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All sourcesNASA NTRSDOE OSTI
NASA NTRS1995

Millimeter and Submillimeter Spectroscopy of Molecules of Atmospheric Importance

In our proposal we laid out work in three areas of relevance to atmospheric science: millimeter and submillimeter spectroscopy, variable temperature pressure broadening, and band and intensity measurements in the FIR. Below we will briefly discuss our progress during the second year of this project. In our millimeter and submillimeter (mm/submm) spectroscopic work, one of our goals has been to work towards the unification of the rotational (primarily obtained by mm/submm techniques) and rotational-vibrational (primarily obtained by infrared techniques) data sets in the context of theoretically well founded models which take advantage of the strengths of the data from each experimental technique. From the point of view of the development of the optimal data base for atmospheric observations, this is clearly a desirable goal. During the first year of this project we did an analysis of a weighted, mixed infrared and mm/submm data set of the n = 0, 1, and 2 torsional states of the ground vibrational state of HOOH. The purpose of this work is to provide a unified understanding of the spectrum, which is applicable in both the rotational and rotational - vibrational regimes. We have succeed in doing this in the context of a single weighted fit which accounts for both data sets to their respective experimental uncertainty (-0.1 and 10 MHz, respectively). Additionally, we have now done a similar analysis on the n = 0 torsional state of v(sub 3) and begun a similar analysis on v(sub 6). For several years we have been working on the mm/submm rotational spectra of the many excited vibrational states of HNO3, again with particular emphasis on the relationships between the mm/submm and infrared spectra. During the first year of this project we were able to use mm/submm spectroscopy to fully resolve the torsional splittings in 2 v(sub 9) and v(sub 5), establish a theoretically well founded quantitative relation between them, and show that both have their physical origin in the torsional motion of the v(sub 9) mode.This result has now been incorporated in a recent reanalysis of the infrared spectrum and has resulted in improved fits - eliminating what was in retrospect a systematic error associated with this previously unknown effect.

DeLucia, Frank C.↗
NASA NTRS1998

Engine Gaseous, Aerosol Precursor and Particulated Flight Altitude Conditions

The overall objective of the NASA Atmospheric Effects of Aviation Project (AEAP) is to develop scientific bases for assessing atmospheric impacts of the exhaust emissions by both current and future fleets of subsonic and supersonic aircraft. Among the six primary elements of the AEAP is Emissions Characterization. The objective of the Emission Characterization effort is to determine the exhaust emission constituents and concentrations at the engine exit plane. The specific objective of this engine test is to obtain a database of gaseous and particulate emissions as a function of fuel sulfur and engine operating conditions. The database of the particulate emission properties is to be used as a comparative baseline with subsequent flight measurement. The engine used in this test was a Pratt & Whitney F1OO-200E turbofan engine. Aviation fuel (Jet A) with a range of fuel sulfur was used. Low and high sulfur values are limited by commercially available fuels and by fuel specification limits of O.3% by weight. Test matrix was set by parametrically varying the combustor inlet temperature (T(sub 3) between idle and maximum power setting at simulated SLS and up to five other altitudes for each fuel. Four diagnostic systems, extractive and non-intrusive, were assembled for the gaseous and particulate emissions characterization measurements study. NASA extractive system includes smoke meter and analyzers for measurement of CO, CO2, NO, NOx, O2, total unburnt hydrocarbons (THC), and SO2. Particulate emissions were characterized by University of Missouri-Rolla Mobile Aerosol Sampling System. A chemical ionization mass spectrometer from the Air Force Research Laboratory at Hanscom AFB was used to measure SO2 and HNO3. Aerodyne Research. Inc. used infrared tunable diode laser absorption to measure SO2, SO3, NO, H2O and CO2.

