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NASA NTRS1991

Measurements in polar stratospheric clouds over Antarctica in September 1989

The results of six balloon flights at McMurdo Station, Antarctica, under varying temperature conditions, are used in a study of polar stratospheric clouds during Sept. 1989. A particle counter, with size resolution in the 0.5 micron radius region, indicates that cloud size distributions are always bimodal. Mode radii ranging from 0.05 to 0.10 microns were observed for the small particle mode, representing the sulfate layer or condensational growth enhancements of it. The data are not inconsistent with the expected increase in size with decreasing temperature of the small particle mode in the sulfate layer owing to deliquescence although this phenomenon is often masked by nitric acid trihydrate (NAT) condensation when temperatures are sufficiently low. Mode radii generally ranged from 1.5 to 3.5 micron for the large particle mode at concentrations 3 to 4 orders of magnitude lower than the small particle mode. The large particle mode, which normally comprises most of the mass, is presumably caused by NAT condensation on larger particles of the sulfate layer and indicates HNO3 mixing ratios of 1 to 5 ppbv for most of the cloud layers observed, suggesting substantial denitrification. On several occasions, distributions were observed with mode radii as high as 7 microns, and correspondingly large inferred mass, indicating water ice clouds in the 12 to 15 km region. On other occasions, absence of such clouds at very low temperatures indicated water vapor mixing ratios of less than 3 ppmv suggesting dehydration. Generally, the inferred HNO3 mixing ratios were higher in the lower stratosphere, suggesting redistribution through particle sedimentation.

Deshler, Terry↗
NASA NTRS1976

The covariance of temperature and ozone due to planetary-wave forcing

The cross-spectra of temperature and ozone mass mixing ratio at 42 km and 28 km has been determined for spring (1971) and summer (1971-2) over Christchurch, New Zealand (44 S, 172 E). The sources of data are the SCR and BUV experiments on Nimbus 4. The observed covariances are compared with a model in which the temperature and ozone perturbations are forced by an upward propagating planetary wave. The agreement between the observations and the model is reasonable. It is suggested that this cross-spectral method permits an estimate of the meridional gradient of ozone mass mixing ratio from measurements of the vertical profile of ozone mass mixing ratio at one location, supported by temperature profiles from at least two locations.

Fraser, G. J.↗
NASA NTRS1991

Spectroscopy and chemistry of the atmosphere of Uranus

A comprehensive review of the chemistry and spectroscopy of the Uranian atmosphere is presented by means of earth-based, earth-orbital, and Voyager 2 observations covering the UV, visible, infrared, and radio wavelength regions. It is inferred from these observations, in concert with the average density of about 1.3 g/cu cm, that the Uranian atmosphere is enriched in heavy elements relative to solar composition. Pre-Voyager earth-based observations of CH4 bands in the visible region and Voyager radio occultation data imply a CH4/H2 volume mixing ratio of about 2 percent corresponding to an enrichment of approximately 24 times the solar value of 0.000835. In contrast to CH4, microwave observations indicate an apparent depletion of NH3 in the 155-to-200-K region of the atmosphere by 100 to 200 times relative to the solar NH3/H2 mixing ratio of -0.000174. It is suggested that the temporal and latitudinal variations deduced for the NH3/H2 mixing ratio in this region of the Uranian atmosphere are due to atmospheric circulation effects.

Fegley, Bruce, Jr.↗
NASA NTRS1990

The distribution of middle tropospheric carbon monoxide during early October 1984

The measurement of Air Pollution from Satellite experiment measured the distribution of middle-tropospheric CO from the Space Shuttle during October 1984. The data represent average mixing ratios between 57 deg N and 57 deg S. Approximately 75,000 individual CO measurements were obtained during the 9-day mission. The data are presented in maps that show the CO mixing ratios averaged over 5 x 5-deg areas for 6 days of the mission. Comparisons with concurrent direct measurements taken aboard aircraft show that the inferred concentrations are systematically low by 20-40 percent, depending upon which direct measurement calibration standard is used. The data show that there are very large CO sources resulting from biomass burning over South America and southern Africa. Measured mixing ratios were high over northeast Asia and were highly variable over Europe.

