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Blatherwick, R. D.

Publications and source records attributed to Blatherwick, R. D..

At least 19 records

Infrared Solar Spectroscopic Measurements of Free Tropospheric CO, C2H6, and HCN above Mauna Loa, Hawaii: Seasonal Variations and Evidence for Enhanced Emissions from the Southeast Asian Tropical Fires of 1997-1998

High spectral resolution (0.003 per cm) infrared solar absorption measurements of CO, C2H6, and HCN have been recorded at the Network for the Detection of Stratospheric Change station on Mauna Loa, Hawaii, (19.5N, 155.6W, altitude 3.4 km). The observations were obtained on over 250 days between August 1995 and February 1998. Column measurements are reported for the 3.4-16 km altitude region, which corresponds approximately to the free troposphere above the station. Average CO mixing ratios computed for this layer have been compared with flask sampling CO measurements obtained in situ at the station during the same time period. Both show asymmetrical seasonal cycles superimposed on significant variability. The first 2 years of observations exhibit a broad January-April maximum and a sharper CO minimum during late summer. The C2H6 and CO 3.4-16 km columns were highly correlated throughout the observing period with the C2H6/CO slope intermediate between higher and lower values derived from similar infrared spectroscopic measurements at 32'N and 45'S latitude, respectively. Variable enhancements in CO, C2H6, and particularly HCN were observed beginning in about September 1997. The maximum HCN free tropospheric monthly mean column observed in November 1997 corresponds to an average 3.4-16 km mixing ratio of 0.7 ppbv (1 ppbv = 10(exp -9) per unit volume), more than a factor of 3 above the background level. The HCN enhancements continued through the end of the observational series. Back-trajectory calculations suggest that the emissions originated at low northern latitudes in southeast Asia. Surface CO mixing ratios and the C2H6 tropospheric columns measured during the same time also showed anomalous autumn 1997 maxima. The intense and widespread tropical wild fires that burned during the strong El Nino warm phase of 1997- 1998 are the likely source of the elevated emission products.

Rinsland, C. P.↗

Infrared Solar Spectroscopic Measurements of Free Tropospheric CO, C2H6, and HCN above Mauna Loa, Hawaii: Seasonal Variations and Evidence for Enhanced Emissions from the Southeast Asian Fires of 1997-1998

High spectral resolution (0.003/ cm) infrared solar absorption measurements of CO, C2H6, and HCN have been recorded at the Network for the Detection of Stratospheric Change station on Mauna Loa, Hawaii, (19.5 deg N, 155.6 deg W, altitude 3.4 km). The observations were obtained on over 250 days between August 1995 and February 1998. Column measurements are reported for the 3.4 - 16 km altitude region, which corresponds approximately to the free troposphere above the station. Average CO mixing ratios computed for this layer have been compared with flask sampling CO measurements obtained in situ at the station during the same time period. Both show asymmetrical seasonal cycles superimposed on significant variability. The first two years of observations exhibit a broad January-April maximum and a sharper CO minimum during late summer. The C2H6 and CO 3.4 - 16 km columns were highly correlated throughout the observing period with the C2H6/CO slope intermediate between higher and lower values derived from similar infrared spectroscopic measurements at 32 deg N and 45 deg S latitude, respectively. Variable enhancements in CO, C2H6, and particularly HCN were observed beginning in about September 1997. The maximum HCN free tropospheric monthly mean column observed in November 1997 corresponds to an average 3.4 - 16 km mixing ratio of 0.7 ppbv (1 ppbv = 10(exp -9) per unit volume), more than a factor of 3 above the background level. The HCN enhancements continued through the end of the observational series. Back-trajectory calculations suggest that the emissions originated at low northern latitudes in southeast Asia. Surface CO mixing ratios and the C2H6 tropospheric columns measured during the same time also showed anomalous autumn 1997 maxima. The intense and widespread tropical wild fires that burned during 3 the strong El Nino warm phase of 1997-1998 are the likely source of the elevated emission products.

Rinsland, C. P.↗

Thermal infrared spectra of the Moon

Contrary to recent assertions in the literature, lunar emission spectra obtained at an altitude of 32 km with a balloon-borne telescope are virtually undistorted by atmospheric absorption, except in the ozone region. These spectra have been found to correlate closely with laboratory emission spectra of returned lunar samples measured in a simulated lunar environment. Thus, lunar spectra obtained with the balloon-borne telescope system are the standards against which groundbased spectral measurements of the Moon should be compared. Comparison of balloon-borne measurements with recent groundbased spectral measurements suggests that the latter suffer from some source of systematic error. When high-quality lunar spectra are available, they will be best interpreted by comparison with returned lunar samples, rather than terrestrial minerals or rocks, because of subtle spectral differences between lunar and terrestrial minerals perhaps associated with incipient alteration of the latter.