Wey, C. C.↗
NASA NTRS1997

Impact of Lightning and Convection on Reactive Nitrogen in the Tropical Free Troposphere

Latitudinal distributions of NO, NO(y), O3, CO, CH3I, and H2O mixing ratios at 8.9-12 km were obtained between 30deg N and 1deg S by DC-8 aircraft measurements made in February 1994 during Pacific Exploratory Mission-West B (PEM-West B). Very low NO(y), mixing ratios with a median value of 51 parts per trillion by volume (pptv) were observed at 9.5-12 km at 1deg N-14deg N during two flights made within 3 days. A very low median O3 mixing ratio of 19 parts per billion by volume (ppbv) and high mixing ratios of H2O and CH3I were simultaneously observed, suggesting that the low NO(y), values were probably due to the convective transport of air from the tropical marine boundary layer to this altitude. The median NO(y)/O3 ratio being a factor of 2 smaller than in the air masses in the tropical marine boundary layer might suggest the possibility that the heterogeneous removal of HNO3 during convective transport further reduced NO(y) levels. In addition to the measurements between 9.5 and 12 km, low values of NO(y) and O3 were observed between 4 and 12 km at 1deg N. Divergent wind fields at 200 and 1000 hPa and infrared (IR) cloud images show that there was large scale convection (greater than 1000 km x 1000 km) in the northeast of New Guinea Island centered around Odeg S and 150deg E as part of systematic convective activity of the Intertropical Convergence Zone (ITCZ) and the South Pacific Convergence Zone (SPCZ). This type of large scale convection could have transported air with low levels of NO(y) and O3 to the middle and upper troposphere over a wide area in the tropics. On the other hand, NO mixing ratios of 50-200 pptv and high NQ,/NOY ratios of 0.4-0.6 were observed at 9.5 km between 4deg S and 10deg S. High H2O Mixing ratios of 600-1200 parts per million by volume (ppmv) and low CO mixing ratios of 65 ppbv observed in the air mass indicated that the high NO values were probably due to NO production by lightning. Satellite observations showed relatively frequent lightning flashes over the New Guinea Island for 3 days prior to the aircraft measurements. These results are considered to be consistent with the idea that, in general, marine convection is not accompanied by lightning activity, whereas convection over land is. Because of the large areal extent of the influences from these processes, the convective transport of low NO(y) air and NO production by lightning should play critical roles in controlling the abundance of reactive nitrogen in the equatorial region.

Kawakami, S.↗
NASA NTRS1999

Air Force F-16 Aircraft Engine Aerosol Emissions Under Cruise Altitude Conditions

Selected results from the June 1997 Third Subsonic Assessment Near-Field Interactions Flight (SNIF-III) Experiment are documented. The primary objectives of the SNIF-III experiment were to determine the partitioning and abundance of sulfur species and to examine the formation and growth of aerosol particles in the exhaust of F-16 aircraft as a function of atmospheric and aircraft operating conditions and fuel sulfur concentration. This information is, in turn, being used to address questions regarding the fate of aircraft fuel sulfur impurities and to evaluate the potential of their oxidation products to perturb aerosol concentrations and surface areas in the upper troposphere. SNIF-III included participation of the Vermont and New Jersey Air National Guard F-16's as source aircraft and the Wallops Flight Facility T-39 Sabreliner as the sampling platform. F-16's were chosen as a source aircraft because they are powered by the modern F-100 Series 220 engine which is projected to be representative of future commercial aircraft engine technology. The T-39 instrument suite included sensors for measuring volatile and non-volatile condensation nuclei (CN), aerosol size distributions over the range from 0.1 to 3.0 (micro)m, 3-D winds, temperature, dewpoint, carbon dioxide (CO2), sulfur dioxide (SO2), sulfuric acid (H2SO4), and nitric acid (HNO3).

Anderson, Bruce E.↗
NASA NTRS1999

Mesospheric Odd Nitrogen Enhancements During Relativistic Electron Precipitation Events

The behavior of mesospheric odd nitrogen species during and following relativistic and diffuse auroral precipitation events is simulated, Below 75 km nitric oxide is enhanced in proportion to the ion pair production function associated with the electron precipitation and the length of the event. Nitrogen dioxide and nitric acid are also enhanced. At 65 km the percentage of odd nitrogen for N is 0.1%, HNO3 is 1.6%, NO2 is 15%, and NO is 83.3%. Between 75 and 85 km NO is depleted during particle events due to the faster destruction of NO by N relative to the production of NO by N reacting with O2. Recovery of NO depends on transport from the lower thermosphere, where NO is produced in abundant amounts during particle events.

