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At least 19 records

New observations of stratospheric N2O5

The unequivocal detection of N2O5 in the stratosphere was reported by Toon et al. based on measurements of the absorption by the N2O5 bands at 1246 and 1720/cm in solar occulation spectra recorded at sunrise near 47 S latitude by the Atmospheric Trace Molecule Spectroscopy (ATMOS) experiment during the Spacelab 3 (SL3) shuttle mission. Additional measurements and analysis of stratospheric N2O5 derived from the ATMOS/SL3 spectra are reported. The primary results are the detection and measurement of N2O5 absorption at sunset in the lower stratosphere, the inversion of a precise (approximately 10 percent) N2O5 sunrise vertical distribution between 25.5 and 37.5 km altitude, and the identification and measurement of absorption by the N2O5 743/cm band at sunrise. Assuming 4.32 x 10(sup -17) and 4.36 x 10(sup -17)/cm/molecule/sq cm respectively for the integrated intensities of the 1246 and 743/cm bands at stratospheric temperatures, retrieved volume mixing ratios in parts per billion by volume (ppbv) at sunrise (47 S latitude) are 1.32 + or - 0.34 at 37.5 km, 1.53 + or - 0.35 at 35.5 km, 1.63 + or - 0.36 at 33.5 km, 1.60 + or - 0.34 at 31.5 km, 1.43 + or - 0.30 at 29.5 km, 1.15 + or - 0.24 at 27.5 km, and 0.73 + or - 0.15 at 25.5 km. Retrieved VMRs in ppbv at sunset (30 N latitude) are 0.13 + or - 0.05 at 29.5 km, 0.14 + or - 0.05 at 27.5 km, and 0.10 + or - 0.04 at 25.5 km. Quoted error limits (1 sigma) include the error in the assumed band intensities (approximately 20 percent). Within the error limits of the measurements, the inferred mixing ratios at sunrise agree with diurnal photochemical model predictions obtained by two groups using current photochemical data. The measured mixing ratios at sunset are lower than the model predictions with differences of about a factor of 2 at 25 km altitude.

Rinsland, C. P.↗

Stratospheric N2O5 profiles at sunrise and sunset from further analysis of the ATMOS/Spacelab 3 solar spectra

Data obtained by the Atmospheric Trace Molecule Spectroscopy (ATMOS) experiment during the Spacelab 3 (SL3) mission (April 29 to May 6, 1985) indicated the presence of N2O5 in the stratosphere. This paper presents additional analyses of the ATMOS/SL3 spectra carried out to obtain quantitative information on stratospheric N2O5. Results of this analysis include the detection and measurement of weak N2O5 absorption at sunset in the lower stratosphere, the inversion of a precise (about 10 percent) N2O5 sunrise vertical distribution between 25.5 and 37.5 km altitude, and the identification and measurement of absorption by the N2O5 743/cm band at sunrise. Results confirm model predictions that not all of the N2O5 is photodissociated during the day, except in polar regions during the extended daylight of summer.

Rinsland, C. P.↗

Theoretical interpretation of N2O5 measurements

Recent measurements by Webster et al. (1990) have confirmed quantitatively the chemistry controlling the nighttime decay of NO2. Simple equations describing the nighttime behavior of NO2 and N2O5 are presented here. With measurements of the nighttime ozone and NO2 concentrations, these equations can be used to predict the amount of N2O5 produced at any time during the night. In this way, the N2O5 nighttime emission measurement of Roscoe (1982), Kunde et al. (1988) and sunrise measurements of the ATMOS experiment are all used to test theory. The measurements are found to be both self consistent and confirm the present understanding of nighttime NO2 conversion to N2O5. The variation of N2O5 by a factor of two between measurements is found to be consistent with theory.

Toumi, R.↗

Detection of stratospheric N2O5 by infrared remote sounding

Measurements of N2O5 absorption (1230 and 1260 per cm) in infrared spectra were carried out using the Atmospheric Trace Molecule Spectroscopy (ATMOS) instruments on board Spacelab 3. The detection of stratospheric N2O5, a temporary reservoir species whose photolysis products catalyze ozone destruction, was confirmed. Preliminary analysis of spectra recorded at sunrise on 1 May 1985 indicates a peak volume mixing ratio of 1.6 x 10 the -9th at 35 km an altitude of 35 km, or a broad concentration peak pf 4 x 10 to the 8th molecules per cu cm between 21 and 35 km. Absorption was not detected in spectra measured at sunset due to the depletion of N2O5 by photolysis during the day. The volume mixing ratio profile of N2O5 between 0 and 75 km altitude is reproduced in graphic form.