Reichle, Henry G., Jr.↗
NASA NTRS2004

Florida Thunderstorms: A Faucet of Reactive Nitrogen to the Upper Troposphere

During the NASA Cirrus Regional Study of Tropical Anvils and Cirrus Layers-Florida Area Cirrus Experiment (CRYSTAL-FACE) enhanced mixing ratios of nitric oxide were measured in the anvils of thunderstorms and in clear air downwind of storm systems on flights of a Wl3-57F high-altitude aircraft. Mixing ratios greater than l0 - 20 times background were readily observed over distances of 25-120 km due to lightning activity. In many of the Florida storms deposition of NO occurred up to near the tropopause but major deposition usually occurred 1 - 2 km below the tropopause, or mostly within the visible anvil volume formed prior to storm decay. Observations from two storms of very different anvil size and electrical activity allowed estimates of the total mass of NO, vented to the middle and upper troposphere. Using the cloud-to ground (CG) flash accumulations from the National Lightning Detection Network, climatological intra-cloud (IC) to CG ratios, and assuming that CG and IC flashes were of equivalent efficiency for NO production, the ranges of production per flash for a moderate-sized and a large storm were (0.51 - 1.0) x l0(exp 26) and (2.3 - 3.1) x 10(exp 26) molecules NO/flash, respectively. Using the recently determined average global flash rate of 44 8, a gross extrapolation of these two storms to represent possible global annual production rates yield 1.6 - 3.2 and 7.3 - 9.9 Tg(N)/yr, respectively. If the more usual assumption is made that IC efficiency is l/l0th that of CG activity, the ranges of production for the moderate-sized and large storm were (1.3 - 2.7) x l0(exp 26) and (6.0 - 8.1) x l0(exp 26) molecules NO/CG flash, respectively. The estimates from the large storm may be high because there is indirect evidence that the IC/CG ratio was larger than would be derived from climatology. These two storms and others studied did not have flash rates that scaled as approx. H(sup 5) where H is the cloud top altitude. The observed CG flash accumulations and NO(x) mass production estimate for the month of July over the Florida area were compared with a representative 3D global Chemistry-Transport Model (CTMJ that uses the Price et al. lightning parameterization. For two land grid points representing the Florida peninsula the model compared well with the observations: CG flash rates were low by only a factor of approx. 2. When the model grid points included the coastal regions of Florida the flash accumulations were lower than observed by a factor of 3.4 - 4.6. It is recommended that models using the Price et al. parameterization allow any global coastal grid point to maintain the land rather than the marine flash rate parameterization. The convection in this CTM underestimated the actual cloud top heights over Florida by 1 - 2 km and thus the total lightning flash rates and the altitude range of reactive nitrogen deposition. Broad scale (20 - 120 km) median mixing ratios of NO within anvils over Florida were significantly larger than in storms previously investigated over Colorado and New Mexico.

Ridley, B.↗
NASA NTRS1976

Spectroscopic detection and vertical distribution of HCl in the troposphere and stratosphere

HCl has been observed in both the troposphere and stratosphere from ground-based and airborne spectroscopic measurements of the 1-0 band at 3-micron wavelength. The results, which are specific to the HCl molecule in the gas phase, show a decreasing mixing ratio with altitude in the lower stratosphere. The stratospheric layer, which commences at about 15 km, reaches its maximum concentration at an altitude above 21 km (the limiting height of the observations to date). The local value for the volume mixing ratio at 21 km is 7 + or - 1 times 10 to the minus 10th. However, the zenith column abundance observed above 21 km implies that the mixing ratios at greater altitudes are unlikely to reach values much in excess of the local value at 21 km.

Farmer, C. B.↗
NASA NTRS1987

Measurement of methane and other light hydrocarbons in the troposphere and lower stratosphere

The volume mixing ratios of methane, acetylene, ethane, and propane were measured in the troposphere and stratosphere on April 5, 1984, at 33 deg N, over New Mexico, using the technique of grab sampling by evacuated spheres on a balloon platform. Tropospheric volume mixing ratios were CH4, 1.59 ppm; C2H2, 358 ppt (parts per trillion); C2H6, 365 ppt; and C3H8, 1440 ppt. In the stratosphere, acetylene was 60 ppt. For ethane and propane the mixing ratios at 11.6 km were 441 ppt and 84 ppt, respectively.