Aikin, A. C.↗
NASA NTRS1999

Effects of Solar Proton Events on the Middle Atmosphere

Solar proton events (SPEs) can result in increases in both HOx (H, OH, HO2) and NOx (N, NO, NO2) constituents in the polar middle atmosphere. Decreases in mesospheric and upper stratospheric ozone caused by HOx constituents produced by SPEs have been observed during several events, however, ozone levels generally recover within a few hours after the end of these events because of the short lifetime of the HOx species. The NOx species feed into the more inclusive odd nitrogen family, NOy (N, NO, NO2, NO3, N2O5, HNO3, HNO4, ClONO2), over a period of hours to weeks. In low sun and lower altitude conditions, the NOy family lasts several months or more in the stratosphere causing prolonged ozone changes over these longer periods. Observations of mesospheric winds during and after SPEs have also indicated some variations as a result of these atmospheric perturbations. An overview of the influence of SPEs on the polar neutral middle atmosphere will be presented in this paper.

Jackman, Charles H.↗
NASA NTRS1998

EOS Interdisciplinary Investigation: Observational and Modeling Studies of Radiative, Chemical, and Dynamical Interactions in the Earth's Atmosphere

A 3-dimensional model of atmospheric dynamics and photochemistry has been developed from the primitive equations in isentropic coordinates. The model extends from the upper troposphere through the middle atmosphere and is driven by observed dynamical and chemical structure in the troposphere. The model's formulation is entirely spectral: Horizontal structure is represented in terms of vector Hough functions, which explicitly partition the motion into its rotational and divergent components. This formulation enables the model's computational performance to be increased dramatically by filtering high-frequency gravity waves, which do not affect PV conservation. Vertical structure is represented in terms of eigenfunctions that follow from the primitive equations in isentropic coordinates. The model's fully spectral formulation enables scale-selective dissipation, necessary for numerical stability, to be applied at 6th order-in all 3 coordinate directions. This feature leaves all but the shortest vertical scales undamped and, consequently, allows potential vorticity and chemical tracers to be conserved quite accurately, distinctly better than in the model's layered counterpart. These dynamical features are complemented by a basic but fairly complete treatment of gas phase photochemistry, which accounts for some 48 chemical species, diurnally-varying SW absorption by O2 and O3, and LW cooling calculated via a detailed band calculation of radiative transfer. Driven by observed tropospheric structure, the 3D model reproduces observed structure in the middle atmosphere, inclusive of transport by the Brewer-Dobson circulation and accompanying chemical variations. Calculated residual motion is consistent with diabatic cooling rates, poleward transport, and descent in the polar night derived from satellite measurements of chemical tracers made from LIMS, SAGE, and UARS. The model also reproduces the observed structure of chemical species like O3, HNO3, and ClO. At the same time, it provides a respectable 3D simulation of the wintertime increase of midlatitude total ozone, as well as its geographical structure observed by Nimbus-7 TOMS. The 3D model has been used to explore the origin of diabatic upwelling in the tropical lower stratosphere, which has been related to planetary wave absorption in the winter- time stratosphere, as well as to influences from tropospheric convection at the tropical tropopause.

Salby, Murry L.↗
NASA NTRS1998

The Influences of Airmass Histories on Radical Species During POLARIS

The POLARIS mission focused on understanding the processes associated with the decrease of polar stratospheric ozone from spring to fall at high latitudes. This decrease is linked primarily to in situ photochemical destruction by reactive nitrogen species, NO and NO2, which also control other catalytic loss cycles. Steady state models have been used to test photochemistry and radical behavior but are not always adequate in simulating radical species observations. In some cases, air mass history can be important and trajectory models give an improved simulation of the radical species. Trajectory chemistry models, however, still consistently underestimate NO and NO2 abundances compared to measurements along the ER-2 flight track. The Goddard chemistry on trajectory model has been used to test updated rate constants for NO2 + OH, NO2 + O and OH + HNO3, key reactions that affect NO and NO2 abundances. We present comparisons between the modified Goddard chemistry on trajectory model, the JPL steady state model and observations from selected flights.

