ALBERT

Description: The meridional distribution of NO(x) in the lower stratosphere and upper troposphere is inferred form 10 flights of the NASA DC-8 in the northern winter of 1992 along with like distributions of NO(y), NO(x)/NO(y), CO, and C2Cl4. In the lowest few km of the stratosphere there is little vertical gradient in NO(x) over the range of latitiudes measured (40 deg-90 deg N). There is a substantial latitudinal gradient, with 50 pptv above the pole and 120 pptv near 40 deg N. In the uppermost few km of the troposphere, background values range from 30 pptv over the pole to 90 pptv near 40 deg N. On two occasions higher values, up to 140 pptv in the mean, were seen 2-3 km below the tropopause in association with frontal systems. The meridional distributions of CO and C2Cl4 show the same feature, suggesting that the source of the elevated NO(x) is near the earth's system.

Description: Results are reported from airborne measurements of NO, NO2, O3, and CO obtained in the free troposphere (FT) and boundary layer (BL) over the western U.S. and eastern Pacific during the NASA Global Tropospheric Experiment Chemical Instrumentation Test and Evaluation 2 (CITE 2) in summer 1986. The aircraft instrumentation and the CITE 2 flight protocols are described, and the results are presented in extensive tables and graphs. Over the ocean the median mixing ratios for NO and NO2 were found to be 4.0 and 10.4 parts per trillion by volume (pptv), respectively, in the BL and 12.4 and 18.0 pptv in the FT; the corresponding values over land were 34.5 and 75.0 pptv in the BL and 13.0 and 36.0 pptv in the FT. in continental air masses. NO(x) is shown to be positively correlated with O3 and CO and negatively correlated with dewpoint over the ocean, whereas over land NO(x) was positively correlated with O3, CO, and dewpoint.

Description: Results are reported from airborne PAN measurements obtained at altitudes 0-6 km over the continental U.S. and the eastern Pacific during the NASA Global Tropospheric Experiment Chemical Instrumentation Test and Evaluation 2 (CITE 2) in summer 1986. The CITE 2 flights and instrumentation are described, and the results are presented in extensive graphs and characterized in detail. It is shown that PAN is an important reactive N-containing species in the troposphere. Although the PAN mixing ratios were highly variable, in general high mixing ratios of 100-300 parts per trillion by volume (pptv) were found at 4-6 km, and very low ratios (5-20 pptv) were detected in the marine boundary layer. Good correlation was seen between the CITE 2 PAN values and those for O3, NO(y), NO(x), HNO3, C2H6, CO, and CFCl3.

Description: Two techniques designed for measurements of NO(x (NO + NO2) were intercompared during aircraft flights made in the spring of 1984 in the middle free troposphere over the eastern Pacific Ocean and southwestern U.S. One NO chemiluminescence instrument was equipped with a ferrous sulphate converter, another with a photolytic converter. The ferrous sulphate-equipped instrument was apparently much less specific for NO2. It registered levels about three times larger than the photolytic converter and gave NO2/NO ratios that were much larger than photochemical calculations would indicate as reasonable. Additionally, the results imply that active NO(x) was only 10-20 percent of the total odd nitrogen in the middle free troposphere.

Description: 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.

Description: Measurements of NO and O3 are presented from 13 aircraft flights made over the Pacific Ocean in the autumn of 1983 during one phase of the NASA Global Tropospheric Experiment. All of the flights were made between 15 deg and 42 deg N and from the coast of California to west of the Hawaiian Islands. Within the upper marine boundary layer the median daytime mixing ratio of NO was near 1 part per trillion by volume (pptv). Values of NO less than 10 pptv were often observed up to altitudes near 6 km. Thus for the location and season of the measurements, a net photochemical destruction of O3 would be anticipated for the boundary layer region and to altitudes of 2-3 km. At higher altitudes of 7-11 km in the free troposphere, larger mixing ratios and greater variability were usually observed for NO. Both features are consistent with observed examples of injection of NO and O3 from the lower stratosphere and with the injection of NO from towering, electrically active, cumulonimbus clouds.