Toon, G. C.↗

Heterogeneous reactions of N2O5 with H2O and HCl on ice surfaces - Implications for Antarctic ozone depletion

This paper reports on the measurements of reaction probabilities for heterogeneous reaction of N2O5 with H2O and HCl on ice surfaces at 195 K, using a fast-flow reactor coupled with a quadrupole mass spectrometer. The reaction probability for N2O5 on pure-water ice was found to be 0.028 + or - 0.011, with nitric acid in the solid phase as the sole product. In the presence of HCl in ice, the probability of N2O5 reaction was enhanced (to 0.037); the reaction produced, besides solid-phase nitric acid, ClNO2 and ClONO which were released into the gas phase within a few milliseconds. The latter two compounds can be readily photolyzed in the austral spring to form active chlorine which would remove stratospheric ozone. It is suggested that, since the polar stratospheric clouds are believed to contain HCl-ice mixture on the surface, the reactions of N2O5 on H2O/HCl particles is a major factor in the Antarctic springtime ozone depletion.

Leu, Ming-Taun↗

Heterogeneous conversion of N2O5 to HNO3 in the post-Mount Pinatubo eruption stratosphere

Simultaneous stratospheric volume mixing ration (VMR) profiles of dinitrogen pentoxide (N2O5) and nitric acid (HNO3) at sunrise between 25 deg N and 15 deg S latitude and profiles of HNO3 at sunset between 42 deg S and 53 deg S latitude have been derived from 0.01/cm resolution infrared solar occultation spectra recorded 9.5 months after the massive eruption of the Mount Pinatubo volcano in the Philippine Islands. The measurements were obtained by the atmospheric trace molecule spectroscopy (ATMOS) Fourier transform spectrometer during the ATLAS 1 shuttle mission (March 24 to April 2, 1992). The measured HNO3 VMRs are higher at all altitudes and latitudes than corresponding values measured by the limb infrared monitor of the stratosphere (LIMS) instrument during the same season in 1979, when the aerosol loading was near background levels. The largest relative increase in the HNO3 VMR occurred near the equator at 30-km altitude, where the ATMOS/ATLAS 1 values are about a factor of 2 higher than the LIMS measurements. Two-dimensional model calculations show that the increase in HNO3 and the ATMOS/ATLAS 1 measurement of a steep decrease in the N2O5 VMR below 30 km can be explained by the enhanced conversion of N2O5 to HNO3 on the surfaces of the Mount Pinatubo sulfate aerosols. Our profile results demonstrate the global impact of the N2O5 + H2O yields 2HNO3 heterogeneous reaction in altering the partitioning of stratospheric odd nitrogen after a major volcanic eruption.

Rinsland, C. P.↗

HNO3, N2O5 and CIONO2 Enhancements after the October-November 2003 Solar Proton Events

The large solar storm in October-November 2003 produced enormous amounts of high-energy protons which reached the Earth and penetrated into the middle atmosphere in the polar regions. At this time, the Michelson Interferometer for Passive Atmospheric Sounding (MIPAS) on board the Environmental Satellite (ENVISAT) was observing the atmosphere in the 6-68 km altitude range. MIPAS observed significant enhancements of the NO(y) components HNO3, N2O5 and CIONO2 in the Northern polar stratosphere after the intense solar proton events. Two distinct HNO3 enhancements were observed. An instantaneous increase of 1-2 ppbv was observed immediately after the SPEs and is attributed to gas-phase chemistry: NO2 + OH + M yields HNO3 + M, accelerated by SPE-produced excess OH. A very large second increase of 1- 5 ppbv started around 10 November and lasted until the end of December. It is attributed to NO(x) (NO+NO2) produced in the mesosphere during the major SPEs in late October/early November and then transported downwards during November and December, partially converted to N2O5 in the upper stratosphere, which finally formed HNO3 via ion cluster reactions. N2O5 was observed to increase by 0.1-0.4 ppbv 1-3 days after the major SPEs and reached down to 30 km altitude. A second, more pronounced N2O5 enhancement of up to 1.2 ppbv at 40 km appeared about 12-13 days after the major SPEs. With a delay of 1-2 days after the major SPEs CIONO2 increased by up to 0.4 ppbv (40%) at 32 km altitude. NO(y) enhancements in the Southern hemisphere were generally less pronounced.