Aikin, A. C.↗
NASA NTRS1989

Water vapor and methane in the upper stratosphere - An examination of some of the Nimbus 7 measurements

The zonal mean volume mixing ratios of water vapor and methane from January to May, 1979, derived from the Nimbus-7 limb IR monitor of the stratosphere and from stratosphere and mesosphere sounder experiments are investigated. The water vapor mixing ratio of air that enters the stratosphere from the troposphere and the yield of water vapor from photochemical oxidation of methane in the stratosphere are examined. The water vapor yield averaged between 1.5 and 2.0, although variability with time and level was relatively large. It is suggested that water vapor yield increases with height in the 16- to 3-mbar range. The average water vapor mixing ratio fo air entering the stratosphere during the study period was about 3.25 X 10 to the -6th.

Hansen, Anthony R.↗
NASA NTRS1983

Photochemistry of methane in the earth's early atmosphere

The photochemical behavior of methane in the early terrestrial atmosphere is investigated with a detailed model in order to determine how much CH4 might have been present and what types of higher hydroocarbons could have been formed. It is found that any primordial methane accumulated during the course of earth accretion would have been dissipated by photochemical reactions in the atmosphere in a geologically short period of time after the segregation of the core. Abiotic sources of methane are not likely to have been large enough to sustain CH4 mixing ratios as high as 10 to the -6th, the threshold for a possible methane greenhouse, with a CO-rich atmosphere being a possible exception. After the origin of life an increasing biogenic source of methane may have driven CH4 mixing ratios well above 10 to the 6th. The rise of atmospheric oxygen in the early Proterozoic may have led to a more rapid photochemical destruction of methane, lowering the mixing ratio to its present value.

Kasting, J. F.↗
NASA NTRS2011

The Observed Relationship Between Water Vapor and Ozone in the Tropical Tropopause Saturation Layer and the Influence of Meridional Transport

We examine balloonsonde observations of water vapor and ozone from three Ticosonde campaigns over San Jose, Costa Rica [10 N, 84 W] during northern summer and a fourth during northern winter. The data from the summer campaigns show that the uppermost portion of the tropical tropopause layer between 360 and 380 K, which we term the tropopause saturation layer or TSL, is characterized by water vapor mixing ratios from proximately 3 to 15 ppmv and ozone from approximately 50 ppbv to 250 ppbv. In contrast, the atmospheric water vapor tape recorder at 380 K and above displays a more restricted 4-7 ppmv range in water vapor mixing ratio. From this perspective, most of the parcels in the TSL fall into two classes - those that need only additional radiative heating to rise into the tape recorder and those requiring some combination of additional dehydration and mixing with drier air. A substantial fraction of the latter class have ozone mixing ratios greater than 150 ppbv, and with water vapor greater than 7 ppmv this air may well have been transported into the tropics from the middle latitudes in conjunction with high-amplitude equatorial waves. We examine this possibility with both trajectory analysis and transport diagnostics based on HIRDLS ozone data. We apply the same approach to study the winter season. Here a very different regime obtains as the ozone-water vapor scatter diagram of the sonde data shows the stratosphere and troposphere to be clearly demarcated with little evidence of mixing in of middle latitude air parcels.

Selkirk, Henry B.↗
NASA NTRS1988

Measurement of nighttime stratospheric N2O5 from infrared emission spectra

The mixing ratio profile of N2O5 has been inferred from high-resolution emission spectra obtained with a balloon-borne Fourier spectrometer. The observations were taken for the period from midnight to predawn on September 16, 1986 at 32 deg N latitude. The inferred volume mixing ratio from nighttime average spectra has a peak of about 1.8 x 10 to the -9th in the 32-35 altitude range. The inferred mixing ratio is generally less than the theoretical predictions from a one-dimensional model.