Pierson, James M.↗
NASA NTRS1987

Infrared Measurements of Several Nitrogen Species Above the South Pole in December 1980 and November - December 1986

In December 1980 and November-December 1986, the University of Denver atmospheric spectroscopy group recorded numerous high-resolution infrared solar absorption spectra from the Amundsen-Scott south pole station. These spectra were obtained by Frank J. Murcray and Frank H. Murcray with a Michelson-type Fourier transform spectrometer and show absorption features of a number of minor and trace atmospheric gases with a minimum of atmospheric water vapor absorption. Quantifications of the total column amounts of O3, CH4, N2O, and H2O from the 1980 observations and RCI from the 1986 observations have been reported along with an atlas of the 750-960/ cm spectral region. In the present study, we report measurements of HNO3 total column amounts deduced from both data sets and NO, and NO2 total column amounts from the 1986 data set. Nitric acid may be important in the chemistry which creates the spring Antarctic ozone minimum, since it may condense in the cold winter polar stratosphere and become the dominant component of polar stratospheric clouds. The present measurements were obtained shortly after the austral spring ozone minimum and define for the first time the ambient levels of these nitrogen species immediately following the breakup of the polar vortex.

Murcray, F. J.↗
NASA NTRS1994

High Resolution Studies of Heavy NO(y) Molecules in Atmospheric Spectra

New line parameters for two heavy odd nitrogen molecules HNO3 in the upsilon(sub 5)/2upsilon(sub 9) region, and ClONO2 in the upsilon(sub 4) region are incorporated in the analysis of high resolution i.r. atmospheric spectra. The line parameters arc tested and renormalized vs laboratory spectra, and then applied to retrievals from balloon-borne and ground-based solar absorption spectra.

Goldman, A.↗
NASA NTRS1998

Ozone Depletion Potential of CH3Br

The ozone depletion potential (ODP) of methyl bromide (CH3Br) can be determined by combining the model-calculated bromine efficiency factor (BEF) for CH3Br and its atmospheric lifetime. This paper examines how changes in several key kinetic data affect BEF. The key reactions highlighted in this study include the reaction of BrO + HO2, the absorption cross section of HOBr, the absorption cross section and the photolysis products of BrONO2, and the heterogeneous conversion of BrONO2 to HOBr and HNO3 on aerosol particles. By combining the calculated BEF with the latest estimate of 0.7 year for the atmospheric lifetime of CH3Br, the likely value of ODP for CH3Br is 0.39. The model-calculated concentration of HBr (approx. 0.3 pptv) in the lower stratosphere is substantially smaller than the reported measured value of about 1 pptv. Recent publications suggested models can reproduce the measured value if one assumes a yield for HBr from the reaction of BrO + OH or from the reaction of BrO + HO2. Although the evaluation concluded any substantial yield of HBr from BrO + HO2 is unlikely, for completeness, we calculate the effects of these assumed yields on BEF for CH3Br. Our calculations show that the effects are minimal: practically no impact for an assumed 1.3% yield of HBr from BrO + OH and 10% smaller for an assumed 0.6% yield from BrO + HO2.

Ko, Malcolm K. W.↗
NASA NTRS1995

Freezing Behavior of Stratospheric Sulfate Aerosols Inferred from Trajectory Studies

Temperature histories based on 10-day back growth trajectories for six ER-2 flights during AASE I (1989) and AAOE (1987) are presented. These trajectories along with the properties of the observed PSC (polar stratospheric cloud) particles are used here to infer the physical state of the pre-existing sulfuric acid aerosols. Of all the ER-2 flights described here, only the PSCs observed on the flights of January 24 and 25, 1989 are consistent with the thermodynamics of liquid ternary solutions of H2SO4/HNO3/H2O Ib PSCs). For these two days, back trajectories indicate that the air mass was exposed to SAT (sulfuric acid tetrahydrate) melting temperatures about 24 hours prior to being sampled by the ER-2. For the remaining ER-2 flights (January, 16, 19, and 20 for the AASE I campaign and August 17 for the AAOE campaign), the observed PSCs were probably composed of amorphous solid solutions of HNO3 and H2O (Type Ic PSCs). Formation of such Type Ic PSCs requires the presence of solid H2SO4 aerosols since liquid aerosols yield ternary solutions. The 10-day back trajectories of these flights indicate that the air mass was not exposed to SAT melting temperatures during the past week and had experienced cooling/warming cycles prior to being sampled by the ER-2. These temperature histories, recent laboratory measurements and the properties of glassy solids suggest that stratospheric H2SO4 aerosols may undergo a phase transition to SAT upon warming at approximately 198 K after going through a cooling cycle to about 194 K or lower.