Lopez-Puertas, M.↗

Reaction of N2O5 with H2O on carbonaceous surfaces

The heterogeneous reaction of N2O5 with commercially available ground charcoal in the absence of H2O revealed a physisorption process (gamma = 0.003), together with a redox reaction generating mostly NO. Slow HNO3 formation was the result of the interaction of N2O5 with H2O that was still adsorbed after prolonged pumping at 0.0001 torr. In the presence of H2O, the same processes with gamma = 0.005 are observed. The redox reaction dominates in the early stages of the reaction, whereas the hydrolysis gains importance later at the expense of the redox reaction. The rate law for HNO3 generation was found to be d(HNO3)/dt = k(bi)(H2O)(N2O5) with k(bi), the effective bimolecular rate constants, for 10 mg of carbon being (1.6 + or - 0.3) x 10 to the -13th cu cm/s.

Brouwer, L.↗

N2O5 photolysis products investigated by fluorescence and optoacoustic techniques

Pulsed laser photolysis of N2O5 near 290 nm, coupled with fluorescence detection (calibrated by NO2 photoloysis), showed that the O(P-3) quantum yield is not more than 0.1. A pulsed laser optoacoustic technique in a flow tube was tested by photolysis of NO2 and then applied to N2O5. Nitric oxide was added to react with NO3 free radicals; the resulting increase in the optoacoustic signal confirmed the presence of NO3 free radicals. Based on the relative optoacoustic signals observed for NO2 and N2O5, the quantum yield for NO3 production is 0.8 + or - 0.2.

Barker, J. R.↗

The equilibrium constant for N2O5 = NO2 + NO3 - Absolute determination by direct measurement from 243 to 397 K

Direct determinations of the equilibrium constant for the reaction N2O5 = NO2 + NO3 were carried out by measuring NO2, NO3, and N2O5 using long-path visible and infrared absorption spectroscopy as a function of temperature from 243 to 397 K. The first-order decay rate constant of N2O5 was experimentally measured as a function of temperature. These results are in turn used to derive a value for the rate coefficient for the NO-forming channel in the reaction of NO3 with NO2. The implications of the results for atmospheric chemistry, the thermodynamics of NO3, and for laboratory kinetics studies are discussed.

Cantrell, C. A.↗

Infrared emission measurements of morning stratospheric N2O5

Infrared emission spectra obtained during a balloon flight of the Air Force Geophysics Laboratory Stratospheric Cryogenic Interferometer Balloon Experiment system by the University of Denver are used to measure stratospheric N2O5 after sunrise over New Mexico (latitude 33 deg N). This is the first daytime measurement of N2O5. Comparisons with photochemical modeling show consistency between the observed and predicted decline of N2O5 during the morning hours.

Blatherwick, R. D.↗

Stratospheric N2O5, CH4, and N2O profiles from IR solar occultation spectra

Stratospheric volume mixing ratio profiles of N2O5, CH4, and N2O have been retrieved from a set of 0.052/cm resolution (FWHM) solar occultation spectra recorded at sunrise during a balloon flight from Aire sur l'Adour, France (44 N latitude) on 12 October 1990. The N2O5 results have been derived from measurements of the integrated absorption by the 1246/cm band. Assuming a total intensity of 4.32 x 10 exp -17 cm/molecule/sq cm independent of temperature, the retrieved N2O5 volume mixing ratios in ppbv, interpolated to 2 km height spacings, are 1.64 +/- 0.49 at 37.5 km, 1.92 +/- 0.56 at 35.5 km, 2.06 +/- 0.47 at 33.5 km, 1.95 +/- 0.42 at 31.5 km, 1.60 +/- 0.33 at 29.5 km, 1.26 +/- 0.28 at 27.5 km, and 0.85 +/- 0.20 at 25.5 km. Error bars indicate the estimated 1-sigma uncertainty including the error in the total band intensity. The retrieved profiles are compared with previous measurements and photochemical model results.