Kunde, V. G.↗
NASA NTRS1990

In situ measurements of BrO in the Arctic stratosphere

Mixing ratios of BrO have been measured in the Arctic lower statosphere with an instrument mounted on the NASA ER-2 aircraft. Observations from fourteen flights above the Arctic Circle in January and February of 1989 defined mixing ratios within the vortex of 4 + or - 2 parts per trillion by volume (pptv) at a potential temperature of 400 K, rising to 8 + or - 2 pptv at 470 K. These values are twice as large as values found at equivalent potential temperatures at lower latitudes, and are comparable to the mixing ratios found inside the antarctic polar vortex. Within the statistical uncertainty of the measurements, no BrO was observed in darkness at any time either inside or outside of the vortex, indicating that active bromine was sequestered in long-lived reservoirs, probably BrONO2 and BrCl. These measurements, in conjuction with measurements of ClO, demonstrate that the interaction of bromine and chlorine could represent a major sink for ozone in the presence of sunlight.

Toohey, D. W.↗
NASA NTRS1990

Peroxyacetyl nitrate measurements during CITE 2 - Atmospheric distribution and precursor relationships

Results are reported from airborne PAN measurements obtained at altitudes 0-6 km over the continental U.S. and the eastern Pacific during the NASA Global Tropospheric Experiment Chemical Instrumentation Test and Evaluation 2 (CITE 2) in summer 1986. The CITE 2 flights and instrumentation are described, and the results are presented in extensive graphs and characterized in detail. It is shown that PAN is an important reactive N-containing species in the troposphere. Although the PAN mixing ratios were highly variable, in general high mixing ratios of 100-300 parts per trillion by volume (pptv) were found at 4-6 km, and very low ratios (5-20 pptv) were detected in the marine boundary layer. Good correlation was seen between the CITE 2 PAN values and those for O3, NO(y), NO(x), HNO3, C2H6, CO, and CFCl3.

Singh, H. B.↗
NASA NTRS2000

Effect of Negative Ions on the Conductivity of the Titan Atmosphere

In an earlier paper, Borucki et al (1987) calculated the electrical conductivity and electrical charge on aerosols in Titan's atmosphere due to the ionization by galactic cosmic rays and electron precipitation from Saturn's magnetosphere. The lower atmosphere was predicted to be substantially more conducting than the atmospheres of Earth and Venus because of the high concentration of free electrons. The prediction of a high conductivity is based on the lack of electrophillic species which form negative ions with low mobility and which reduce the number of free electrons. At that time, no molecular species capable of forming negative ions in concentrations sufficient to perturb the atmospheric conductivity were identified. Recently, E. Bakes and her colleagues have been investigating the formation of nitrogenous macromolecules using quantum mechanical methods. Their calculations indicate that the molecules will be highly electrophillic and are likely to be present in the atmosphere at mixing ratios of order 10(exp -7). This mixing ratio is sufficiently large that a substantial reduction in the conductivity is expected at altitudes below 100 km. Revision of the atmospheric model to accommodate the presence of negative ions and to increase the fidelity of the modeling will be described.

Borucki, W. J.↗
NASA NTRS2006

Ozone Production from the 2004 North American Boreal Fires

We examine the ozone production from boreal forest fires based on a case study of wildfires in Alaska and Canada in summer 2004. The model simulations were performed with the chemistry transport model, MOZART-4, and were evaluated by comparison with a comprehensive set of aircraft measurements. In the analysis we use measurements and model simulations of carbon monoxide (CO) and ozone (O3) at the PICO-NARE station located in the Azores within the pathway of North American outflow. The modeled mixing ratios were used to test the robustness of the enhancement ratio deltaO3/deltaCO (defined as the excess O3 mixing ratio normalized by the increase in CO) and the feasibility for using this ratio in estimating the O3 production from the wildfires. Modeled and observed enhancement ratios are about 0.25 ppbv/ppbv which is in the range of values found in the literature, and results in a global net O3 production of 12.9 2 Tg O3 during summer 2004. This matches the net O3 production calculated in the model for a region extending from Alaska to the East Atlantic (9-11 Tg O3) indicating that observations at PICO-NARE representing photochemically well-aged plumes provide a good measure of the O3 production of North American boreal fires. However, net chemical loss of fire related O3 dominates in regions far downwind from the fires (e.g. Europe and Asia) resulting in a global net O3 production of 6 Tg O3 during the same time period. On average, the fires increased the O3 burden (surface-300 mbar) over Alaska and Canada during summer 2004 by about 7-9%, and over Europe by about 2-3%.