Salisbury, John W.↗

Infrared spectroscopic measurements of the ethane (C2H6) total column abundance above Mauna Loa, Hawaii -- seasonal variations

About 200 i.r. solar spectra recorded at 0.01/cm resolution on 71 days between November 1991 and July 1993 at the Network for the Detection of Stratospheric Change (NDSC) station at Mauna Loa, Hawaii (latitude 19.53 deg N, longitude 155.58 deg W, elevation 3.459 km) have been analyzed with a nonlinear least-squares spectral fitting technique to study temporal variations in the total column of atmospheric ethane (C2H6) above the site. The results were derived from the analysis of the unresolved nu(sub 7) band (P)Q(sub 3) subbranch at 2976.8/cm. A distinct seasonal cycle is observed with a factor of 2 variation, a maximum total column of 1.16 x 10(exp 16) mol/sq cm at the end of winter, and a minimum total column of 0.53 x 10(exp 16) mol/sq cm at the end of summer. Our measurements are compared with previous observations and model predictions.

Rinsland, C. P.↗

High resolution studies of heacy NO(y) molecules in atmospheric spectra

New line parameters for two heavy odd nitrogen molecules HNO3 in the nu(sub 5)/2nu(sub 9) region, and ClONO2 in the nu(sub 4) region are incorporated in the analysis of high resolution i.r. atmospheric spectra. The line parameters are tested and renormalized vs laboratory spectra, and then applied to retrievals from balloon-borne and ground-based solar absorption spectra.

Goldman, A.↗

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↗

Infrared Spectroscopic Measurements of the Ethane (C2H6) Total Column Abundance Above Mauna Loa, Hawaii: Seasonal Variations

About 200 i.r. solar spectra recorded at 0.01/ cm resolution on 71 days between November 1991 and July 1993 at the Network for the Detection of Stratospheric Change (NDSC) station at Mauna Loa, Hawaii (latitude 19.53 deg N, longitude 155.58 deg W, elevation 3.459 km) have been analyzed with a nonlinear least-squares spectral fitting technique to study temporal variations in the total column of atmospheric ethane (C2H6) above the site. The results were derived from the analysis of the unresolved nu(sub 7) band (sup P)Q(sub 3) subbranch at 2976.8/cm. A distinct seasonal cycle is observed with a factor of 2 variation, a maximum total column of 1.1 6 x 10(exp 16) mol /sq cm at the end of winter, and a minimum total column of 0.53 x 10(exp 16) mol/sq cm at the end of summer. Our measurements are compared with previous observations and model predictions.

Rinsland, C. P.↗

High Resolution Studies of Heavy NO(y) Molecules in Atmospheric Spectra

New line parameters for two heavy odd nitrogen molecules HNO3 in the upsilon(sub 5)/2upsilon(sub 9) region, and ClONO2 in the upsilon(sub 4) region are incorporated in the analysis of high resolution i.r. atmospheric spectra. The line parameters arc tested and renormalized vs laboratory spectra, and then applied to retrievals from balloon-borne and ground-based solar absorption spectra.

Goldman, A.↗

The nu(sub 2) and 2nu(sub 2) - nu(sub 2) bands of N-14 (16)O2: Electron Spin-Rotation and Hyperfine Contact Resonances in the (010) Vibrational State

High-resolution Fourier transform spectra covering the 720-9-10/ cm spectral region have been used to perform a reanalysis of the 2nu(sub 2) band ((010) - (000) vibrational transition) together with the first analysis of the nu(sub 2) - nu(sub 2) hot band of nitrogen dioxide ((020)-(010) vibrational transition). The high-quality spectra show that, for numerous nu(sub 2) lines, the hyperfine structure is easily observable in the case of resonances due to the hyperfine Fermi-type operator. By performing a full treatment of the spin-rotation and of the hyperfine operators, a near line list of the nu(sub 2) band (positions and intensities) has been generated, and it is in excellent agreement with the experimental spectrum. Also, a thorough analysis of the -2nu(sub 2) nu(sub 2) hot band has been performed leading to an extended set of new (020) spin-rotation levels, These levels, together with the (100), (020), (001) spin-rotation levels deduced previously from the analysis of thenu(sub 1), 2nu(sub 2), and nu(sub 3) cold bands performed in the 6.3 - to 7.5 microns spectral range were least-squares fitted, allowing one to derive a new set of vibrational band centers and rotational. spin-rotation, and interaction constants for the {(100)(020)(001)} interacting states of N-14(16)O2.