Camy-Peyret, C.↗

Heterogeneous reactions of HNO3(g) + NaCl(s) yields HCl(g) + NaNO3(s) and N2O5(g) + NaCl(s) yields ClNO2(g) + NaNO3(s)

The heterogeneous reactions of HNO3(g) + NaCl(s) yields HCl(g) + NaNO3(s) (eq 1) and N2O5(g) + NaCl(s) yields ClNO2(g) + NaNO3(S) (eq 2) were investigated over the temperature range 223-296 K in a flow-tube reactor coupled to a quadrupole mass spectrometer. Either a chemical ionization mass spectrometer (CIMS) or an electron-impact ionization mass spectrometer (EIMS) was used to provide suitable detection sensitivity and selectivity. In order to mimic atmospheric conditions, partial pressures of HNO3 and N2O5 in the range 6 x 10(exp -8) - 2 x 10(exp -6) Torr were used. Granule sizes and surface roughness of the solid NaCl substrates were determined by using a scanning electron microscope. For dry NaCl substrates, decay rates of HNO3 were used to obtain gamma(1) = 0.013 +/- 0.004 (1sigma) at 296 K and > 0.008 at 223 K, respectively. The error quoted is the statistical error. After all corrections were made, the overall error, including systematic error, was estimated to be about a factor of 2. HCl was found to be the sole gas-phase product of reaction 1. The mechanism changed from heterogeneous reaction to predominantly physical adsorption when the reactor was cooled from 296 to 223 K. For reaction 2 using dry salts, gamma(2) was found to be less than 1.0 x 10(exp -4) at both 223 and 296 K. The gas-phase reaction product was identified as ClNO2 in previous studies using an infrared spectrometer. An enhancement in reaction probability was observed if water was not completely removed from salt surfaces, probably due to the reaction of N2O5(g) + H2O(s) yields 2HNO3(g). Our results are compared with previous literature values obtained using different experimental techniques and conditions. The implications of the present results for the enhancement of the hydrogen chloride column density in the lower stratosphere after the El Chichon volcanic eruption and for the chemistry of HCl and HNO3 in the marine troposphere are discussed.

Leu, Ming-Taun↗

Stratospheric N2O5, CH4, and N2O Profiles from IR Solar Occultation Spectra

Stratospheric volume mixing ratio profiles of N2O5, CH4, and N2O have been retrieved from a set of 0.052/ cm resolution (FWHM) solar occultation spectra recorded at sunrise during a balloon flight from Aire sur I'Adour, France (44 deg N latitude) on 12 October 1990. The N2O5 results have been derived from measurements of the integrated absorption by the 1246/ cm band. Assuming a total intensity of 4.32 x 10(exp 17)cm(exp -1) molecule sq cm(exp -2) independent of temperature, the retrieved N2O5 volume mixing ratios in ppbv (parts per billion by volume, 10(exp -9)), interpolated to 2 km height spacings, are 1.64 +/- 0.49 at 37.5 km, 1.92 +/- 0.56 at 35.5 km, 2.06 +/- 0.47 at 33.5 km, 1.95 +/- 0.42 at 31.5 km, 1.60 +/- 0.33 at 29.5 km, 1.26 +/- 0.28 at 27.5 km, and 0.85 +/- 0.20 at 25.5 km. Error bars indicate the estimated I-sigma uncertainty including the error in the total band intensity (+/- 20% has been assumed). The retrieved profiles are compared with previous measurements and photochemical model results.