Pfister, G. G.↗
NASA NTRS1990

Stratus: An interactive steady state mixed layer model for personal computers

A steady-state, horizontally homogeneous, cloud-topped marine boundary layer model based primarily on the work of Lilly (1968) and Schubert et al., (1979) is presented. The conservative thermodynamic variables are equivalent potential temperature, theta(sub e), and total water mixing ratio, q + l. Some of the differences between this and Lilly's (1968) model are: radiation is allowed to penetrate into the boundary layer; cloud top values of longwave radiation, equivalent potential temperature, and water vapor mixing ratio are linear functions of height derived from climatological data at California coastal stations; and the closure assumption assumes a weighted average of Lilly's (1968) maximum and minimum entrainment theories. This model was programmed in FORTRAN and will run interactively on an IBM-compatible personal computer. The program allows the user to specify the geographical location, the wind speed, the sea-surface temperature, the large scale horizontal divergence, and the initial guess for cloud top height. Output includes the steady state values of cloud top and cloud base height, mixed layer equivalent potential temperature and total water mixing ratio, and the associated convective and radiative fluxes.

Guinn, Thomas A.↗
NASA NTRS2021

Quantifying the Hypervolatile Abundances in Jupiter-family Comet 46P/Wirtanen

We present analysis of IR and optical spectroscopy of Jupiter-family comet (JFC) 46P/Wirtanen obtained in 2019 January, when the comet had sufficient geocentric velocity to enable studies of the hypervolatiles CO and CH4, as well as [OI] emission. These species could not be studied near closest approach in mid-December because there was insufficient Doppler shift to separate the cometary emission from their corresponding telluric absorption lines. We employed the [OI] observations as a proxy for the CO2/H2O ratio, as CO2 cannot be observed directly from the ground, and space-based assets sensitive to CO2 were not able to observe 46P during this apparition. We focused our analysis on H2O, CO, CH4, C2H6, CH3OH, and CO2 (via [OI] emission). We detected strong emissions from H2O, C2H6, and CH3OH. Over the 3 nights, we found evidence for changing mixing ratios, mostly due to a variable H2O production rate. In 46P, C2H6 and CH3OH are enriched compared to cometary averages, with mixing ratios relative to H2O of ∼1% and ∼3%, respectively. Measurements of CH4 and CO have been especially rare in JFCs. We report significant 3σ upper limits on CH4/H2O<0.97% and CO/H2O<0.54%. They place CH4 being near-average or depleted, and CO being strongly depleted in 46P compared with Oort cloud comets. 46P has comparable CO/H2O to the few other measurements in JFCs, but enriched in C2H6 and CH3OH. Our inferred CO2/H2O mixing ratio is∼15%, though accounting for systematic uncertainties from the lack of knowledge of [OI] photochemistry means a value between 10% and 20% is likely. The compositional profile of46P is similar to another small, hyperactive comet: 103P/Hartley 2. The mechanism of CO2-driven water-rich ice grain production proposed for 103P/Hartley 2 may be operating on 46P as well.

Comets↗
NASA NTRS1991

Depletion of Arctic ozone in the winter 1990

Ozone mixing ratios were measured by ozonesondes on board balloons launched from Esrange, near Kiruna, Sweden (68 deg N, 20 deg E) from January 11 to February 9, 1990. The data obtained prior to a sudden warming on February 7, 1990 show that at potential temperatures between 460 and 640 K, the ozone mixing ratio just inside the polar vortex was systematically smaller than that outside, the largest difference being 29 percent at around 525 K. The ozone mixing ratio at 525 K inside the vortex decreased at a rate of about 1.5 percent per day between January 26 and February 4. The temperatures simultaneously observed were quite often low enough to allow for formation of nitric acid trihydrate particles around this altitude. Depletion of ozone due to highly perturbed chemical conditions in late January and early February is strongly suggested.

Koike, M.↗