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Hard, T. M.

Publications and source records attributed to Hard, T. M..

Diurnal HO2 cycles at clean air and urban sites in the troposphere

HO2 concentrations at two Oregon sites were determined for continuous periods of 36 to 48 hours, using fluorescence assay with gas expansion. At the sea level coastal site, NNW winds prevailed during daytime, and a point measurement of very low total nonmethane hydrocarbon concentration indicated the presence of remote tropospheric air of oceanic origin. At the urban site, HO2 was determined during moderately low ozone pollution levels. At both sites, maximum daily (HO2) was in the range of 1-2 x 10 exp 8/cu cm under clear-sky conditions, with an estimated overall uncertainty of 40 percent. HO2 was detected by continuous low-pressure sampling with flowing chemical conversion to HO, which was detected by laser-excited fluorescence. The instrumental response to HO2 was calibrated by the self-decay of HO2 at atmospheric pressure. Interference in the measured daytime HO2 concentrations by RO2 was estimated at less than 20 percent.

Hard, T. M.↗

FAGE measurements of tropospheric HO with measurements and model of interferences

Ambient HO measurements by low-pressure laser-excited fluorescence with chemical modulation, and supporting ozone and water-vapor data, are presented for periods in May and August 1987. The observed peak daytime ambient HO concentrations are in the range (2.5 to 8) x 10 exp 6 molecules/cu cm and show small negative offsets due to photochemical interference. Direct measurements of the interference at fixed (O3) give the dependence on ambient (H2O) and on the modulating reagent (isobutane). At ambient (O3) = 30 ppb and 10 torr H2O, with excitation and detection at a total pressure of 4 torr, the net interference is equal to (HO) = -1.3 x 10 exp 6 molecules/cu cm. Production of HO by the reaction of isobutane with O(1D) accounts for the negative interference. Quenching of HO fluorescence by the modulating reagent contributes a smaller positive term to the interference; kinetic measurements of the quenching rate coefficient are reported. The experimental interference results are compared with a detailed kinetic model of HO production, excitation, relaxation, and detection; reasonable agreement is found.

Hard, T. M.↗

Third-generation FAGE instrument for tropospheric hydroxyl radical measurement

A single-stage, frequency-doubled, copper vapor laser-pumped dye laser has been constructed to be used in the measurement of atmospheric hydroxyl radical concentrations. A new photon counting instrument is used for HO fluorescence detection. Theoretical and experimental studies of instrument performance show better sensitivities and reduced photolytic interferences than have been possible with previous systems based upon Nd:YAG pumping.

Chan, C. Y.↗

Tropospheric HO determination by FAGE

In the detection of tropospheric HO by laser excited fluorescence, and alternative air-sampling method, named FAGE (Fluorescence Assay with Gas Expansion) was introduced. Here the air is expanded through a nozzle prior to excitation, in order to improve the ratio of the HO signal to the scattered, fluorescent, and photolytic backgrounds. The improvement comes from the differing pressure dependence of the intensities of these four terms, as well as the distinguishability of their temporal waveforms at low pressures when excited by a pulsed laser. HO has been excited by a YAG/dye laser. Other lasers and pumping paths may perform as well or better in this method. With FAGE, chemical modulation of the HO signal was achieved by hydrocarbon addition to the nozzle flow, converting photolytic HO from an interference to a background. Chemical calibration of the instrumental response to external HO was also achieved, by hydrocarbon decay, at HO concentrations within the ambient range.

Hard, T. M.↗

Tropospheric HO2 determination by FAGE

The detection efficiency is greatest at low pressures, where the subsequent removal of the HO product by the NO reagent (via HO + NO + M yields HONO + M) is relatively slow. Moreover, nozzle expansion of the air from ambient to low pressures produces a turbulent zone that assists in mixing the reagent with the sample. If the HO product is observed by laser-excited fluorescence, then the other advantages of low-pressure detection by FAGE (Fluorescence Assay with Gas Expansion) also apply. The FAGE instrumental response was calibrated to external HO2 by observing NO decay in the photolysis of HO-CH2O mixtures and by choosing conditions in which HO2 + NO is the only significant NO destruction path. HO2 was determined in urban air.

Obrien, R. J.↗

Laser wavelength selector and output coupler

Optical system eliminates displacement occurring when wavelengths are selected in multiple wavelength laser utilizing intracavity wavelength selection by first-order Littrow reflection of plane grating. Output coupling varies direction of output beam as different wavelengths are selected by grating rotation.

Hard, T. M.↗