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Harward, C. N.

Publications and source records attributed to Harward, C. N..

In-Situ Measurements of HCN and CH3CN in the Pacific Troposphere: Sources, Sinks, and Comparisons with Spectroscopic Observations

We report the first in-situ measurements of hydrogen cyanide (HCN) and acetonitrile (CH3CN) from the Pacific troposphere (0-12 km) obtained during the NASA/Trace-P mission (Feb.-April, 2001). Mean HCN and CH3CN mixing ratios of 243 (+/-118) ppt and 149 (+/-56) ppt respectively, were measured. The in-situ observations correspond to a total HCN column of 4.4-4.9 x 10(exp 15) molec. cm(exp -2) and a CH3CN column of 2.8-3.0 x 10(exp 15) molec. cm(exp -2). This HCN column is in good agreement with available spectroscopic observations. The atmospheric concentrations of HCN and CH3CN were greatly influenced by outflow of pollution from Asia. There is a linear relationship between the mixing ratios of HCN and CH3CN, and in turn these are well correlated with tracers of biomass combustion (e.g. CH3Cl, CO). Relative enhancements with respect to known tracers of biomass combustion within selected plumes in the free troposphere, and pollution episodes in the boundary layer allow an estimation of a global biomass burning source of 0.8+/-0.4 Tg (N)/y for HCN and 0.4+/-0.1 Tg (N)/y for CH3CN. In comparison, emissions from automobiles and industry are quite small (<0.05 Tg (N)/y). The vertical structure of HCN and CH3CN indicated reduced mixing ratios in the MBL (Marine Boundary Layer). Using, a simple box model, the observed gradients across the top of the MBL are used to derive an oceanic flux of 6.7 x 10(exp -15) g (N) cm(exp -2)/s for HCN and 4.8 x 10(exp -15) g (N) cm(exp -2)/s for CH3CN. An air-sea exchange model is used to conclude that this flux can be maintained if the oceans are under-saturated in HCN and CH3CN by 23% and 17%, respectively. It is inferred that oceanic loss is a dominant sink for these nitrites, and they deposit some 1.3 Tg (N) of nitrogen annually to the oceans. Assuming reaction with OH radicals and loss to the oceans as the major removal processes, a mean atmospheric residence time of 4.7 months for HCN and 5.1 months for CH3CN is calculated. A global budget analysis shows that the sources and sinks of HCN and CH3CN are roughly in balance. There are indications that biogenic sources may also be present. Mechanisms involved in nitrate formation during combustion and removal in the oceans are poorly understood.

Singh, Hanwant B.↗

N2 pressure - broadened O3 line widths and strengths near 1129.4 cm-1

A Beer's Law experiment was performed with a tunable diode laser to find the N2 pressure broadening characteristics of a single 03 absorption line at 1129.426 cm for N2 pressures from 10 to 100 torr (O3 pressure = 3.16 torr). SO2 line positions were used for wavelength calibration. Line shapes were interatively fitted to a Lorentz function. Results were delta (HWHM in MHz) = 47.44 (+ or - 5.34) MHz + 1.730 (+ or - 0.088) MHz/torr *p(torr) with sigma = 0.9897. This intercept compares well with the Doppler O3 - O3 broadened (at 3.16 torr) width of 44.52 Hz. This result in a HWHM line width of 0.44 cm atm at 760 torr and 285 K. The line strengths integrated over delta nu = 0.55 cm were found to be N2 pressure dependent.

Copeland, G. E.↗

High resolution atmospheric spectroscopy using a diode laser heterodyne spectrometer

Ultrahigh resolution (0.007 per cm) atmospheric solar absorption spectra that have been obtained from a tunable infrared heterodyne radiometer are discussed. The radiometer was developed for ground based observations in the 8-12 micron region, and tunability is achieved through the use of Pb-salt semiconductor laser local oscillators. Spectra have been obtained in a piecewise fashion from 9.1 to 11.1 microns using laser emission modes that exhibit characteristics suitable for local-oscillator operation. Spectra showing absorption features of HNO3, O3, CO2, and H2O are presented along with comparisons of experimental and synthetic spectra calculated using a line-by-line atmospheric transmission model.

