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Global and regional N2O measurements

Real-time N2O measurements have been made in situ at the South Pole, Antarctica, north and south of the equator from on board the Alpha Helix and over the Pacific Ocean on several aircraft flights from the U.S. to New Zealand, Australia and 90 deg S. In addition, an automated EC-GC has been operated for the past year intermittently monitoring N2O in surface air at a rural site in the wheatlands of eastern Washington state. The data obtained are consistent and in agreement with the data obtained from the analyses of a large number of samples collected both from ground stations and a variety of aircraft flights made in the southern and northern hemisphere. The observed global data show no interhemispheric differences. The present concentration of N2O in the troposphere is measured to be 330 + or - 3 ppbv. Its vertical distribution in the troposphere is very uniform. A small decrease (2-3 percent) across the tropopause is characteristically observed in the high-altitude flights.

Rasmussen, R. A.

Stratospheric N2O mixing ratio profile from high-resolution balloon-borne solar absorption spectra and laboratory spectra near 1880/cm

A nonlinear least-squares fitting procedure is used to derive the stratospheric N2O mixing ratio profile from balloon-borne solar absorption spectra and laboratory spectra near 1880/cm. The atmospheric spectra analyzed here were recorded during sunset from a float altitude of 33 km with the University of Denver's 0.02/cm resolution interferometer near Alamogordo, N.M. (33 deg N) on Oct. 10, 1979. The laboratory data are used to determine the N2O line intensities. The measurements suggest an N2O mixing ratio of 264 ppbv near 15 km, decreasing to 155 ppbv near 28 km.

Rinsland, C. P.

In situ aircraft measurements of enhanced levels of N2O associated with thunderstorm lightning

A series of measurements of enhanced levels of atmospheric N2O associated with thunderstorm lightning are reported. The data were gathered by instrumentation on-board an aircraft operated as part of the NASA Storm Hazards Project. Air samples were taken both during storms and in clear conditions to have a basis for comparisons; sample bottles were filled at altitudes from 11,000-40,000 ft. Gas chromatography was employed for sample composition analyses, revealing clear air N2O concentrations of about 310 ppbv, while storm concentrations reached, for example, 490, 729, and 393 ppbv. Although the measurements did not precisely characterize the actual lightning contributions, the enhancements being present during electrically active storms did confirm that trace gases are produced by lightning. Calculations are presented to demonstrate that the 3 to greater than 12 keV X rays detected in storm clouds are of sufficient energy to drive the production of N2O from the reaction of metastable nitrogen with molecular oxygen.

Levine, J. S.

Comparison of the frequencies of NH3, CO2, H2O, N2O, CO, and CH4 as infrared calibration standards

The absolute accuracies of infrared calibration standards for the line positions have been investigated using a 0.0056-kayser-resolution (unapodized) Fourier-transform spectrum recorded from 550 to 5000 kayser. The spectrum has been obtained using a multicell arrangement containing the various molecular species. Detailed comoparisons reveal that standards for CO2, CH4, and N2O obtained from laser research and NH3 from Fourier-transform spectrometer research are consistent within the accuracies of the present data (+ or 0.0001 kayser). However, certain N2O, H2O, and CO values in the 1100-to 2300 kayser region are systematically high by 0.0001 to 0.0004 kayser. Correction factors for the H2O and CO standards are obtained to bring these into agreement with the laser values. In addition, corrected values for the 2nu-2 and nu-1 bands of N2O at 9 microns are reported.

Brown, L. R.

Measurements of CCl3F, CCl2F2, CCl4, N2O and SF6 in the Northern Hemisphere stratosphere

An overview of the Department of Energy's High Altitude Sampling Program and some recent trace gas measurement results are presented. Analysis of whole air samples, collected in pressurized bottles, provides information on stratospheric inventories and distributions for CCl3F, CCl2F2, CCl4, N2O and SF6 in the Northern Hemisphere. Based on a linear regression analysis of the data the estimated mean Northern Hemisphere stratospheric concentration of each gas increased as follows: CCl3F changed from 54 to 142 p1/1 (4/74-11/83); CCl2F2 changed from 133 to 268 p1/1 (4/76-11/83); SF6 changed from 160 to 480 f1/1 (4/74-11/83); CC1, changed from 58 to 91 p1/1 (4/75-11/83); N2O changed from 246 to 261 n1/1 (4/76-11/83). The calculated mean Northern Hemisphere stratospheric concentrations of N2O, CCl3F, CCl2F2, and CCl4 after 1980 show larger than expected fluctuations with time. Recent volcanic activity may be a partial cause for these fluctuations through induced changes in stratospheric dynamical processes.

