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Results on NO2 instruments are reported from the NASA Global Tropospheric Experiment Chemical Instrumentation Test and Evaluation 2 (CITE 2) program in summer 1986. The instruments tested were (1) a two-photon LIF system using a laser for NO2-NO photolysis, (2) a chemiluminescence (CL) detector using FeSO4 for NO2-NO conversion, (3) a CL detector using an arc lamp for NO2-NO photolysis, and (4) a tunable-laser-diode multipath-absorption system. The procedures for the CITE 2 ground-based and flight tests are described in detail, and the results are presented in extensive graphs. Instrument (2) was eliminated because the FeSO4 converted atmospheric PAN to NO, resulting in spuriously high NO2 values. The remaining instruments gave readings in 30-40-percent agreement at NO2 mixing ratios of 100-200 parts per trillion by volume (pptv). At ratios below 50 pptv, the correlation among the measurements was very poor, with a tendency for system (4) to give higher values than (1) or (3).

Airborne measurements of NO2/NO ratios in the free troposphere, obtained using two-photon LIF (TP-LIF) and chemiluminescence (CL) detectors during the NASA Global Tropospheric Experiment Chemical Instrumentation Test and Evaluation 2 (CITE 2) program in summer 1986, are analyzed and compared with the predictions of a photochemical model. The derivation of the model is outlined, with an emphasis on the role of peroxy radicals in the fast photochemical cycling of NO and NO2 and the production of O3; the CITE 2 instruments and flight protocols are described; and the results are presented in extensive tables and graphs and discussed in detail. It was found that on three CITE 2 flights the CL data were systematically greater than the TP-LIF data; when these data were removed, the averaged values of the two instruments agreed to within 1 percent. The NO2/NO ratios predicted by the model are shown to be consistent with the measurements, although usually 20-25 percent lower.

The operating principle, design, and performance of a two-photon LIF (TP-LIF) sensor for simultaneous measurements of NO, NO(x) (NO + NO2), and NO2 are described. In this instrument, NO is first measured by direct spectroscopic TP-LIF detection; NO2 is converted to NO by photofragmentation using an XeF excimer laser operating at 353 nm; and the resulting NO is then detected quantitatively by TP-LIF. The detection limits of the instrument are found to be 3.5 parts per trillion by volume (pptv) of NO and 10 pptv for NO2, with integration times of 2 and 6 min, respectively. The in-flight performance of the instrument was evaluated during the NASA Global Tropospheric Experiment Chemical Instrumentation Test and Evaluation 2 program in summer 1986, as reported by Gregory et al. (1990).

During the NASA GTE/CITE 1 fall 1983 airborne field operation the NASA Convair 990 penetrated the anvils of two active cumulonimbus clouds. While NO levels outside the anvils averaged about 20 parts per trillion per volume (pptv), the average NO inside the anvils was about 440 pptv. Extrapolation of this observation along with data on the amount of air typically advected out of cumulonimbus clouds and the total number of thunderclouds occurring over the globe at any moment, implies a rate of nitrogen fixation in electrified clouds of about 7 x 10 to the 6th trillion/yr. Although the data base used to make this estimate is quite limited, the approach differs from that used in previous studies of the global production of nitrogen oxides by lightning, and thus represents an independent assessment of the role of electrified clouds in the atmospheric nitrogen oxide budget.

Reported in this paper are the Georgia Institute of Technology NO results from the fall 1983 NASA GTE/CITE 1 Airborne Field Sampling Program. These data were predominantly collected over a geographical area defined by the eastern and central North Pacific Ocean, spanning the latitude range of 15-42 deg N. These NO measurements were taken using the two-photon laser-induced fluorescence technique. The data show a general trend of increasing levels of NO from the boundary layer up to altitudes of nearly 10 km. The average midday value of NO at altitudes of less than or equal to 1.8 km was 4 parts per trillion by volume (pptv), and at about 6 km, 20 pptv, whereas that at about 9 km was 25-35 pptv, the higher value reflecting the inclusion of NO data collected from the outflow region of two electrically active cumulonimbus clouds. The high-altitude NO data strongly suggest that at least during the time of the GTE flight operation, the major sources of NO for remote regions of the Pacific Ocean were those resulting from lightning and the downward transport of stratospheric air.