Tabazadeh, A.↗
NASA NTRS1995

Design of a Three-Layer Antireflection Coating for High Efficiency Indium Phosphide Solar Cells Using a Chemical Oxide as First Layer

It is well known that the behavior of III-V compound based solar cells is largely controlled by their surface, since the majority of light generated carriers (63% for GaAs and 79% for InP) are created within 0.2 microns of the illuminated surface of the cell. Consequently, the always observed high surface recombination velocity (SRV) on these cells is a serious limiting factor for their high efficiency performance, especially for those with the p-n junction made by either thermal diffusion or ion implantation. A good surface passivation layer, ideally, a grown oxide as opposed to a deposited one, will cause a significant reduction in the SRV without adding interface problems, thus improving the performance of III-V compound based solar cells. Another significant benefit to the overall performance of the solar cells can be achieved by a substantial reduction of their large surface optical reflection by the use of a well designed antireflection (AR) coating. In this paper, we demonstrate the effectiveness of using a chemically grown, thermally and chemically stable oxide, not only for surface passivation but also as an integral part of a 3- layer AR coating for thermally diffused p(+)n InP solar cells. A phosphorus-rich interfacial oxide, In(PO3)3, is grown at the surface of the p(+) emitter using an etchant based on HNO3, o-H3PO4 and H2O2. This oxide has the unique properties of passivating the surface as well as serving as a fairly efficient antireflective layer yielding a measured record high AM0, 25 C, open-circuit voltage of 890.3 mV on a thermally diffused InP(Cd,S) solar cell. Unlike conventional single layer AR coatings such as ZnS, Sb2O3, SiO or double layer AR coatings such as ZnS/MgF2 deposited by e-beam or resistive evaporation, this oxide preserves the stoichiometry of the InP surface. We show that it is possible to design a three-layer AR coating for a thermally diffused InP solar cell using the In(PO3)3 grown oxide as the first layer and Al2O3, MgF2 or ZnS, MgF2 as the second and third layers respectively, so as to yield an overall theoretical reflectance of less than 2%. Since chemical oxides are readily grown on III-V semiconductor materials, the technique of using the grown oxide layer to both passivate the surface as well as serve as the first of a multilayer AR coating, should work well for essentially all III-V compound-based solar cells.

Moulot, Jacques↗
NASA NTRS2000

Update on N2O4 Molecular Sieving with 3A Material at NASA/KSC

During its operational life, the Shuttle Program has experienced numerous failures in the Nitrogen Tetroxide (N2O4) portion of Reaction Control System (RCS), many of which were attributed to iron-nitrate contamination. Since the mid-1980's, N2O4 has been processed through a molecular sieve at the N2O4 manufacturer's facility which results in an iron content typically less than 0.5 parts-per-million-by-weight (ppmw). In February 1995, a Tiger Team was formed to attempt to resolve the iron nitrate problem. Eighteen specific actions were recommended as possibly reducing system failures. Those recommended actions include additional N2O4 molecular sieving at the Shuttle launch site. Testing at NASA White Sands Test Facility (WSTF) determined an alternative molecular sieve material could also reduce the water-equivalent content (free water and HNO3) and thereby further reduce the natural production of iron nitrate in N2O4 while stored in iron-alloy storage tanks. Since April '96, NASA Kennedy Space Center (KSC) has been processing N2O4 through the alternative molecular sieve material prior to delivery to Shuttle launch pad N2O4 storage tanks. A new, much larger capacity molecular sieve unit has also been used. This paper will evaluate the effectiveness of N2O4 molecular sieving on a large-scale basis and attempt to determine if the resultant lower-iron and lower-water content N2O4 maintains this new purity level in pad storage tanks and shuttle flight systems.

