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Infrared solar spectra recorded at the International Scientific Station of the Jungfraujoch (3580 m altitude), Switzerland, in 1950-1951 and from 1984 to 1992 have been analyzed to determine vertical column abundances of nitrous oxide (N2O) above the station. The best fit to the relatively dense set of measurements made between 1984 and 1992 indicates a mean exponential rate of increase equal to 0.36 +/- 0.06%/yr (1 sigma) and a seasonal modulation of 7.2% peak to peak, the minimum occurring at the end of the winter and the maximum in early September. The column abundances for April of the years 1951, 1984, and 1992 were found equal to 3.49 x 10(exp 18), 3.76 x 10(exp 18), and 3.87 x 10(exp 18) molecules/sq cm, respectively; they translate into N2O concentrations at the altitude of the Jungfraujoch equal to 275, 296, and 305 parts per billion by volume. These results indicate that the exponential rate of increase for 1951-1984 was equal to 0.23 +/- 0.04%/yr (1 sigma), thus substantially lower than for the 1984-1992 time interval and that the so-called preindustrial levels of N2O pertained until 1951 with most of the increase in atmospheric N2O occurring thereafter.

Attention is given to total vertical column abundances of carbonyl sulfide (OCS) derived from time series of high-resolution IR solar absorption spectra recorded near Tucson, Arizona, and in the Swiss Alps. The analysis of both data sets is based on nonlinear least squares spectral fittings of narrow intervals centered on lines of the intense nu3 band of OCS, the P(37) transition at 2045.5788/cm, and the P(15) transition at 2055.8609/cm, with a consistent set of spectroscopic line parameters. The Arizona measurements, recorded on 20 different days between May 1977 and March 1991, show a 10-percent peak-to-peak seasonal cycle with a summer maximum and a winter minimum and a trend in the total column abundance equal to (0.1 +/-0.2) percent/yr, 2sigma. The Alpine total columns exhibit a more complex seasonal variation than noted in the Arizona data. The results from the two sites indicate that there has been no significant change in the OCS total column abundance at northern midlatitudes over the last decade.

Results derived from a spectroscopic analysis of the nu5 band R19 transition of C2H2 observed in solar spectra recorded at the Jungfraujoch station, Switzerland, between June 1986 and April 1991 are reported. A least-squares sine fit to the data reveals a seasonal variability with an amplitude of about +/-40 percent of the mean; the maximum occurs during mid-winter and the minimum in summer. In general, the observed seasonal observations are comparable with those derived from airborne in-situ measurements and those reported from ground-based stations.

The secular trend and the seasonal cycle of the total and the tropospheric column abundances of C2H6 over the Jungfraujoch Station (Switzerland) were deduced from infrared solar spectra recorded in 1951 and from 1984 to 1988. Results show a definite seasonal variation in the total vertical column abundance of C2H6, with a maximum of (1.43 + or - 0.03) x 10 to the 16th molecules/sq cm during March and April and a minimum in the fall; the ratio between the maximum and the minimum column abundances was found to be 1.62 + or - 0.11. The secular trend in the tropospheric burden above the Jungfraujoch was found to be (0.85 + or - 0.3) percent/yr.

Measuring trends in ozone, and most other geophysical variables, requires that a small systematic change with time be determined from signals that have large periodic and aperiodic variations. Their time scales range from the day-to-day changes due to atmospheric motions through seasonal and annual variations to 11 year cycles resulting from changes in the sun UV output. Because of the magnitude of all of these variations is not well known and highly variable, it is necessary to measure over more than one period of the variations to remove their effects. This means that at least 2 or more times the 11 year sunspot cycle. Thus, the first requirement is for a long term data record. The second related requirement is that the record be consistent. A third requirement is for reasonable global sampling, to ensure that the effects are representative of the entire Earth. The various observational methods relevant to trend detection are reviewed to characterize their quality and time and space coverage. Available data are then examined for long term trends or recent changes in ozone total content and vertical distribution, as well as related parameters such as stratospheric temperature, source gases and aerosols.

The secular increase of the total vertical column abundance of carbon monoxide has been derived from sets of infrared solar spectra recorded from an altitude of 3.58 km at the Jungfraujoch Station, Switzerland, in 1950-1951 and in 1985-1987. The results are based on equivalent width measurements of the R3 line of the 1-0 vibration-rotation band of (C-12)(0-16) at 2159.30/cm. The set of 1985-1987 observations indicates a strong seasonal cycle in the total column abundance of CO, with a + or - 25 percent modulation between minimum values in late summer and the maximum values in late winter. Variability on shorter time scales is also present in both the old and recent data sets. The mean cumulative rate of increase of the total column abundance of CO above the Jungfraujoch is found to be (0.85 + or - 0.20) percent/yr between 1950-1951 and 1985-1987. The present findings are compared with trends reported in earlier studies.

