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Murcray, Frank J.

Publications and source records attributed to Murcray, Frank J..

At least 19 records

Northern and Southern Hemisphere Ground-Based Infrared Spectroscopic Measurements of Tropospheric Carbon Monoxide and Ethane

Time series of CO and C2H, measurements have been derived from high-resolution infrared solar spectra recorded in Lauder, New Zealand (45.0 degrees S, 169.7 degrees E, altitude 0.37 km), and at the U.S. National Solar Observatory (31.9 degrees N, 11, 1.6 degrees W, altitude 2.09 km) on Kitt Peak. Lauder observations were obtained between July 1993 and November 1997, while the Kitt Peak measurements were recorded between May 1977 and December 1997. Both databases were analyzed with spectroscopic parameters that included significant improvements for C2H6 relative to previous studies. Target CO and C2H6 lines were selected to achieve similar vertical samplings based on averaging kernels. These calculations show that partial columns from layers extending from the surface to the mean tropopause and from the mean tropopause to 100 km are nearly independent. Retrievals based on a semiempirical application of the Rodgers optimal estimation technique are reported for the lower layer, which has a broad maximum in sensitivity in the upper troposphere. The Lauder CO and C2H, partial columns exhibit highly asymmetrical seasonal cycles with minima in austral autumn and sharp peaks in austral spring. The spring maxima are the result of tropical biomass burning emissions followed by deep convective vertical transport to the upper troposphere and long-range horizontal transport. Significant year-to-year variations are observed for both CO and C2H6, but the measured trends, (+0.37 +/- 0.57)% yr(exp -1) and (-0.64 +/- 0.79)% yr(exp -1), I sigma, respectively, indicate no significant long-term changes. The Kitt Peak data also exhibit CO and C2H6, seasonal variations in the lower layer with trends equal to (-0.27 +/- 0.17)% yr(exp -1) and (-1.20 +/- 0.35)% yr(exp -1), 1 sigma, respectively. Hence a decrease in the Kitt Peak tropospheric C2H6 column has been detected, though the CO trend is not significant. Both measurement sets are compared with previous observations, reported trends, and three-dimensional model calculations.

Rinsland, Curtis P.↗

Measurements of the Downward Longwave Radiation Spectrum over the Antarctic Plateau and Comparisons with a Line-by-Line Radiative Transfer Model for Clear Skies

A 1-year field program was conducted at South Pole Station in 1992 to measure the downward infrared radiance spectrum at a resolution of 1/ cm over the spectral range 550-1667 cm-'. The atmosphere over the Antarctic Plateau is the coldest and driest on Earth, where in winter, surface temperatures average about -60 C, the total column water vapor is as low as 300 pm of precipitable water, and the clear-sky downward longwave flux is usually less than 80 W/sq m. Three clear-sky test cases are selected, one each for summer, winter, and spring, for which high- quality radiance data are available.as well as ancillary data to construct model atmospheres from radiosondes, ozonesondes, and other measurements. The model atmospheres are used in conjunction with the line-by-line radiative transfer model (LBLRTM) to compare model calculations with the spectral radiance measurements. The high-resolution calculations of LBLRTM (approx. = 0.001/ cm) are matched to the lower-resolution measurements (1/ cm) by adjusting their spectral resolution and by applying a correction for the finite field of view of the interferometer. In summer the uncertainties in temperature and water vapor profiles dominate the radiance error in the LBLRTM calculations. In winter the uncertainty in viewing zenith angle becomes important as well as the choice of atmospheric levels in the strong near-surface temperature inversion. The spectral radiance calculated for each of the three test cases generally agrees with that measured, to within twice the total estimated radiance error, thus validating LBLRTM to this level of accuracy for Antarctic conditions. However, the discrepancy exceeds twice the estimated error in the gaps between spectral lines in the region 1250-1500/ cm, where emission is dominated by the foreign-broadened water vapor continuum.

Walden, Von P.↗

Retrieval of HCl and HNO3 Profiles from Ground-Based FTIR Data Using SFIT2

A recently developed algorithm, SFIT2, is used to assess profile information available in ground-based FTIR measurements of HCl and HNO3 and to analyze spectra recorded at Lauder, New Zealand, and Arrival Heights, Antarctica. It is shown that the altitude range of HCI retrievals may be extended by using multiple spectral lines. A preliminary analysis of a five year record of HNO3 at Lauder shows that the Pinatubo aerosol caused a large increase of HNO3 in a layer at about 20-30 km while having little effect at lower altitude.