Leifer, R.

Ozone perturbations by enhanced levels of CFCs, N2O, and CH4 A two-dimensional diabatic circulation study including uncertainty estimates

Observations made over the last few years suggest that the tropospheric concentrations of N2O, CH4, and O3 are increasing. Increases in the concentration of chlorofluorocarbons (CFCs) have been observed for some time. The present study is concerned with combined scenarios of future releases of N2O, CH4, and CFCs, which can affect the height profiles of ozone, while changes in latitudinal gradients of ozone may also be expected. Ozone perturbation calculations performed in the two-dimensional transport-chemistry model described by Stordal et al. (1985) are also presented, and the effects of increased levels of CFCs, N2O, and CH4 are examined. It is found that CH4 may be the most important ozone-perturbing trace species in connection with future tropospheric climatic impacts. A substantial increase in the tropospheric abundancy of CH4 could lead to large future ozone enhancements throughout the troposphere and lower stratosphere at middle and low latitudes.

Isaksen, I. S. A.

Effect of computed horizontal diffusion coefficients on two-dimensional N2O model distributions

The effects of horizontal diffusion coefficients K(yy) and K(yz), computed directly from the residual circulation, on the N2O distribution in a photochemical model were investigated, using a modified version of the two-dimensional model of Guthrie et al. (1984). The residual circulation was computed using the NMC's temperature data and the heating rates reported by Rosenfield et al. (1987). As compared with the effect of the residual circulation alone, the use of horizontal diffusion coefficients produced substantial changes in the N2O distribution and increased the N2O's lifetime values by a few percent. It is suggested that trace gases, such as CH4, CFCl3, CF2Cl2, CH3Cl, and CCl4, which impact the NO(x), HO(x), and Cl(x) radical distributions and therefore ozone, will be influenced in a similar manner by the addition of more realistic diffusion fields.

Jackman, Charles H.

In situ stratospheric measurements of CH4, (C-13)H4, N2O, and OC(O-18) using the BLISS tunable diode laser spectrometer

Simultaneous in situ measurements of stratospheric CH4, (C-13)H4, N2O, OC(O-18), pressure, and temperature have been made from Palestine, Texas (32 deg N) in September 1988 with the JPL Balloon-borne Laser In Situ Sensor. Measurements of CH4 and N2O in the altitude range 30-35 km agree well with other measurements, except for an anomalously high value for the N2O at 31 km. Measurements of CH4 support earlier observations of fold in the vertical profile. A ratio for stratospheric (C-13)H4/CH4 of 0.0105 +/- 0.0010 implies an enrichment of delta(C-13) = -45 +/- 92 parts per thousand over the PDB value, in agreement with previous measurements in the troposphere. A large mixing ratio of 1.9 +/- 0.2 ppmv for OC(O-18) is measured, corresponding to an enrichment of delta(O-18) = 280 +/- 50 parts per thousand for the (O-18) isotopic species over the SMOW value.

Webster, Christopher R.

A toy model for estimating N2O emissions from natural soils

A model of N2O emissions from natural soils, whose ultimate objective is to evaluate what contribution natural ecosystems make to the global N2O budget and how the contribution would change with global change, is presented. Topics covered include carbon and nitrogen available in the soil, delivery of nitrifiable N, soil water and oxygen status, soil water budget model, effects of drainage, nitrification and denitrification potentials, soil fertility, N2O production, and a model evaluation. A major implication of the toy model is that the tropics account for more than 80 percent of global emission.

Fung, Inez

Detection of interstellar N2O: A new molecule containing an N-O bond

A new interstellar molecule, N2O, known as nitrous oxide or 'laughing gas,' has been detected using the NRAO 12 m telescope. The J = 3 - 2, 4 - 3, 5 - 4, and 6 - 5 rotational transitions of this species at 75, 100, 125, and 150 GHz, respectively, were observed toward Sgr B2(M). The column density derived for N2O in this source is N(sub tot) approx. 10(exp 15)/sq. cm, which corresponds to a fractional abundance of approx. 10(exp -9), relative to H2. This value implies abundance ratios of N2O/NO approx. 0.1 and N2O/HNO approx. 3 in the Galactic center. Such ratios are in excellent agreement with predictions of ion-molecule models of interstellar chemistry using early-time calculations and primarily neutral-neutral reactions. N2O is the third interstellar molecule detected thus far containing an N-O bond. Such bonds cannot be so rare as previously thought.