Davis, Chuck↗
NASA NTRS2001

Sources, Sinks, and the Distribution of OH in the Lower Stratosphere

Extensive measurement campaigns by the NASA ER-2 research aircraft have obtained a nearly pole-to-pole database of the species that control HOx (OH + HO2) chemistry. The wide dynamic range of these in situ measurements provides an opportunity to demonstrate empirically the mechanisms that control the HOx system. Measurements in the lower stratosphere show a remarkably tight correlation of OH concentration with the solar zenith angle (SZA). This correlation is nearly invariant over latitudes ranging from 70 S to 90 N and all seasons. An analysis of the production and loss of HOx in terms of the rate determining steps of reaction sequences developed by Johnston and Podolske and Johnston and Kinnison is used to clarify the behavior of the system and to directly test our understanding of the system with observations. Calculations using in situ measurements show that the production rate of HOx is proportional to O3 and ultraviolet radiation flux. The loss rate is proportional to the concentration and the partitioning of NOy (reactive nitrogen) and the concentration of HO2. In the absence of heterogeneous reactions, the partitioning of NOy is controlled by O3 and NOx and the concentration of HO2 is controlled by NOy and O3, so that the removal rate of OH is buffered against changes in the correlation of O3 and NOy. The heterogeneous conversion of NO2 to HNO3 is not an important net source of HO, because production and removal sequences are nearly balanced. Changes in NOy partitioning resulting from heterogeneous chemistry have a large effect on the loss rates of HOx, but little or no impact on the measured abundance of OH. The enhanced loss rates at high NO2/HNO3 are offset in the data set examined here by enhanced production rates resulting from increased photolysis rates resulting from the decreased O3 column above the ER-2.

Hanisco, T. F.↗
NASA NTRS2001

Impact and Collisional Processes in the Solar System

A series of impact experiments on anhydrite CaSO4, in which vaporized sample accelerates an element in a velocity interferometer, generate velocity data that we have recently reanalyzed using an explicit entropy generating finite difference code. The shock pressure required from the onset, and complete vaporization of 30% porous and 70% crystal density anhydrite is 52 +/- 3 and 122 +/- 13 GPa. Using observed acid leaching in non-marine K/T ejecta in North America, and the sharp global increase in Sr-87/Sr-86 ratios recorded at 65 Ma in marine rocks, we demonstrated that global acidification is primarily due to the SO2 released by anhydrite volatilization, and not HNO3 formed from bolide-induced air pyrolysis. Shock temperatures for crystal CaCO3 are measured from 3000 to 7000 K in the 90 to 160 GPa pressure range. These temperatures are much lower than calculated theoretically indicating that possibly bond breakdown at the shock front is occurring. This is the first mineral in which this effect has ever been seen. New data defining the ion species which are produced upon impact of volatilization of metals and minerals using a pulse ultraviolet laser to simulate intense shock heating from a projectile impact indicate that in shock experiments we can for the first time study the speciation of neutrals using a moderate resolution time-of-flight mass spectrometer. Measurements of the gas species from a series of proposed impact experiments appear to be quite feasible. We will attempt these experiments in the next year. Measurements of the impact induced shock wave decay in SiO2 and GeO2 glass are underway to measure these pure oxide properties. Predictive calculations indicate that the pressure will decay as r(exp -2.7) in the phase transition regime, versus a much lower rate of r(exp -1.18), if a phase transition does not occur.