Connor, Brian↗

Northern and Southern Hemisphere Ground-Based Infrared Spectroscopic Measurements of Tropospheric Carbon Monoxide and Ethane

Time series of CO and C2H6 measurements have been derived from high resolution infrared solar spectra recorded in Lauder, New Zealand (45.0 deg S, 169.7 deg E, altitude 0.37 km) and at the U. S. National Solar Observatory (31.90 deg N, 111.6 deg W, altitude 2.09 km) on Kitt Peak. Lauder observations were obtained between July 1993 and November 1997 while the Kitt Peak measurements were recorded between May 1977 and December 1997. Both databases were analyzed with spectroscopic parameters that included significant improvements for C2H6 relative to previous studies. Target CO and C2H6 lines were selected to achieve similar vertical samplings based on averaging kernels. These calculations show that partial columns from layers extending from the surface to the mean tropopause and from the mean tropopause to 100 km are nearly independent. Retrievals based on a semiempirical application of the Rodgers optimal estimation technique are reported for the lower layer, which has a broad maximum in sensitivity in the upper troposphere. The Lauder CO and C2H6 partial columns exhibit highly asymmetrical seasonal cycles with minima in austral autumn and sharp peaks in austral spring. The spring maxima are the result of tropical biomass burning emissions followed by deep convective vertical transport to the upper troposphere and long-range horizontal transport. Significant year-to-year variations are observed for both CO and C2H6, but the measured trends, (+0.37 +/- 0.57)%/ yr and (-0.64 +/- 0.79)%/ yr, 1 sigma, respectively, indicate no significant long-term changes. The Kitt Peak data also exhibit CO and C2H6 seasonal variations in the lower layer with trends equal to (-0.27 +/- 0.17)%/ yr and (-1.20 +/- 0.35)%/ yr, 1 sigma, respectively. Hence, a decrease in the Kitt Peak tropospheric C2H6 column has been detected, though the CO trend is not significant. Both measurement sets are compared with previous observations, reported trends, and three-dimensional model calculations.

Rinsland, Curtis P.↗

Seasonal variation of atmospheric nitric acid over the South Pole in 1992

We conducted year-around measurements of mid infrared atmospheric emission over the South Pole in 1992. We were able to observe a large seasonal change of the total column of nitric acid (HNO3) vapor. During the summer the HNO3 column abundance was about 2 x 10(exp 16) molecules/sq cm. There was a small increase in the fall. A rapid decrease of 50% was observed in late June, soon after the stratospheric temperature reached the threshold for formation of type I polar stratospheric clouds (PSCs). By early July, the stratospheric temperature was cold enough to form type II PSCs, and the HNO3 column decreased to 7 x 10(exp 15) molecules/sq cm. Measured nitric acid values in the spring remained extremely low even after the stratosphere warmed well above PSC temperatures. This may indicate permanent removal of HNO3 by gravitational settling, or long-term sequestering in large particles. Normal summer values were not observed until the vortex dissipated and allowed the lateral transport of HNO3 to the south polar region.

Allen, Renate Van↗

The effect of the Mt. Pinatubo aerosol on the NHO3 column over Mauna Loa, Hawaii

A very high resolution infrared solar spectrometer system for the Network for Detection of Stratospheric Change has been routinely operated at the Mauna Loa Observatory in Hawaii since November, 1991. Solar absorption spectra are normally taken one day a week at sunrise. We report the analysis of these spectra for the vertical column amount of nitric acid (HNO3) vapor. The observations began four months after the arrival of volcanic aerosols from Mt. Pinatubo over the site. Although quite variable, total HNO3 columns were initially about 7 x 10(exp 15) molecules/sq cm and have decreased about 30% in the following two years.

David, Shelle J.↗

Measurements of stratospheric odd nitrogen at Arrival Heights, Antarctica, in 1991

An FTIR spectrometer was installed at Arrival Heights, Antarctica (78 deg S, 167 deg E) in February 1991 to measure the evolution of stratospheric HNO3 during the year. In particular, it was the intention to make the first observations of HNO3 trends during autumn, concurrently with ongoing measurements of column NO2 made with a grating spectrometer. The time-series of NO2 in the Antarctic shows a rapid decline in the column amount during autumn, and a slow recovery in spring, as the photochemical conditions move the species to and from higher storage reservoirs. The new nitric acid data show for the first time that during autumn the vertical column increases from approximately 1.9 x 10(exp 16) molecule cm(exp -2) at day 30 to approximately 3.1 x 10(exp 16) molecule cm(exp -2) by day 100. When the sun returns in spring, it is found that the column amount has fallen to about half the value at the end of autumn. Spring amounts are variable, but as found in the data from previous years remain low inside the vortex. The autumn increase is attributed to the heterogeneous conversion of N2O5 to gas-phase HNO3 on background aerosols. Low nitric acid column amounts at the start of spring suggest that the HNO3 has moved from the gas to the condensed phase on polar stratospheric clouds with the advent of low temperatures during the polar night.

