NO2- and NO3- in inoculated zeoponic substrate were in excess of plant up-take. Acidification as a result of NH4+ oxidation resulted in a pH decline, and the zeoponic substrate showed limited buffering capacity.
NASA Discipline Life Support Systems↗
Nitrogen Species in the Post-Pinatubo Stratosphere: Model Analysis Utilizing UARS Measurements
We present an analysis of the impact of heterogeneous chemistry on the partitioning of nitrogen species measured by the Upper Atmosphere Research Satellite (UARS) instruments. The UARS measurements utilized include: N2O, HNO3 and ClONO2 (Cryogen Limb Array Etalon Spectrometer (CLAES), version 7), temperature, methane, ozone, H2O, HCI, NO and NO2 (HALogen Occultation Experiment (HALOE), version 18). The analysis is carried out for the data from January 1992 to September 1994 in the 100-1 mbar (approximately 17-47 km) altitude range and over 10 degree latitude bins from 70 deg S to 70 deg N. Temporal-spatial evolution of aerosol surface area density (SAD) is adopted according to the Stratospheric Aerosol and Gas Experiment (SAGE) II data. A diurnal steady-state photochemical box model, constrained by the temperature, ozone, H2O, CH4, aerosol SAD and columns of O2 and O3 above the point of interest, has been used as the main tool to analyze these data. Total inorganic nitrogen (NOy) is obtained by three different methods: (1) as a sum of the UARS measured NO, NO2, HNO3, and CIONO2; (2) from the N2O-NOy correlation, (3) from the CH4-NOy correlation. To validate our current understanding of stratospheric heterogeneous chemistry for post-Pinatubo conditions, the model-calculated NOx/NOy ratios and the NO, NO2, and HNO3 profiles are compared to the UARS-derived data. In general, the UARS-constrained box model captures the main features of nitrogen species partitioning in the post-Pinatubo years. However, the model underestimates the NO2 content, particularly, in the 30-7 mbar (approximately 23-32 km) range. Comparisons of the calculated temporal behavior of the partial columns of NO2 and HNO3 and ground based measurements at 45 deg S and 45 deg N are also presented. Our analysis indicates that ground-based and HALOE v.18 measurements of the NO2 vertical columns are consistent within the range of their uncertainties and are systematically higher (up to 50%) than the model results at mid-latitudes in both hemispheres. Reasonable agreement is obtained for HNO3 columns at 45 deg S suggesting some problems with nitrogen species partitioning in the model. Outstanding uncertainties are discussed.
Danilin, M. Y.↗