ALBERT

Description: Measurements of peroxyacetyl nitrate (PAN), NO, NO2, HNO3, NOy (total odd nitrogen), and O3 were made in the high-latitude troposphere over North America and Greenland (35 degrees to 82 degrees N) during the Arctic Boundary Layer Expedition (ABLE 3A) (July-August 1988) throughout 0-to 6-km altitudes. These data are analyzed to quantitatively describe the relationships between various odd nitrogen species and assess their significance to global tropospheric chemistry. In the free troposphere, PAN was as much as 25 times more abundant than NOx. PAN to NOx ratio increased with increasing altitude and latitude. PAN was found to be the single most abundant reactive nitrogen species in the free troposphere and constituted a major fraction of NOy, PAN to NOy ratios were about 0.1 in the boundary layer and increased to 0.4 in the free troposphere. A 2-D global photochemical model with C1-C3 hydrocarbon chemistry is used to compare model predictions with measured results. A sizable portion (approximately 50%) of the gaseous reactive nitrogen budget is unaccounted for, and unknown organic nitrates and pernitrates are expected to be present. Model calculations (August 1, 70 degrees N) show that a major fraction of the observed NOx (50 to 70% of median) may find its source in the available PAN reservoir. PAN and the unknown reservoir species may have the potential to control virtually the entire NOx availability of the high latitude troposphere. It is predicted that the summer NOx and O3 mixing ratios in the Arctic/sub-Arctic troposphere would be considerably lower in the absence of the ubiquitous PAN reservoir. Conversely, this PAN reservoir may be responsible for the observed temporal increase in tropospheric O3 at high latitudes.

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: The chemistry of ethane and propane is studied using a global two-dimensional 'zonally averaged' height- and latitude-dependent tropospheric model. The purpose of the study is to derive theoretical estimates of the seasonal and latitudinal distributions of a variety of intermediate organic compounds formed by the photochemical oxidation of C2H6 and C3H8. It is shown that C2H6 and C3H8 emitted at rates of 16 Tg C2H6/a and 23 Tg C3H8/a do not affect the overall photochemistry of the troposphere significantly. Major global effects on O3 and OH concentrations are suggested to be coming from the formation of peroxyacetyl nitrate by the interactions of NOx with other hydrocarbons with strong and spatially correlated anthropogenic or natural sources at the earth's surface. It is pointed out that attention should be given to organic nitrates produced by the oxidation of NMHC other than C2H6 and C3H8.

Description: An analysis is presented on the distribution and variability of PAN as well as its relationship with measured chemical and meteorological parameters. The chemicals of most interest for which measurements were available are PAN, NO(x), O3, CO, and C2Cl4. PAN was measured by the electron capture gas chromatographic technique, and the technique for calibrations and measurements are detailed. Data show that significant concentrations of PAN (5-125 ppt) are present during the wet season and this PAN is 1-5 times more abundant than NO(x). PAN levels at different atmospheric locations are discussed, and it is noted that PAN shows evidence of a possible latitudinal gradient in the free troposphere, with values falling rapidly from the northern midlatitudes toward the equator. High correlations between O3 and PAN levels suggest that nonmethane hydrocarbons may contribute significantly to high O3 in the free troposphere. Evidence indicates that virtually all of the NO(x) above 4 km could result from PAN decomposition.

Description: The role of chlorine atoms in the oxidation of methane and nonmethane hydrocarbons (NMHCs) in the marine troposphere and lower stratosphere was investigated using a one-dimensional photochemical model that incorporated the chemistry of CH4, NMHCs, NO(x), O(x), and HO(x), as well as organic and inorganic halogens in the troposphere and lower stratosphere. The model predicted that chlorine atoms are present in the marine troposphere at the concentrations of about 1000/cu cm, mostly as a product of the reaction between OH and HCl released from sea spray. The results indicate that Cl atoms cause 20 to 40 percent of NMHC oxidation in the troposphere and 40 to 90 percent in the lower stratosphere. At 15 km, the NMHC-Cl reactions account for nearly 80 percent of the PAN produced. Where available, experimental data confirmed the model predictions.

Description: Budgets of O3, NO(x), and NO(y), and acetic acid in the Arctic Boundary Layer Expedition (ABLE 3A) flight region are constructed using photochemical model statistics based on aircraft observations. A Lagrangian model is used to reconstruct the photochemical history of two aged biomass fire plumes sampled by the ABLE 3A aircraft. It is shown that anthropogenic influence on O3 levels in the Arctic may manifest itself not by long-range transport of pollution-derived O3, but rather by a decrease of the regional photochemical sink due to the presence of small amounts of NO(x). The low concentrations of NO(x) measured in ABLE 3A were sufficient to reduce the rate of photochemical loss appreciably relative to a NO(x)-free atmosphere, thus increasing the O3 lifetime. It is shown that decomposition of PAN can account for most of the NO(x) measured below 4-km altitude, but for only 20 percent at 6-km altitude. A lifetime of 29 days is estimated for NO(y) in the ABLE 23A flight region.

Description: Measurements of NO, NO2, PAN and NO(y) are presented for the summertime middle/lower troposphere over northern high latitudes. Chemical signatures from concurrent measurements of O3, CO, C2H2, C2H6, C3H8, C2Cl4, and H2O are used to characterize factors affecting the budget and distribution of N(x)O(y) in the Arctic and Sub-Arctic tropospheric air masses sampled over Alaska during the NASA Arctic Boundary Layer Expedition (ABLE 3A). The results implicate biomass burning in Siberia as the probable source of about one-third of the NO(y) abundance within the middle lower troposphere over Alaska and the downward transport of air from altitude in the vicinity of the tropopause as a major contributor to the abundance of NO(y) within the lower 6 km column over Alaska.

Description: The first study is presented in which the mixing ratios of peroxyactyl nitrate (PAN) and nitrogen oxides, as well as those of peroxypropionyl nitrate and O3 and relevant meteorological parameters, were measured concurrently at a location that receives clean, continental air. The results show that, in clean conditions, nitrogen oxides present in the form of PAN can be as much or more abundant than the inorganic form. In addition, PAN can be an important source of peroxyacetyl radicals which may be important to oxidation processes in the gas as well as liquid phases.