Peyeret, C. Camy↗

Materials Data on CdRe2H8C2(N2O5)2 by Materials Project

Re2CdC2H8(N2O5)2 crystallizes in the monoclinic P2_1/c space group. The structure is one-dimensional and consists of two Re2CdC2H8(N2O5)2 ribbons oriented in the (1, 0, 0) direction. there are two inequivalent Re7+ sites. In the first Re7+ site, Re7+ is bonded to four O2- atoms to form ReO4 tetrahedra that share corners with two equivalent CdO6 octahedra. The corner-sharing octahedra tilt angles range from 37–42°. There are a spread of Re–O bond distances ranging from 1.74–1.77 Å. In the second Re7+ site, Re7+ is bonded to four O2- atoms to form ReO4 tetrahedra that share corners with two equivalent CdO6 octahedra. The corner-sharing octahedra tilt angles range from 30–44°. There are a spread of Re–O bond distances ranging from 1.74–1.77 Å. Cd2+ is bonded to six O2- atoms to form CdO6 octahedra that share corners with four ReO4 tetrahedra. There are a spread of Cd–O bond distances ranging from 2.24–2.40 Å. There are two inequivalent C4+ sites. In the first C4+ site, C4+ is bonded in a trigonal planar geometry to two N3- and one O2- atom. Both C–N bond lengths are 1.34 Å. The C–O bond length is 1.29 Å. In the second C4+ site, C4+ is bonded in a trigonal planar geometry to two N3- and one O2- atom. Both C–N bond lengths are 1.35 Å. The C–O bond length is 1.28 Å. There are four inequivalent N3- sites. In the first N3- site, N3- is bonded in a trigonal planar geometry to one C4+ and two H1+ atoms. Both N–H bond lengths are 1.02 Å. In the second N3- site, N3- is bonded in a trigonal planar geometry to one C4+ and two H1+ atoms. Both N–H bond lengths are 1.02 Å. In the third N3- site, N3- is bonded in a trigonal planar geometry to one C4+ and two H1+ atoms. Both N–H bond lengths are 1.01 Å. In the fourth N3- site, N3- is bonded in a trigonal planar geometry to one C4+ and two H1+ atoms. There is one shorter (1.01 Å) and one longer (1.02 Å) N–H bond length. There are eight inequivalent H1+ sites. In the first H1+ site, H1+ is bonded in a single-bond geometry to one N3- atom. In the second H1+ site, H1+ is bonded in a single-bond geometry to one N3- atom. In the third H1+ site, H1+ is bonded in a single-bond geometry to one N3- atom. In the fourth H1+ site, H1+ is bonded in a single-bond geometry to one N3- atom. In the fifth H1+ site, H1+ is bonded in a single-bond geometry to one N3- atom. In the sixth H1+ site, H1+ is bonded in a single-bond geometry to one N3- atom. In the seventh H1+ site, H1+ is bonded in a single-bond geometry to one N3- atom. In the eighth H1+ site, H1+ is bonded in a single-bond geometry to one N3- atom. There are ten inequivalent O2- sites. In the first O2- site, O2- is bonded in a distorted bent 150 degrees geometry to one Re7+ and one Cd2+ atom. In the second O2- site, O2- is bonded in a distorted bent 150 degrees geometry to one Re7+ and one Cd2+ atom. In the third O2- site, O2- is bonded in a single-bond geometry to one Re7+ atom. In the fourth O2- site, O2- is bonded in a single-bond geometry to one Re7+ atom. In the fifth O2- site, O2- is bonded in a bent 150 degrees geometry to one Re7+ and one Cd2+ atom. In the sixth O2- site, O2- is bonded in a 2-coordinate geometry to one Re7+ and one Cd2+ atom. In the seventh O2- site, O2- is bonded in a single-bond geometry to one Re7+ atom. In the eighth O2- site, O2- is bonded in a single-bond geometry to one Re7+ atom. In the ninth O2- site, O2- is bonded in a distorted bent 120 degrees geometry to one Cd2+ and one C4+ atom. In the tenth O2- site, O2- is bonded in a distorted bent 120 degrees geometry to one Cd2+ and one C4+ atom.

