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O'Brien, R. J.

Publications and source records attributed to O'Brien, R. J..

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.↗

Prototype FAGE determination of NO2

A low pressure laser-excited-fluorescence technique for the direct determination of atmospheric NO2 has been developed. Using a frequency-doubled Nd-YAG pump laser and a signal collection time of 20 s (10 s each signal and background), a detection limit of 450 pptv is calculated under laboratory conditions. Improved sensitivities will be possible with a higher repetition rate laser and lower fluorescence cell pressures.

George, L. A.↗

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.↗