Nitrogen dioxide in the stratosphere and troposphere measured by ground-based absorption spectroscopy

The NO(2) abundance in the stratosphere has been determined from ground-based spectra of the rising and setting sun and moon and of the twilight sky near 4500 angstroms. The spectra were taken at the Fritz Peak Observatory, at an altitude of 3 kilometers in the Colorado mountains. Separation of the stratospheric contribution requires observations at a relatively unpolluted site; direct measurement of the tropospheric absorption in the Colorado mountains often yields an upper limit on the tropospheric mixing ratio of 0.1 part per billion. The stratospheric NO(2) abundance is two to three times greater at night than during the day and increases significantly during the course of a sunlit day; these changes are related to photolytic decomposition of NO(2) and N(2)O(5) in the daytime stratosphere. Absorption by NO(3) was sought but not found; the results set an upper limit of 2 percent on the nighttime abundance ratio of NO(3) to NO(2) in the stratosphere.     

Chlorine monoxide radical, ozone, and hydrogen peroxide: stratospheric measurements by microwave limb sounding

Profiles of stratospheric ozone and chlorine monoxide radical (C1O) have been obtained from balloon measurements of atmospheric limb thermal emission at millimeter wavelengths. The C1O measurements, important for assessing the predicted depletion of stratospheric ozone by chlorine from industrial sources, are in close agreement with present theory, The predicted decrease of C1O at sunset was measured. A tentative value for the stratospheric abundance of hydrogen peroxide was also determined.     

Potential environmental impact of a hydrogen economy on the stratosphere

The widespread use of hydrogen fuel cells could have hitherto unknown environmental impacts due to unintended emissions of molecular hydrogen, including an increase in the abundance of water vapor in the stratosphere (plausibly by as much as approximately 1 part per million by volume). This would cause stratospheric cooling, enhancement of the heterogeneous chemistry that destroys ozone, an increase in noctilucent clouds, and changes in tropospheric chemistry and atmosphere-biosphere interactions.     

Enhanced upper tropical tropospheric COS: impact on the stratospheric aerosol layer

Carbonyl sulfide (COS) is considered to be a major source of the stratospheric sulfate aerosol during periods of volcanic quiescence. We measured COS at the tropical tropopause and find mixing ratios to be 20 to 50% larger than are assumed in models. The enhanced COS levels are correlated with high concentrations of biomass-burning pollutants like carbon monoxide (CO) and hydrogen cyanide (HCN). The analysis of backward trajectories and global maps of fire statistics suggest that biomass-burning emissions transported upward by deep convection are the source of the enhanced COS in the upper tropical troposphere.     

Jupiter's atmospheric composition from the Cassini thermal infrared spectroscopy experiment

The Composite Infrared Spectrometer observed Jupiter in the thermal infrared during the swing-by of the Cassini spacecraft. Results include the detection of two new stratospheric species, the methyl radical and diacetylene, gaseous species present in the north and south auroral infrared hot spots; determination of the variations with latitude of acetylene and ethane, the latter a tracer of atmospheric motion; observations of unexpected spatial distributions of carbon dioxide and hydrogen cyanide, both considered to be products of comet Shoemaker-Levy 9 impacts; characterization of the morphology of the auroral infrared hot spot acetylene emission; and a new evaluation of the energetics of the northern auroral infrared hot spot.     

Absorption of visible radiation by aerosols in the volcanic plume of mount st. Helens

Samples of particles from Mount St. Helens were collected in both the stratosphere and troposphere for measurement of the light absorption coefficient. Results indicate that the stratospheric dust had a small but finite absorption coefficient ranging up to 2 x 10(-7) per meter at a wavelength of 0.55 micrometer, which is estimated to yield an albedo for single scatter of 0.98 or greater. Tropospheric results showed similar high values of an albedo for single scatter.     

Resolving the structure of ionized helium in the intergalactic medium with the far ultraviolet spectroscopic explorer

The neutral hydrogen (H I) and ionized helium (He II) absorption in the spectra of quasars are unique probes of structure in the early universe. We present Far-Ultraviolet Spectroscopic Explorer observations of the line of sight to the quasar HE2347-4342 in the 1000 to 1187 angstrom band at a resolving power of 15,000. We resolve the He II Lyman alpha (Lyalpha) absorption as a discrete forest of absorption lines in the redshift range 2.3 to 2.7. About 50 percent of these features have H I counterparts with column densities N(H I) > 10(12.3) per square centimeter that account for most of the observed opacity in He II Lyalpha. The He II to H I column density ratio ranges from 1 to >1000, with an average of approximately 80. Ratios of <100 are consistent with photoionization of the absorbing gas by a hard ionizing spectrum resulting from the integrated light of quasars, but ratios of >100 in many locations indicate additional contributions from starburst galaxies or heavily filtered quasar radiation. The presence of He II Lyalpha absorbers with no H I counterparts indicates that structure is present even in low-density regions, consistent with theoretical predictions of structure formation through gravitational instability.     