The role of photochemistry in the budget of tropospheric ozone is studied. Measurements of O3, NO, CO, H2O vapor, and temperature obtained during the fall of 1983 during the GTE/CITE project over the eastern and central North Pacific Ocean are analyzed. The effect of altitude on the measurements is discussed. The analysis reveals a correlation between ozone and NO levels; both increase in concentration and variability with altitude. It is observed that an additional source of secondary importance associated wih CO-rich air parcels exists. A photochemical model is utilized to calculate the net rate of ozone production by photochemical reactions. A net photochemical source of ozone in the free troposphere and a net sink in the boundary layer are detected. The relation between the ozone source in the free troposphere and NO is examined. It is estimated that photochemistry provides a net ozone source to the free troposphere overlying the eastern and central North Pacific Ocean of about 5 x 10 to the 10th molecules/sq cm sec and a net sink of ozone to the boundary layer overlying this region of about 3 x 10 to the 10th molecules/sq cm sec.

A number of techniques have been proposed for detecting atmospheric OH radicals. Of these, the laser-induced fluorescence (LIF) technique has been used by the largest number of investigators. One of the problems arising in connection with the implementation of this technique is related to the perturbing effect of the UV (lambda approximately 282 nm) laser beam used for OH monitoring, while another problem relates to signal extraction. Several new LIF approaches have been or are currently under development with the objective to bring both problems under control. The present paper deals with the experimental features of one of these new approaches. The considered approach is referred to as 2-lambda laser-induced fluorescence (2-lambda LIF). It is shown that the 2-lambda LIF system provides significant advantages over earlier 1-lambda LIF OH measurement instruments operating at ambient pressure.

Results from an intercomparison of techniques to measure tropospheric levels of nitric oxide (NO) are discussed. The intercomparison was part of the National Aeronautics and Space Administration's Global Tropospheric Experiment and was conducted at Wallops Island, VA, in July 1983. Instruments intercompared included a laser-induced fluorescence system and two chemiluminescence instruments. The intercomparisons were performed with ambient air at NO mixing ratios ranging from 10 to 60 pptv and NO-enriched ambient air at mixing ratios from 20 to 170 pptv. All instruments sampled from a common manifold. The techniques exhibited a high degree of correlation among themselves and with changes in the NO mixing ratio. Agreement among the three techniques was placed at approximately + or - 30 percent. Within this level of agreement, no artifacts or species interferences were identified.

This paper reports on a new two-photon laser-induced fluorescence (TP-LIF) sensor capable of making routine measurements at the few parts per trillion volume level. This direct spectroscopic detection method has been demonstrated to be a reliable instrument while performing both on the ground and in the air. As currently designed it is unique in being 'signal' rather than 'signal-to-noise' limited. The latter characteristic enables the TP-LIF sensor to make atmospheric measurements of NO under environmental conditions that might normally be considered unsuitable for a laser technique. These include clouds, rain, and, in general, high-atmospheric-aerosol loading conditions. Of special interest is the insensitivity of the TP-LIF NO instrument to changes in pressure while operating in the troposphere. This characteristic has enabled this sensor to be used to record real-time altitude profiles of NO. Future improvements should make possible two measurement opportunities: (1) NO flux measurements via the airborne eddy-correlation method and (2) nitrogen isotopic distribution measurements (e.g., (N-15)(0-16) versus (N-14)(0-16) as a means of identifying specific NO(x) sources.

Results from an intercomparison of methods to measure carbon monoxide (CO), nitric oxide (NO), and the hydroxyl radical (OH) are discussed. The intercomparison was conducted at Wallops Island, Virginia, in July 1983 and included a laser differential absorption and three grab sample/gas chromatograph methods for CO, a laser-induced fluorescence (LIF) and two chemiluminescence methods for NO, and two LIF methods and a radiocarbon tracer method for OH. The intercomparison was conducted as a field measurement program involving ambient measurements of CO (150-300 ppbv) and NO (10-180 pptv) from a common manifold with controlled injection of CO in incremental steps from 20 to 500 ppbv and NO in steps from 10 to 220 pptv. Only ambient measurements of OH were made. The agreement between the techniques was on the order of 14 percent for CO and 17 percent for NO. Hardware difficulties during the OH tests resulted in a data base with insufficient data and uncertanties too large to permit a meaningful intercomposition.