Hoell, J. M., Jr.↗

Ambient ammonia measurements using laser photo-acoustic spectroscopy

Ammonia concentrations reached minimal levels (approximately 0.1 ppb) in early winter, followed by a sudden later winter increase. A direct relationship between ambient ammonia levels and air temperature was inferred from the data (linear correlation coefficient r=0.53). Ammonia concentrations were determined to be directly related to the absolute humidity of the air (r=0.72); a weaker relationship between ammonia concentrations and relative humidity was discovered (r=0.37). The data also indicated that ammonia levels were generally higher within continental air masses than those of maritime origin. Soil parameters such as pH and moisture content were found to have a major bearing on the release of gaseous ammonia from soils in the region.

Aldridge, M. D., III↗

Ozone air broadening coefficients in the 9-micron region

Air broadening coefficients and line strengths are reported for selected ozone lines in the 8.8 to 10 micron spectral region. These parameters were obtained from a least squares fit of the Voigt line shape to experimental ozone absorption spectra obtained with a tunable diode laser. Analysis of 11 lines in the nu 1 and 18 lines in the nu 3 band suggest a transition dependent coefficient, although no definitive relationship was identified. The average air broadening coefficient for the nu 1 and nu 3 ozone lines is 0.077 and 0.083 per cm/atm, respectively. The measured line strengths are typically 10% to a factor of 2 larger than those given in the AFGL compilation.

Hoell, J. M.↗

Atmospheric ammonia - Measurements and modeling

Ammonia possesses a unique position in the terrestrial atmosphere in that it is the only gaseous basic constituent. Ammonia readily forms aerosols, and by virtue of its high solubility controls the pH of cloud droplets and precipitation. Over the past year a ground-based solar viewing Infrared Heterodyne Radiometer has been used at Langley Research Center to infer the vertical distribution of ammonia. Ground level in situ measurements of ammonia have also been obtained to supplement the profile data. The ammonia profiles have been analyzed and interpreted with a one-dimensional photochemical model of the troposphere to assess the sources and sinks of NH3.

Hoell, J. M., Jr.↗

High-resolution atmospheric spectroscopy using a diode laser heterodyne spectrometer

A tunable-diode-laser radiometer with a spectral resolution of 0.007/cm was used to obtain IR solar absorption spectra in the 9.1-11.1 micron region. Spectra exhibiting absorption by HNO3, CO2, O3, and H2O were obtained in a piecewise manner using emission modes from a single Pb-salt laser local oscillator. The measured spectra were compared to synthetic atmospheric spectra calculated using a line-by-line model. The results demonstrate that high-resolution IR solar absorption spectroscopy and atmospheric extinction measurements can be routinely performed over wide spectral regions using semiconductor lasers.

Hoell, J. M., Jr.↗

Atmospheric solar absorption measurements in the 9 to 11 mu m region using a diode laser heterodyne spectrometer

A tunable diode laser heterodyne radiometer was developed for ground-based measurements of atmospheric solar absorption spectra in the 8 to 12 microns spectral range. The performance and operating characteristics of this Tunable Infrared Heterodyne Radiometer (TIHR) are discussed along with atmospheric solar absorption spectra of HNO3, O3, CO2, and H2O in the 9 to 11 microns spectral region.

Harward, C. N.↗

Excess noise in Pb(1-x)Sn(x)Se semiconductor lasers

The noise characteristics of the TDL were studied for frequencies less than 20 kHz. For heterodyne applications, the high frequency ( 1 MHz) characteristics are also important. Therefore, the high frequency noise characteristics of the TDL were studied as a part of a full TDL characterization program which has been implemented for the improvement of the TDL as a local oscillator in the LHS system. It was observed that all the devices showed similar high frequency noise characteristics even though they were all constructed using different techniques. These common high frequency noise characteristics are reported.