Perrin, A.↗

Measurements and model calculations of HCl column amounts and related parameters over McMurdo during the austral spring in 1989

Solar spectra obtained from a ground-based Fourier transform infrared instrument at McMurdo (Antarctica) in the spring of 1989 have been analyzed to determine total HCl column amounts. A one-dimensional photochemical model was used to simulate the rate of recovery of HCl in the springtime. Low column amounts (about 1 x 10 exp 15 molecules/sq cm) were observed in early September and may be attributed to the heterogeneous conversion of HCl to active chlorine species during the polar night. The rate of recovery of HCl is consistent with its production by chlorine atoms reacting with methane and is dependent on concentrations of active chlorine species and NO molecules in the altitude region from 12 to 22 km. High HCl column amounts (about 7 x 10 exp 15 molecules/sq cm) were observed following recovery in late October, suggesting that the lower stratosphere in the polar region had descended relative to mid-latitudes and that the degree of dechlorination of the transported air was very small.

Liu, X.↗

Stratospheric HNO3 measurements from 0.002/cm resolution solar occultation spectra and improved spectroscopic line parameters in the 5.8-micron region

Very-high-resolution FWHM solar-occultation spectra are investigated with a balloon-borne interferometer using revised spectroscopic line parameters for HNO3, O3, and H2O. The O3 and H2O data are evaluated to determine their capacity for interference in the HNO3 line which is studied in the nu sub 2 band at 5.8 microns. The line parameters developed with the stratospheric data are compared to data based on a HITRAN compilation as well as laboratory spectra with a 0.002/cm resolution. The line list is calculated and shown to include J and Ka transitions which improve the line parameters for HNO3 by accounting for the weaker absorption features in the stratospheric spectra. The stratospheric HNO3 profile developed analytically is compared to those based on reported measurements, and the one developed with the stratospheric solar spectra is found to be consistent with the measurements and confirm inherent measurement biases.

Goldman, A.↗

Mt. Pinatubo SO2 column measurements from Mauna Loa

Absorption features of the nu sub 1 band of SO2 are identified in high-resolution IR solar-absorption spectra recorded from Mauna Loa, Hawaii, on July 9 and 12, 1991, shortly after the arrival of the first eruption plume from the Mt. Pinatubo volcano. A total SO2 vertical column amount of (5.1 +/- 0.5) x 10 exp 16 molecules/sq cm on July 9 is retrieved based on nonlinear least-squares spectral fittings of 9 selected SO2 absorption features with an updated set of SO2 spectral parameters. A SO2 total-column upper limit of 0.9 x 10 exp 16 molecules/sq cm deduced from measurements on September 20-24, 1991, is consistent with the dispersion of the SO2 cloud and the rapid conversion of the SO2 vapor into volcanic aerosol particles.

Goldman, A.↗

Mt. Pinatubo SO2 Column Measurements From Mauna Loa

Absorption features of the nu(sub 1) band of SO2 have been identified in high resolution infrared solar absorption spectra recorded from Mauna Loa, Hawaii, on July 9 and 12, 1991, shortly after the arrival of the first eruption plume from the Mt. Pinatubo volcano in the Phillipines. A total SO2 vertical column amount of (5.1 +/- 0.5) x 10(exp 16) molecules/sq cm on July 9 has been retrieved based on nonlinear least- squares spectral fittings of 9 selected SO2 absorption features with an updated set of SO2 spectral parameters. A SO2 total column upper limit of 0.9 x 10(esp 16) molecules/sq cm deduced from measurements on September 20-24, 1991, is consistent with the dispersion of the SO2 cloud and the rapid conversion of the SO2 vapor into volcanic aerosol particles.