Ziurys, L. M.

Northern hemisphere mid-stratosphere vortex processes diagnosed from H2O, N2O and potential vorticity

Microwave Limb Sounder (MLS) H2O Cryogenic Limb Array Etalon Spectrometer (CLAES) N2O and potential vorticity calculated from UK Meteorological Office data are used to study mid-stratospheric vortex processes in the northern hemisphere winter of 1991-1992. Areas of moist air (at approx. 20 hPa) and N2O-poor air (at approx. 10hPa) are well-correlated with high values of potential vorticity and there is little or no large scale mixing across the vortex edge. We find evidence for the descent of relatively dry mesospheric air to the 840 K (approx. 10 hPa) level, as well as descent of moist air from the upper stratosphere to the 655 K (approx. 20 hPa) level. A reduction in the areas of the vortex and both the moist and H2O-poor regions is observed and there is evidence of moist and N2O-poor air parcels being extruded from the vortex.

Lahoz, W. A.

Tracer-tracer relationships and lower stratospheric dynamics: CO2 and N2O correlations during SPADE

Simultaneous measurements of CO2 and N2O from the NASA ER-2 aircraft during SPADE deployments in November 1992, April/May 1993, and October 1993 provide new information on transport rates in the lower stratosphere. The tropospheric seasonal cycle in CO2, superimposed on the long-term trend, is observed to propagate into the statosphere. The compact correlations observed between CO2 and N2O indicate that meridional transport is sufficiently rapid to create a uniform set of relationships over the northern hemisphere up to at least 21 km even though CO2 changes significantly on a time scale of 8 to 12 weeks. the observed seasonal dependence of the correlations indicates that vertical transport above 20 km is slower in northern summer than in winter and slow throughout the year between 19 km and the tropopause. The inferred amplitude of the seasonal CO2 oscillation in the statopshere, viewed relative to N2O, places constraints on the mean latitude for air entering the statosphere.

Boering, Kristie A.

N2O as an indicator of Arctic vortex dynamics: Correlations with O3 over Thule, Greenland in February and March, 1992

We have recovered vertical profiles of stratospheric N2O from spectra observed using a ground-based mm-wave spectrometer during the Arctic spring. The measurements were made from Thule, Greenland (76.3 deg N, 68.4 deg W) on nine occasions from late February to late March, 1992 as part of the Upper Atmosphere Research Satellite (UARS) Correlative Measurements Program and the European Arctic Stratospheric Ozone Experiment (EASOE). During late February Thule was under inside edge of the Arctic vortex and mixing ratio profiles measured in that period are substantially reduced from typical high-latitude summer values. By late March the polar vortex had moved well away from Thule and N2O mixing ratios were greatly increased, coinciding with a basic change in circulation that brought in air from the Aleutian high. The motion of the vortex is also illustrated in the change in potential vorticity above Thule. A correlation with ozone balloonsonde data from Thule is made and compared to similar analyses of the Airborne Arctic Stratospheric Expedition (AASE) measurements. Within the sensitivity of our analysis, the correlation of N2O and O3 shows no evidence of ozone depletion within the vortex during this period; however, there is a distinct difference in the correlation inside and outside the vortex.

Emmons, L. K.

NO(y) Correlation with N2O and CH4 in the Midlatitude Stratosphere

Total reactive nitrogen (NO(y)), nitrous oxide (NO2), methane (CH4), and ozone (03) were measured on board a balloon launched from Aire sur l'Adour (44 deg N, 0 deg W), France on October 12, 1994. Generally, NO(y) was highly anti-correlated with N2O and CH4 at altitudes between 15 and 32 km. The linear NO(y) - N2O and NO(y) - CH4 relationships obtained by the present observations are very similar to those obtained on board ER-2 and DC-8 aircraft previously at altitude below 20 km in the northern hemisphere. They also agree well with the data obtained by the Atmospheric Trace Molecule Spectroscopy (ATMOS) instrument at 41 deg N in November 1994. Slight departures from linear correlations occurred around 29 km, where N2O and CH4 mixing ratios were larger than typical midlatitude values, suggesting horizontal transport of tropical airmasses to northern midlatitudes in a confined altitude region.

Kondo, Y.