Keys, J. Gordon↗

Determination of Total Ozone over Mauna Loa Using Very High Resolution Infrared Solar Spectra

A very high resolution infrared Fourier transform spectrometer has been used to record solar spectra at the Mauna Loa Observatory in Hawaii. Spectra are normally taken one day a week at sunrise. These spectra have been analyzed for ozone and N2O total columns, and the ozone column compared with the value reported by tile Mauna Loa Dobson spectrophotometer. Aside from the FTIR reporting about 5% lower values than the Dobson (which may be due to a systematic difference in the treatment of tropospheric ozone), the FTIR and Dobson agree to within 2.7% (RMS) during this period.

David, Shelle J.↗

Atmospheric sulfur hexafluoride - Sources, sinks and greenhouse warming

An estimate is obtained of worldwide production of SF6, from which a global emission rate is derived and extrapolated for the next 20 years. The atmospheric lifetime of SF6 is then estimated based on a known mechanism (e.g., photolysis and atmospheric oxidation) and/or on the mass balance method. Finally, the radiative forcing of SF6 is calculated based on recent laboratory IR absorption data, and the expected warming over the time period 1950-2010 is computed for several emission scenarios. Calculations showed that SF6 is 3 times more effective as a greenhouse gas compared to CFC 11 on a per-molecule basis. However, based on projected emission scenarios, the expected warming from SF6 through 2010 is small (0.004 C), compared to the warming from CO2 and other trace gases (0.8 C).

Ko, Malcolm K. W.↗

Atmospheric Sulfur Hexafluoride: Sources, Sinks and Greenhouse Warming

Model calculations using estimated reaction rates of sulfur hexafluoride (SF6) with OH and 0('D) indicate that the atmospheric lifetime due to these processes may be very long (25,000 years). An upper limit for the UV cross section would suggest a photolysis lifetime much longer than 1000 years. The possibility of other removal mechanisms are discussed. The estimated lifetimes are consistent with other estimated values based on recent laboratory measurements. There appears to be no known natural source of SF6. An estimate of the current production rate of SF6 is about 5 kt/yr. Based on historical emission rates, we calculated a present-day atmospheric concentrations for SF6 of about 2.5 parts per trillion by volume (pptv) and compared the results with available atmospheric measurements. It is difficult to estimate the atmospheric lifetime of SF6 based on mass balance of the emission rate and observed abundance. There are large uncertainties concerning what portion of the SF6 is released to the atmosphere. Even if the emission rate were precisely known, it would be difficult to distinguish among lifetimes longer than 100 years since the current abundance of SF6 is due to emission in the past three decades. More information on the measured trends over the past decade and observed vertical and latitudinal distributions of SF6 in the lower stratosphere will help to narrow the uncertainty in the lifetime. Based on laboratory-measured IR absorption cross section for SF6, we showed that SF6 is about 3 times more effective as a greenhouse gas compared to CFC 11 on a per molecule basis. However, its effect on atmospheric warming will be minimal because of its very small concentration. We estimated the future concentration of SF6 at 2010 to be 8 and 10 pptv based on two projected emission scenarios. The corresponding equilibrium warming of 0.0035 C and 0.0043 C is to be compared with the estimated warming due to CO2 increase of about 0.8 C in the same period.

Sze, Nien Dak↗

High resolution solar spectrometer system for measuring atmospheric constituents

A mid-IR Michelson interferometer capable of obtaining 0.002/cm resolution solar spectra has been developed for balloon use. The interferometer is based on the Bomem self-aligning instrument, and is equipped with a solar tracking system, telemetry, and recording systems, as well as temperature control and gondola orientation. The interferometer has made two successful flights in the 7-14-micron interval up to 40 km. The basic systems are described and sample spectra are presented.