Harward, C. N.↗

Atmospheric solar absorption measurements in the 9-11 micron region using a diode laser heterodyne spectrometer

A tunable diode laser heterodyne radiometer was developed for ground based measurements of atmospheric solar absorption spectra in the 9 to 12 micron spectral range. The performance and operating characteristics of this tunable infrared heterodyne radiometer (TIHR) is discussed along with recently measured heterodyne solar absorption spectra in the 10 to 11 micron spectral region.

Harward, C. N.↗

Remote infrared heterodyne radiometer measurements of atmospheric ammonia profiles

An infrared heterodyne radiometer has been used to study the seasonal variation of the vertical distribution of atmospheric ammonia. The ammonia profiles are inferred from high-resolution atmospheric solar transmittance measurements around the ammonia absorption feature at 927.32323 kaysers. The transmittance data are obtained from six IF channels with spectral resolutions ranging from .0067 to .033 kaysers. Results from this study show a marked decrease in the tropospheric ammonia level with a decrease at ground level from approximately 10 ppb in March 1979 to 1.3 ppb in August 1979.

Hoell, J. M.↗

Tunable diode laser heterodyne radiometer measurement of atmospheric absorption of solar radiation

A tunable infrared heterodyne radiometer (TIHR) which uses a diode laser as the local oscillator is described as well as methods for the evaluation of the excess noise characteristics of the tunable diode laser. Preliminary atmospheric absorption data taken with the TIHR are presented and show the capability of the TIHR for making the highest resolution atmospheric measurements to date.

Harward, C. N.↗

Optical feedback effects on the performance of Pb/1-x/Sn/x/Se semiconductor lasers

The effects of optical feedback on the performance of Pb(1-x)Sn(x)Se semiconductor lasers are reported. Experimental results are presented to demonstrate that uncontrolled optical feedback can occur from optics external to the laser cavity and that these external optical elements can result in the formation of a composite cavity. This composite cavity can sustain a number of narrow closely spaced emission modes with the spectral characteristics of these modes dependent upon the parameters of the cavity. With weak feedback, the spectral width of the amplitude envelope of the new lasing modes resembles that of the original laser mode with no optical feedback. With strongly coupled feedback the envelope of the external cavity modes substantially broadens the apparent linewidth of the laser. It is shown that these effects can be eliminated, and, moreover, they offer the potential for obtaining spectrally narrow single-mode emission from Pb-salt lasers through the use of carefully designed external cavities.

Harward, C. N.↗

The evaluation of a HgCdTe photomixer with a Tunable Diode Laser (TDL) and the evaluation of TDL's as a local oscillator in a heterodyne detection system

Heterodyne systems would be much more versatile if a broadly tunable laser, such as a semiconductor diode laser (TDL), could be used as the local oscillator (LO). Previous studies have shown that while a TDL can be used as an LO, the TDL lack sufficient power to cause the signal-to-noise ratio to be shot noise limited. The heterodyne system with a HgCdTe photodiode as the LO was characterized and the beat frequency response of the heterodyne systems was mapped out.

Harward, C. N.↗

Temperature and pressure dependence of dichloro-difluoromethane (CF2C12) absorption coefficients for CO2 waveguide laser radiation

Measurements were performed to determine the pressure and temperature dependence of CFM-12 absorption coefficients for CO2 waveguide laser radiation. The absorption coefficients of CFM-12 for CO2 waveguide laser radiation were found to have no spectral structure within small spectral bandwidths around the CO2 waveguide laser lines in the CO2 spectral band for pressures above 20 torr. All of the absorption coefficients for the CO2 laser lines studied are independent of pressure above 100 torr, except for the P(36) laser CO2 spectral band. The absorption coefficients associated with the P(42) line in the same band showed the greatest change with temperature, and it also has the largest value of all the lines studied.

Harward, C. N.↗