Conditions for purine synthesis: did prebiotic synthesis occur at low temperatures?

The rate of polymerization of hydrogen cyanide to aminomalononitrile and the tetramer, diaminomalonodinitrile, is quadratic in the total cyanide concentration. Since the reactions form part of a plausible prebiotic purine synthesis and since they compete with hydrolysis, concentration of cyanide may have been important. This may be achieved usefully by cooling to separate out ice.     

The persistently variable "background" stratospheric aerosol layer and global climate change

Recent measurements demonstrate that the "background" stratospheric aerosol layer is persistently variable rather than constant, even in the absence of major volcanic eruptions. Several independent data sets show that stratospheric aerosols have increased in abundance since 2000. Near-global satellite aerosol data imply a negative radiative forcing due to stratospheric aerosol changes over this period of about -0.1 watt per square meter, reducing the recent global warming that would otherwise have occurred. Observations from earlier periods are limited but suggest an additional negative radiative forcing of about -0.1 watt per square meter from 1960 to 1990. Climate model projections neglecting these changes would continue to overestimate the radiative forcing and global warming in coming decades if these aerosols remain present at current values or increase.     

Is there any chlorine monoxide in the stratosphere?

A ground-based search for stratospheric chlorine monoxide was carried out during May and October 1981 with an infrared heterodyne spectrometer in the solar absorption mode. Lines due to stratospheric nitric acid and tropospheric carbonyl sulfide were detected at about 0.2 percent absorptance levels, but the expected 0.1 percent lines of chlorine monoxide in this same region were not seen. Stratospheric chlorine monoxide is less abundant by at least a factor of 7 than is indicated by in situ measurements, and the upper limit for the integrated vertical column density of chlorine monoxide is 2.3 x 10(13) molecules per square centimeter at the 95 percent confidence level. These results imply that the release of chlorofluorocarbons may be significantly less important for the destruction of stratospheric ozone than is currently thought.     

Deceleration of interstellar hydrogen at the heliospheric interface

High-resolution spectra of nearby stars show absorption lines due to material in the local interstellar cloud. This cloud is deduced to be moving at 26 kilometers per second with respect to the sun, and in the same direction as the "interstellar wind" flowing through the solar system. Measurements by the Ulysses spacecraft show that neutral helium is drifting through the solar system at the same velocity, but neutral hydrogen appears to be moving at only 20 kilometers per second, a result confirmed by new measurements of the hydrogen emission line taken by the High-Resolution Spectrograph on the Hubble Space Telescope. These results indicate that neutral hydrogen atoms from the local interstellar cloud are preferentially decelerated at the heliospheric interface, most likely by charge-exchange with interstellar protons, while neutral helium is unaffected by the plasma. The magnitude of the observed deceleration implies an interstellar plasma density of 0.06 to 0.10 per cubic centimeter, which in turn implies that the heliospheric shock should be less than 100 astronomical units from the sun.     

Volatile-rich lunar soil: evidence of possible cometary impact

A subsurface Apollo 16 soil, 61221, is much richer in volatile compounds than soils from any other locations or sites as shown by thermal analysis-gas release measurements. A weight loss of 0.03 percent during the interval 175 degrees to 350 degrees C was associated with the release of water, carbon dioxide, methane, hydrogen cyanide, hydrogen, and minor amounts of hydrocarbons and other species. These volatile components may have been brought to this site by a comet, which may have formed North Ray crater.     

Atmospheric halocarbons, hydrocarbons, and sulfur hexafluoride: global distributions, sources, and sinks

The global distribution of fluorocarbon-12 and fluorocarbon-11 is used to establish a relatively fast interhemispheric exchange rate of 1 to 1.2 years. Atmospheric residence times of 65 to 70 years for fluorocarbon-12 and 40 to 45 years for fluorocarbon-l1 best fit the observational data. These residence times rule out the possibility of any significant missing sinks that may prevent these fluorocarbons from entering the stratosphere. Atmospheric measurements of methyl chloroform support an 8-to 10-year residence time and suggest global average hydroxyl radical (HO) concentrations of 3 x 10(5) to 4 x 10(5) molecules per cubic centimeter. These are a factor of 5 lower than predicted by models. Additionally, methyl chloroform global distribution supports Southern Hemispheric HO levels that are a factor of 1.5 or more larger than the Northern Hemispheric values. The long residence time and the rapid growth of methyl chloroform cause it to be a potentially significant depleter of stratospheric ozone. The oceanic sink for atmospheric carbon tetrachloride is about half as important as the stratospheric sink. A major source of methyl chloride (3 x 10(12)grams per year), sufficient to account for nearly all the atmospheric methyl chloride, has been identified in the ocean.     