Ahrens, Thomas J.↗
NASA NTRS2001

Tunable Far Infrared Studies in Support of Stratospheric Measurements

This report summarizes research done under NASA Grant NAG5-4653. The research performed under this grant has been a collaboration between institutions including the Smithsonian Astrophysical Observatory, the National Institute of Standards and Technology, the University of Oregon, and the NASA Langley Research Center. The program has included fully line-resolved measurements of submillimeter and far infrared spectroscopic line parameters (pressure broadening coefficients and their temperature dependences, and line positions) for the analysis of field measurements of stratospheric constituents, far infrared database improvements, and studies for improved satellite measurements of the Earth's atmosphere. This research program is designed to enable the full utilization of spectra obtained in far infrared/submillimeter field measurements, such as FIRS-2, FILOS, IBEX, SLS, EosMLS, and proposed European Space Agency measurements of OH (e.g., PIRAMHYD and SFINX) for the retrieval of accurate stratospheric altitude profiles of key trace gases involved in ozone layer photochemistry. For the analysis of the spectra obtained in the stratosphere from far infrared measurements it is necessary to have accurate values of the molecular parameters (line positions, strengths, and pressure broadening coefficients) for the measured molecules and for possible interfering species. Knowledge of line positions is in increasingly good shape, with some notable exceptions. The increase in position information includes research that has been performed in the present program of research on HO2, H2O, H2O2, O3, HCl, HF, HBr, HI, CO, OH, and ClO. Examples where further line position studies are necessary include hot band and minor isotopomer lines of some of the major trace species (H2O, O3) and normal lines of some triatomic and larger molecules (NO2). Knowledge of strengths is in generally good shape, since most of the lines are from electric dipole transitions whose intensities are well determined from Stark effect measurements; exceptions include some molecules with large vibration-rotation interactions (NO2) and internal motions (H2O2 above the lowest torsional state). The line parameters that are still the least well determined are pressure broadening coefficients, and their temperature coefficients, These are strongly dependent on the quantum states involved in the transitions, in a way that is much more complex than the simple projection by directional cosine matrix elements involved in determination of rotational line strengths from static dipole moments. The following molecules have now been measured or detected in the atmosphere using far infrared and millimeter-wave emission spectroscopy from balloon- and satellite-borne spectrometers: OH, HO2, H2O (including minor isotopomers and hot band lines), H2O2, O3P, O2 (including minor isotopomers), O3 (including minor isotopomers and hot band lines), HOCl, HCl, HF, HBr, CIO, CO, CO2, N2O, NO2, N2O5, HNO3, ClNO3, and HCN. Many of these species have spectral lines that are saturated in stratospheric spectra. In these cases, the measured line equivalent widths are proportional to (line strength x Lorentz width) (exp 1/2) so that the pressure broadening coefficients are as important as the line intensities in determining concentration profiles. Interpretation of field measurements for these species have required ongoing measurement programs of pressure broadening measurements. Other species (HO2, HGCl, H2O2, HBr, and NO2, as examples) have required further line position studies in order to fully analyze the field measurements.

Chance, Kelly V.↗
NASA NTRS1997

Upper Tropospheric/Lower Stratospheric Distribution of Reactive Nitrogen and Ozone

In-situ measurements of a large number of trace chemicals from upper troposphere/lower stratosphere (UT/LS) were performed with the NASA DC-8 aircraft during February/March 1994 over the Pacific Ocean (10 S to 60 N). Mixing ratios in the UT were relatively low in the warm tropical and subtropical air south of the polar jetstream (approx. =28 N) but increased sharply with latitude in the cold polar air north of the jetstream. At about 45 N, high concentrations of PAN (300 ppt) coexisted with extremely low (approx. = 20 ppt) concentrations of NOx. Elevated NOx levels in the UT did not always correspond to continental outflow conditions. Deepest penetrations into the stratosphere (550 ppb O3, 279 ppb NOx, and 350 K potential temperature) corresponded to a region that has been defined as the 'lowermost stratosphere' (LS) by Holton et al. Analysis of data shows that the mixing ratios of long-lived tracer species (e.g., CH4, HNO3, NOy, CFCs, HCFCs) are linearly correlated with those of O3 and N2O. A delta-NOY/delta-O3 of 0.0054 ppb/ppb and delta-NOy/delta-N2O of -0.081 ppb/ppb is in good agreement with other reported measurements from the DC-8. These slopes are however, somewhat steeper than those reported from the ER-2 studies. We find that the reactive nitrogen budget in the UT/LS is largely balanced with shortfalls that are no greater than 15%. A number of oxygenated species (e.g., acetone, H2O2) are present and may provide an important in-situ source of HOx in the UT/LS region.

Singh, H. S.↗