Murcray, Frank J.↗

Infrared measurements of atmospheric constituents

The objective of this program is to obtain data concerning the concentration versus altitude of various constituents of interest in the photochemistry of the stratospheric ozone layer. Data pertinent to this objective are obtained using balloon-borne instruments to measure the atmospheric transmission and emission in the mid infrared. In addition to obtaining constituent profile information, the spectral data obtained are also used to identify absorption or emission features which may interfere with the retrieval of constituent data from satellite instruments using lower spectral resolution. The spectral resolution obtained with the solar spectral system is 0.0025 cm(exp -1) and represents about a factor of 5 greater resolution than any solar spectra previously obtained in this spectral region. As a result of the increase in spectral resolution, a large number of features are observed in these spectra which were not observed in previous studies. Identification and analysis of these features is in progress. The results of this analysis to date shows a number of HNO3 features which have not been observed before, and these occur where they will interfere with the retrieval of other constituents. An example of the interference is the occurrence of features in the 780.2 cm(exp -1) region which overlap the ClONO2 feature which will be used for retrieval of ClONO2 by the CLAES instrument on UARS. A number of features due to COF2 were also identified in the 1250 cm(exp -1) region which may interfere with retrieval of N2O5.

Murcray, David G.↗

Collecting, analyzing and archiving of ground based infrared solar spectra obtained from several locations

The infrared solar spectrum as observed from the ground under high resolution contains thousands of absorption lines. The majority of these lines are due to compounds that are present in the Earth's atmosphere. Ground based infrared solar spectra contain information concerning the composition of the atmosphere at the time the spectra were obtained. The objective of this program is to record solar spectra from various ground locations, and to analyze and archive these spectra. The analysis consists of determining, for as many of the absorption lines as possible, the molecular species responsible for the absorption, and to verify that current models of infrared transmission match the observed spectra. Archiving is an important part of the program, since a number of the features in the spectra have not been identified. At some later time, when the features are identified, it will be possible to determine the amount of that compound that was present in the atmosphere at the time the spectrum was taken.

Murcray, David G.↗

Analysis of atmospheric spectra for trace gases

The objective is the comprehensive analysis of high resolution atmospheric spectra recorded in the middle-infrared region to obtain simultaneous measurements of coupled parameters (gas concentrations of key trace constituents, total column amounts, pressure, and temperature) in the stratosphere and upper troposphere. Solar absorption spectra recorded at 0.002 and 0.02 cm exp -1 resolutions with the University of Denver group's balloon-borne, aircraft borne, and ground-based interferometers and 0.005 to 0.01 cm exp -1 resolution solar spectra from Kitt Peak are used in the analyses.

Rinsland, Curtis P.↗

HNO3 and HCl amounts over McMurdo during the spring of 1987

Infrared solar spectra were obtained from the ground at McMurdo, Antarctica, during September and October 1987. Absorption features due to HNO3 and HCl have been analyzed to determine the vertical column content of these compounds for the days when observations were made. The variation of these column amounts with time is presented and discussed.

Murcray, Frank J.↗

NH3 column abundances over Lauder, New Zealand

Gaseous NH3 has been observed in the atmosphere over central New Zealand with infrared absorption spectra. The amount of NH3 shows marked variability, which is strongly correlated with time of day and season. The pattern is similar to data obtained in Denver, Colorado, but is much more variable than data from Hampton, Virginia. The rapid variability indicates a residence time of 8 hours in some cases.

Murcray, Frank J.↗

Measurements of several atmospheric gases above the South Pole in December 1986 from high-resolution 3- to 4-micron solar spectra

This paper reports the quantitative analysis of absorption features of a number of atmospheric gases in 0.02/cm resolution 3- to 4-micron solar spectra recorded at the Amundsen-Scott South Pole Station. The measurements were obtained shortly after the austral spring ozone minimum and define, for the first time, the ambient levels of the species immediately following the breakup of the polar vortex. The retrieved total vertical column amounts in molecules per sq cm are: 2.4 + or - 0.4 x 10 to the 21st for H2(O-16), 4.5 + or - 0.5 x 10 to the 18th for H2(O-18), 3.9 + or - 0.4 x 10 to the 17th for HDO, 2.1 + or - 0.2 x 10 to the 19th for CH4, 5.1 + or - 0.5 x 10 to the 21st for CO2, 3.9 + or - 0.4 x 10 to the 18th for N2O, and 3.7 + or - 0.5 x 10 to the 15th for C2H6. Identification of (C-12)H3D absorption features and a search for H2CO absorption in the spectral data are also described.

Goldman, Aaron↗

Infrared measurements of increased CF2Cl2 (CFC-12) absorption above the South Pole

An increase in the CF2Cl2 total vertical column above the South pole of 1.24 + or - 0.15 over a 6-year period from 1980 to 1986, corresponding to an average increase of 3.6 + or - 2.1 percent, is found by high-resolution, ground-based solar spectra analyzed in the nu(8) band Q branches at 1161/cm of CF2Cl. This rate of increase is lower than indicated by in situ measurements at the South Pole over the same period, but substantial agreement results when the rather large error margins of the spectral analysis results are considered.

Rinsland, Curtis P.↗