Source gases are defined as those gases that, by their breakdown, introduce into the stratosphere halogen, hydrogen, and nitrogen compounds that are important in stratospheric ozone destruction. Given here is an update of the existing concentration time series for chlorocarbons, nitrous oxide, and methane. Also reviewed is information on halogen containing species and the use of these data for establishing trends. Also reviewed is evidence on trends in trace gases that influence tropospheric chemistry and thus the tropospheric lifetimes of source gases, such as carbon dioxide, carbon monoxide, or nitrogen oxides. Much of the information is given in tabular form.

The long path absorption spectroscopy (LPA) measurement of OH utilizes the strong UV absorption spectrum of the molecule with well resolved rotational lines around 308 nm. The light source consists of an Ar ion laser pumped CW dye laser, the output of which is frequency doubled to emit a spectrally smooth light profile of 0.1 nm FWHM at 308 nm. This is considerably broader than the sharp (0.0018 nm wide) absorption features of OH and also wider than the total spectral region (0.06 nm) scanned around the OH lines. For field measurements a Cassegrain-type telescope expands the small diameter of the original laser beam by a factor of 50 to about a 0.25-m diameter in order to reduce the divergence of the beam as well as its mean photon flux density, thus reducing the maximum self-generated OH concentration to 40,000 cu. cm. The light is passed into the open atmosphere and reflected at about 5 km distance resulting in a 10-km light path length. A telescope focuses the returning light onto the entrance slit of a monochromator the single exit slit of which is replaced by a mechanical scanning device operating at a scan repetition rate of 6.6 KHz. For a typical measurement (1h duration) some 20,000,000 scans are averaged, rendering the contribution of atmospheric turbulence to the spectral noise negligible.

The atmospheric cycles of nitrogenous trace compounds for the Northern and Southern Hemispheres are discussed. Source strengths and destruction rates for the nitrogen oxides: NO, NO2 and HNO3 -(NOX) and ammonia (NH3) are given as a function of latitude over continents and oceans. The global amounts of NOX-N and NH3-N produced annually in the period 1950 to 1975 (34 + 5 x one trillion g NOx-N/yr and 29 + or - 6 x one trillion g NH3-N/yr) are much less than previously assumed. Globally, natural and anthropogenic emissions are of similar magnitude. The NOx emission from anthropogenic sources is 1.5 times that from natural processes in the Northern Hemisphere, whereas in the Southern Hemisphere, it is a factor of 3 or 4 less. More than 80% of atmospheric ammonia seems to be derived from excrements of domestic animals, mostly by bulk deposition: 24 + or - 9 x one trillion g NO3 -N/yr and 21 + or - 9 x one trillion g NH4+-N/yr. Another fraction may be removed by absorption on vegetation and soils.

On 23 May 1973 a cryogenic air sampler was flown on an Aerobee rocket from White Sands Missile Range. A large air sample was collected between 40 and 50 km altitude and successfully recovered for water vapor and trace gas analysis. The results were as follows: water vapor, 4.0 (+1.3 or - 0.9) ppmV; methane, 0.37 + or - 0.01 ppmV; molecular hydrogen, 0.47 + or - 0.02 ppmV; carbon monoxide, 0.05 + or - 0.01 ppmV; carbon dioxide, 316.2 + or - 2.8 ppmV; and nitrous oxide, 3 + or - 7 ppb.

It is argued from the central limit theorem that the uncertainty in model predicted changes of the ozone column density is best represented by a normal probability density distribution. This conclusion is validated by comparison with a probability distribution generated by a Monte Carlo technique. In the case of the CFM-induced ozone depletion, and based on the estimated uncertainties in the reaction rate coefficients alone the relative mean standard deviation of this normal distribution is estimated to be 0.29.

Molecular hydrogen, methane, water vapor and tritium concentrations near stratopause from air samples collected on Aerobee flight with liquid hydrogen cooled cryocondenser

The methane concentration of an air sample collected near the stratopause was measured by gas chromatography and determined to be 0.25 plus or minus 0.02 ppm by volume. The integrity of the air sample with respect to its methane content, the method of analysis, and the result are briefly discussed.