The Seasonal and Interannual Variability of the Budgets of N2O and CCl3F

The 6-year wind archives from the Goddard Institute for Space Studies/Global Climate-Middle Atmosphere Model (GISS/GCMAM) were in- put to the GISS/Harvard/Irvine Chemical Transport Model (G/H/I CTM) to study the seasonal and interannual variability of the budgets and distributions of nitrous oxide (N2O) and trichlorofluoromethane (CCl3F), with the corresponding chemical loss frequencies recycled and boundary conditions kept unchanged from year to year. The effects of ozone feedback and quasi-biennial oscillation (QBO) were not included. However, the role of circulation variation in driving the lifetime variability is investigated. It was found that the global loss rates of these tracers are related to the extratropical planetary wave activity, which drives the tropical upward mass flux. For N2O, a semiannual signal in the loss rate variation is associated with the interhemispheric asymmetry in the upper stratospheric wave activity. For CCl3F, the semiannual signal is weaker, associated with the comparatively uniform wave episodes in the lower stratosphere. The loss rates lag behind the wave activity by about 1-2 months. The interannual variation of the GCM generated winds drives the interannual variation of the annually averaged lifetime. The year-to-year variations of the annually averaged lifetimes can be about 3% for N2O and 4% for CCl3F.

Wong, Sun

Mean Ages of Stratospheric Air Derived From in Situ Observations of CO2, CH4, and N2O

Accurate mean ages for stratospheric air have been derived from a spatially and temporally comprehensive set of in situ observations of CO2, CH4, and N2O obtained from 1992 to 1998 from the NASA ER-2 aircraft and balloon flights. Errors associated with the tropospheric CO2 seasonal cycle and interannual variations in the CO2 growth rate are less than 0.5 year throughout the stratosphere and less than 0.3 year for air older than 2 years (N2O less than 275 ppbv), indicating that the age spectra are broad enough to attenuate these influences over the time period covered by these observations. The distribution of mean age with latitude and altitude provides detailed, quantitative information about the general circulation of the stratosphere. At 20 km, sharp meridional gradients in the mean age are observed across the subtropics. Between 20 and 30 km, the average difference in mean age between the tropics and midlatitudes is approximately 2 years, with slightly smaller differences at higher and lower altitudes. The mean age in the midlatitude middle stratosphere (approx. 25-32 km) is relatively constant with respect to altitude at 5 plus or minus 0.5 years. Comparison with earlier balloon observations of CO2 dating back to the 1970s indicates that the mean age of air in this region has remained within 11 year of its current value over the last 25 years. A climatology of mean age is derived from the observed compact relationship between mean age and N2O. These characteristics of the distribution of mean age in the stratosphere will serve as critically needed diagnostics for models of stratospheric transport.

Andrews, A. E.

UV Absorption Cross Sections of Nitrous Oxide (N2O) and Carbon Tetrachloride (CCl4) Between 210 and 350 K and the Atmospheric Implications

Absorption cross sections of nitrous oxide (N2O) and carbon tetrachloride (CCl4) are reported at five atomic UV lines (184.95, 202.548, 206.200, 213.857, and 228.8 nm) at 27 temperatures in the range 210-350 K. In addition, UV absorption spectra of CCl4 are reported between 200-235 nm as a function of temperature (225-350 K). The results from this work are critically compared with results from earlier studies. For N2O, the present results are in good agreement with the current JPL recommendation enabling a reduction in the estimated uncertainty in the N2O atmospheric photolysis rate. For CCl4, the present cross section results are systematically greater than the current recommendation at the reduced temperatures most relevant to stratospheric photolysis. The new cross sections result in a 5-7% increase in the modeled CCl4 photolysis loss, and a slight decrease in the stratospheric lifetime, from 51 to 50 years, for present day conditions. The corresponding changes in modeled inorganic chlorine and ozone in the stratosphere are quite small. A CCl4 cross section parameterization for use in 37 atmospheric model calculations is presented.

Carlon, Nabilah Rontu

Infrared Spectra and Band Strengths of Amorphous and Crystalline N2O

Infrared transmission spectra from 4000 to 400 cm (exp -1), and associated band strengths and absorption coefficients, are presented for the first time for both amorphous and crystalline N2O. Changes in the spectra as a function of ice thickness and ice temperature are shown. New measurements of density, refractive index, and specific refraction are reported for amorphous and crystalline N2O. Comparisons are made to published results, and the most-likely reason for some recent disagreements in the literature is discussed. As with CO2, its isoelectronic congener, the formation of amorphous N2O is found to require greater care than the formation of amorphous solids from more-polar molecules.

Infrared spectra