Goldman, A.↗

Analysis of atmospheric trace constituents from high resolution infrared balloon-borne and ground-based solar absorption spectra

Results of ongoing studies of high-resolution solar absorption spectra aimed at the identification and quantification of trace constituents of importance in the chemistry of the stratosphere and upper troposphere are presented. An analysis of balloon-borne and ground-based spectra obtained at 0.0025/cm covering the 700-2200/cm interval is presented. The 0.0025/cm spectra, along with corresponding laboratory spectra, improves the spectral line parameters, and thus the accuracy of quantifying trace constituents. Results for COF2, F22, SF6, and other species are presented. The retrieval methods used for total column density and altitude distribution for both ground-based and balloon-borne spectra are also discussed.

Goldman, A.↗

Determination of the altitude of the nitric acid layer from very high resolution ground-based IR solar spectra

A ground-based solar spectrum at a spectral resolution of about 0.002/cm is used to determine the altitude of the HNO3 layer. The 870/cm spectral region, which is essentially free from absorptions from other species, is employed. The data were obtained with the University of Denver 2.5-m maximum path difference Fourier Transform interferometer spectrometer system. A set of 13 HNO3 vertical profiles were used in the analysis. The best fit obtained for the 'starting' profile (which is centered at 24 km), and the best fit for the profile centered at 26 km are shown. For displacements of greater than 2 km, the discrepancy between the synthetic and observed spectra becomes readily discernible by inspection of the spectra. It is shown that the 'best fit' rms residuals are quite sensitive to the assumed altitude of the HNO3 layer.

Blatherwick, R. D.↗

High-resolution studies of atmospheric IR emission spectra

Atmospheric emission spectra obtained with two different spectrometer systems are presented. The first system (the BOMEM Michelson interferometer) is designed for emission work. Spectra were obtained under adverse conditions in the Antarctic, and are still of good absolute accuracy. The second system (a modified Bruker Instruments IFS120 very high spectral resolution interferometer) demonstrates the sensitivity that can be achieved even at higher spectral resolution. This system shows that mid-IR atmospheric emission spectra can be obtained with a good SNR in a reasonable length of time at a relatively high resolution. A properly designed high resolution system should achieve high accuracy, sensitivity, and resolution, thereby permitting measurements of many atmospheric constituents when solar spectra cannot be obtained.

Murcray, F. J.↗

Analysis of Atmospheric Trace Constituents from High Resolution Infrared Balloon-Borne and Ground-Based Solar Absorption Spectra

Recent results and ongoing studies of high resolution solar absorption spectra will be presented. The analysis of these spectra is aimed at the identification and quantification of trace constituents important in atmospheric chemistry of the stratosphere and upper troposphere. Analysis of balloon-borne and ground-based spectra obtained at 0.0025/ cm covering the 700-2200/ cm interval will be presented. Results from ground-based 0.02/ cm solar spectra, from several locations such as Denver, South Pole, M. Loa, and New Zealand will also be shown. The 0.0025/ cm spectra show many new spectroscopic features. The analysis of these spectra, along with corresponding laboratory spectra, improves the spectral line parameters, and thus the accuracy of trace constituents quantification. The combination of the recent balloon flights, with earlier flights data since 1978 at 0.02/ cm resolution, provides trends analysis of several stratospheric trace species. Results for COF2, F22, SF6, and other species will be presented. Analysis of several ground-based solar spectra provides trends for HCl, HF and other species. The retrieval methods used for total column density and altitude distribution for both ground-based and balloon-borne spectra will be presented. These are extended for the analysis of the ground-based spectra to be obtained by the high resolution interferometers of the Network for Detection of Stratospheric Change (NDSC). Progress or the University of Denver studies for the NDSC will be presented. This will include intercomparison of solar spectra and trace gases retrievals obtained from simultaneous scans by the high resolution (0.0025/ cm) interferometers of BRUKER and BOMEM.

Goldman, A.↗

Long-term trends in the concentrations of SF6, CHClF2, and COF2 in the lower stratosphere from analysis of high-resolution infrared solar occultation spectra

Long-term trends in the concentrations of SF6, CHClF2 in the lower stratosphere are derived using results from analyses of the 1980 and of several more recently obtained IR solar occultation spectra. Results show that the increase rates of SF6 and CHClF2 were about 7.4/yr and 9.4/yr, respectively, which correspond to cumulative increases by factors of about 1.7 and 2.0 in the concentrations of these gases over the 7.2 yr measurement period. The average increase rate for COF2 was 10.3/yr over the same time period. The present results are compared with previously reported observations and trends and with one-dimensional model calculations.

Rinsland, C. P.↗