Ozone monitoring with an infrared heterodyne radiometer

Measurements of the total burden and of the concentration versus altitude profiles of ozone have been made with a ground-based heterodyne radiometer at Pasadena, California. The measurements were made in the 9.5-micrometer wavelength region, where a strong ozone infrared absorption band exists. The radiometer measured solar absorption at selected wavelengths, with a spectral resolution of 0.001 reciprocal centimeter, equivalent to the half-width of an ozone absorption line at the 10-millibar altitude level. A carbon dioxide laser served as the local oscillator. This technique can be used to gather important data on both tropospheric and stratospheric ozone, which are not readily accessible with other remote-sensing techniques.     

Increase in the stratospheric background sulfuric Acid aerosol mass in the past 10 years

Data obtained from measurements of the stratospheric aerosol at Laramie, Wyoming (41 degrees N), indicate that the background or nonvolcanic stratospheric sulfuric acid aerosol mass at northern mid-latitudes has increased by about 5 +/- 2 percent per year during the past 10 years. Whether this increase is natural or anthropogenic could not be determined at this time because of inadequate information on sulfur sources, in particular, carbonyl sulfide, which is thought to be the dominant nonvolcanic source of stratospheric sulfuric acid vapor. An increase in stratospheric sulfate levels has important climatic implications as well as heterogeneous chemical effects that may alter the concentration of stratospheric ozone.     

Emission of methyl bromide from biomass burning

Bromine is, per atom, far more efficient than chlorine in destroying stratospheric ozone, and methyl bromide is the single largest source of stratospheric bromine. The two main previously known sources of this compound are emissions from the ocean and from the compound's use as an agricultural pesticide. Laboratory biomass combustion experiments showed that methyl bromide was emitted in the smoke from various fuels tested. Methyl bromide was also found in smoke plumes from wildfires in savannas, chaparral, and boreal forest. Global emissions of methyl bromide from biomass burning are estimated to be in the range of 10 to 50 gigagrams per year, which is comparable to the amount produced by ocean emission and pesticide use and represents a major contribution ( approximately 30 percent) to the stratospheric bromine budget.     

Volcanic contribution of chlorine to the stratosphere: more significant to ozone than previously estimated?

Earlier estimates of the chlorine emission from volcanoes, based upon evaluations of the preeruption magmatic chlorine content, are too low for some explosive volcanoes by a factor of 20 to 40 or more. Degassing of ash erupted during 1976 by Augustine Volcano in Alaska released 525 x 10(6) kilograms of chlorine (+/- 40 percent), of which 82 x 10(6) to 175 x 10(6) kilograms may have been ejected into the stratosphere as hydrogen chloride. This stratospheric contribution is equivalent to 17 to 36 percent of the 1975 world industrial production of chlorine in fluorocarbons.     

Hydrogen Cyanide Production During Reduction of Nitric Oxide over Platinum Catalysts: Transient Effects

The formation of hydrogen cyanide during the catalytic reduction of nitric oxide (NO) with carbon monoxide and hydrogen was studied with a bench-scale flow reactor. The previously reported inhibition by sulfur dioxide of the formation of hydrogen cyanide was found to be counteracted by transient admission of oxygen to the catalyst. These results are discussed in the context of the control of automotive emissions of NO and the prevention of hydrogen cyanide production during such control.     

Hydrogen peroxide on the surface of Europa

Spatially resolved infrared and ultraviolet wavelength spectra of Europa's leading, anti-jovian quadrant observed from the Galileo spacecraft show absorption features resulting from hydrogen peroxide. Comparisons with laboratory measurements indicate surface hydrogen peroxide concentrations of about 0.13 percent, by number, relative to water ice. The inferred abundance is consistent with radiolytic production of hydrogen peroxide by intense energetic particle bombardment and demonstrates that Europa's surface chemistry is dominated by radiolysis.     

Chlorine oxide in the stratospheric ozone layer: ground-based detection and measurement

Stratospheric chlorine oxide, a significant intermediate product in the catalytic destruction of ozone by atomic chlorine, has been detected and measured by a ground-based 204-gigahertz, millimeter-wave receiver. Data taken at latitude 42 degrees N on 17 days between 10 January and 18 February 1980 yield an average chlorine oxide column density of approximately 1.05 x 10(14) per square centimeter or approximately 2/3 that of the average of eight in situ balloon flight measurements (excluding the anomalously high data of 14 July 1977) made over the past 4 years at 32 degrees N. We find less chlorine oxide below 35 kilometers and a larger vertical gradient than predicted by theoretical models of the stratospheric ozone layer.