36 MATERIALS SCIENCE↗

Materials Data on CdRe2C2(N2O5)2 by Materials Project

Re2CdC2(N2O5)2 crystallizes in the monoclinic P2_1/c space group. The structure is one-dimensional and consists of two Re2CdC2(N2O5)2 ribbons oriented in the (1, 0, 0) direction. there are two inequivalent Re7+ sites. In the first Re7+ site, Re7+ is bonded to four O2- atoms to form ReO4 tetrahedra that share corners with two equivalent CdO6 octahedra. The corner-sharing octahedra tilt angles range from 33–49°. There are a spread of Re–O bond distances ranging from 1.73–1.78 Å. In the second Re7+ site, Re7+ is bonded to four O2- atoms to form ReO4 tetrahedra that share corners with two equivalent CdO6 octahedra. The corner-sharing octahedra tilt angles range from 26–40°. There are a spread of Re–O bond distances ranging from 1.73–1.78 Å. Cd2+ is bonded to six O2- atoms to form CdO6 octahedra that share corners with four ReO4 tetrahedra. There are a spread of Cd–O bond distances ranging from 2.23–2.46 Å. There are two inequivalent C4+ sites. In the first C4+ site, C4+ is bonded in a 1-coordinate geometry to two N1- and one O2- atom. Both C–N bond lengths are 1.38 Å. The C–O bond length is 1.21 Å. In the second C4+ site, C4+ is bonded in a 1-coordinate geometry to two N1- and one O2- atom. Both C–N bond lengths are 1.38 Å. The C–O bond length is 1.21 Å. There are four inequivalent N1- sites. In the first N1- site, N1- is bonded in a distorted single-bond geometry to one C4+ atom. In the second N1- site, N1- is bonded in a 1-coordinate geometry to one C4+ and one N1- atom. The N–N bond length is 1.33 Å. In the third N1- site, N1- is bonded in a 1-coordinate geometry to one C4+ atom. In the fourth N1- site, N1- is bonded in a 1-coordinate geometry to one C4+ and one N1- atom. There are ten inequivalent O2- sites. In the first O2- site, O2- is bonded in a single-bond geometry to one Re7+ atom. In the second O2- site, O2- is bonded in a distorted bent 120 degrees geometry to one Re7+ and one Cd2+ atom. In the third O2- site, O2- is bonded in a distorted bent 150 degrees geometry to one Re7+ and one Cd2+ atom. In the fourth O2- site, O2- is bonded in a bent 150 degrees geometry to one Re7+ and one Cd2+ atom. In the fifth O2- site, O2- is bonded in a distorted bent 120 degrees geometry to one Cd2+ and one C4+ atom. In the sixth O2- site, O2- is bonded in a single-bond geometry to one Re7+ atom. In the seventh O2- site, O2- is bonded in a distorted bent 120 degrees geometry to one Cd2+ and one C4+ atom. In the eighth O2- site, O2- is bonded in a bent 150 degrees geometry to one Re7+ and one Cd2+ atom. In the ninth O2- site, O2- is bonded in a single-bond geometry to one Re7+ atom. In the tenth O2- site, O2- is bonded in a single-bond geometry to one Re7+ atom.

36 MATERIALS SCIENCE↗

Pressure and temperature dependence of the reaction NO2 + NO3 + M yields N2O5 + M

The pressure and temperature dependences of the reaction NO2 + NO3 + M which yields N2O5 + M are investigated by using the flash photolysis/visible absorption technique in which the pseudo-first-order decay of NO3 is monitored as a function of total pressure (20-700 torr), diluent gas (M = He and N2), and temperature (236-358 K). The reaction is found to be in the falloff region in the 20-700 torr pressure range with collision efficiencies increasing in the order He less than N2. Falloff parameters are obtained by fitting the experimental data to the falloff equation of Troe and co-workers. The expression for k1(N2 concentration, T) is obtained and compared with the evaluations presented in the NASA (DeMore, 1983) and CODATA (Baulch et al., 1982) reviews of kinetic data for atmospheric chemistry. Both evaluations are based on N2O5 thermal decomposition data coupled with estimates of the equilibrium constant. The significance of the reactions for atmospheric chemistry rests not only on their rates but on the extent to which they result in a permanent sink for NOX.

Kircher, C. C.↗

Antarctic ozone depletion chemistry - Reactions of N2O5 with H2O and HCl on ice surfaces

In a study concerning Antarctic ozone depletion, reactions of dinitrogen pentoxide with water and hydrochloric acid were studied on ice surfaces in a Knudsen cell flow reactor. The N2O5 reacted on ice at 185 K to form condensed-phase nitric acid (HNO3). This reaction may provide a sink for odd nitrogen, NO(x), during the polar winter, a requirement in nearly all models of Antarctic ozone depletion. The reaction of N2O5 on HCl-ice surfaces at 185 K produced gaseous nitryl chloride (ClNO2) and condensed-phase HNO3 and proceeded until all of the HCl within the ice was depleted. The ClNO2 which did not react or condense on ice at 185 K, can be readily photolyzed in the Antarctic spring to form atomic chlorine for catalytic ozone destruction cycles. The other photolysis product, gaseous nitrogen dioxide may be important in the partitioning of NO(x) between gaseous and condensed phases in the Antarctic winter.

Tolbert, Margaret A.↗