Description: Measurements of NO, NO(x) (NO + NO2), O3, and CO are presented from seven aircraft flights made over the eastern Pacific Ocean and the southwestern United States in spring of 1984. The sampling region was characterized by large- and small-scale variability for all of the measurements, likely as a result of vigorous synoptic scale meteorology and the influence of tropopause folds. Median values for NO, NO(x), O3, and CO from the flights made over the ocean in the region of 5.8-7.6 km were 10 parts per trillion by volume (pptv), 32 pptv, 46 parts per billion by volume (ppbv), and 120 ppbv, respectively. Corresponding values from two flights made over the continent at similar altitudes were 16 pptv, 38 pptv, 42 ppbv, and 111 ppbv. There was a strong tendency for NO or NO(x) to be correlated positively with O3 and to be anticorrelated with dew-point/frost-point measurements. No significant overall correlation occurred between NO(x) and CO for the ocean data. The variability of NO(x) was such that regions of net destruction and regions of net production of O(3) were sampled both over the ocean and over the continent. However, in the middle free troposphere over the ocean, net O(3) destruction was predominant.

Description: The July 2004 CRYSTAL-FACE field program, based from Key West, Florida, showed that long-lived thin tropopause cirrus (TTC) layers were common above thunderstorm anvils. This paper investigates the origins of these cloud using airborne measurements. The horizontal dimensions of the TTC were nearly identical to the convectively formed anvil beneath. However, the TTC did not appear to have originated from convective detrainment. Rather it appears to have formed in stably stratified air derived from high altitudes near the tropopause. The TTC was separated from the anvil by approx. 1 km, it lacked precipitation particles, and it was strongly depleted in HDO. Nonetheless, compared to surrounding clear air near the tropopause, the TTC was enriched in moisture and trace gases in a manner consistent with it having mixed with the same convective airmass that produced the anvil. Unlike surrounding air, the TTC had embedded a monochromatic gravity wave with a wavelength of 2 km and an amplitude of several hundred meters. Combined, this evidence, supported by a photograph from CRYSTAL-FACE, leads to the conjecture that the TTC originated as a pileus cloud layer, which formed near the tropopause ahead of vigorous convective uplift. We hypothesize that the pileus was penetrated by the convection, moistened through mixing, and once the convection subsided, it was sustained by radiative cooling due to the presence of the anvil layer beneath.

Description: During the NASA Cirrus Regional Study of Tropical Anvils and Cirrus Layers-Florida Area Cirrus Experiment (CRYSTAL-FACE) enhanced mixing ratios of nitric oxide were measured in the anvils of thunderstorms and in clear air downwind of storm systems on flights of a Wl3-57F high-altitude aircraft. Mixing ratios greater than l0 - 20 times background were readily observed over distances of 25-120 km due to lightning activity. In many of the Florida storms deposition of NO occurred up to near the tropopause but major deposition usually occurred 1 - 2 km below the tropopause, or mostly within the visible anvil volume formed prior to storm decay. Observations from two storms of very different anvil size and electrical activity allowed estimates of the total mass of NO, vented to the middle and upper troposphere. Using the cloud-to ground (CG) flash accumulations from the National Lightning Detection Network, climatological intra-cloud (IC) to CG ratios, and assuming that CG and IC flashes were of equivalent efficiency for NO production, the ranges of production per flash for a moderate-sized and a large storm were (0.51 - 1.0) x l0(exp 26) and (2.3 - 3.1) x 10(exp 26) molecules NO/flash, respectively. Using the recently determined average global flash rate of 44 8, a gross extrapolation of these two storms to represent possible global annual production rates yield 1.6 - 3.2 and 7.3 - 9.9 Tg(N)/yr, respectively. If the more usual assumption is made that IC efficiency is l/l0th that of CG activity, the ranges of production for the moderate-sized and large storm were (1.3 - 2.7) x l0(exp 26) and (6.0 - 8.1) x l0(exp 26) molecules NO/CG flash, respectively. The estimates from the large storm may be high because there is indirect evidence that the IC/CG ratio was larger than would be derived from climatology. These two storms and others studied did not have flash rates that scaled as approx. H(sup 5) where H is the cloud top altitude. The observed CG flash accumulations and NO(x) mass production estimate for the month of July over the Florida area were compared with a representative 3D global Chemistry-Transport Model (CTMJ that uses the Price et al. lightning parameterization. For two land grid points representing the Florida peninsula the model compared well with the observations: CG flash rates were low by only a factor of approx. 2. When the model grid points included the coastal regions of Florida the flash accumulations were lower than observed by a factor of 3.4 - 4.6. It is recommended that models using the Price et al. parameterization allow any global coastal grid point to maintain the land rather than the marine flash rate parameterization. The convection in this CTM underestimated the actual cloud top heights over Florida by 1 - 2 km and thus the total lightning flash rates and the altitude range of reactive nitrogen deposition. Broad scale (20 - 120 km) median mixing ratios of NO within anvils over Florida were significantly larger than in storms previously investigated over Colorado and New Mexico.