ALBERT

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: The TP-LIF OH sensor is based on the principle that a molecule having multiple energy states, all of which are bonding, can be pumped into the highest state with the resulting fluorescence being blue-shifted relative to all pumping wavelengths. In this way, one can successfully discriminate against virtually all noise sources in the system using long wavelength blocking filters in conjunction with solar-blind photomultiplier tubes. Thus, these systems tend to be signal limited rather than signal-to-noise limited as is true of the SP-LIF technique as well as other conventional analytical methods. The trick to achieving the above sampling scheme, with high efficiency, is in the use of high photon fluxes of short time duration. Obviously, the latter type of light source is fulfilled nicely by available pulsed lasers. From an operational point of view, however, this laser source needs to be tunable. The latter characteristic permits extremely high selectivity for the detection of a diatomic or simple polyatomic molecule by taking advantage of the high-resolution spectroscopic features of these type species.

Description: Results are presented from two sets of measurements made by the High-resolution Interferometer Sounder (HIS) during two aircraft flights over the Cooperative-Huntsville-Meteorological-Experiment region on June 15 and 19, 1986. It is shown that the temperature and the dew-point field retrieved from HIS spectra contain distinct mesoscale structures. The features in the HIS dew-point fields agreed well with the cloud and moisture structures observed in visible and 6.7 micron GOES imagery.

Description: Elevated concentrations of hydrocarbons, CO, and nitrogen oxides were observed in extensive haze layers over northeastern Canada in the summer of 1990, during ABLE 3B. Halocarbon concentrations remained near background in most layers, indicating a source from biomass wildfires. Elevated concentrations of C2Cl4 provided a sensitive indicator for pollution from urban/industrial sources. Detailed analysis of regional budgets for CO and hydrocarbons indicates that biomass fires accounted for approximately equal to 70% of the input to the subarctic for most hydrocarbons and for acetone and more than 50% for CO. Regional sources for many species (including CO) exceeded chemical sinks during summer, and the boreal region provided a net source to midlatitudes. Interannual variations and long-term trends in atmospheric composition are sensitive to climatic change; a shift to warmer, drier conditions could increase the areas burned and thus the sources of many trace gases.

Description: Measurements of reactive nitrogen oxides (NO(x) and NO(y)) and ozone (O3) were made in the planetary boundary layer (PBL) above a taiga woodland in northern Quebec, Canada, during June-August, 1990, as part of NASA Artic Boundary Layer Expedition (ABLE) 3B. Levels of nitrogen oxides and O3 were strongly modulated by the synoptic scale meteorology that brought air from various source regions to the site. Industrial pollution from the Great Lakes region of the U.S. and Canada appears to be a major source for periodic elevation of NO(x), and NO(y) and O3. We find that NO/NO2 ratios at this site at midday were approximately 50% those expected from a simple photochemical steady state between NO(x) and O3, in contrast to our earlier results from the ABLE 3A tundra site. The difference between the taiga and tundra sites is likely due to much larger emissions of biogenic hydrocarbons (particularly isoprene) from the taiga vegetation. Hydrocarbon photooxidation leads to relatively rapid production of peroxy radicals, which convert NO to NO2, at the taiga site. Ratios of NO(x) to NO(y) were typically 2-3 times higher in the PBL during ABLE 3B than during ABLE 3A. This is probably the result of high PAN levels and suppressed formation of HNO3 from NO2 due to high levels of biogenic hydrocarbons at the ABLE 3B site.

Description: Acetone (CH3COCH3) was found to be the dominant nonmethane organic species present in the atmosphere sampled primarily over eastern Canada (0-6 km, 35 deg-65 deg N) during ABLE3B (July to August 1990). A concentration range of 357 to 2310 ppt (= 10(exp -12) v/v) with a mean value of 1140 +/- 413 ppt was measured. Under extremely clean conditions, generally involving Arctic flows, lowest (background) mixing ratios of 550 +/- 100 ppt were present in much of the troposphere studied. Correlations between atmospheric mixing ratios of acetone and select species such as C2H2, CO, C3H8, C2Cl4 and isoprene provided important clues to its possible sources and to the causes of its atmospheric variability. Biomass burning as a source of acetone has been identified for the first time. By using atmospheric data and three-dimensional photochemical models, a global acetone source of 40-60 Tg (= 10(exp 12) g)/yr is estimated to be present. Secondary formation from the atmospheric oxidation of precursor hydrocarbons (principally propane, isobutane, and isobutene) provides the single largest source (51%). The remainder is attributable to biomass burning (26%), direct biogenic emissions (21%), and primary anthropogenic emissions (3%). Atmospheric removal of acetone is estimated to be due to photolysis (64%), reaction with OH radicals (24%), and deposition (12%). Model calculations also suggest that acetone photolysis contributed significantly to PAN formation (100-200 ppt) in the middle and upper troposphere of the sampled region and may be important globally. While the source-sink equation appears to be roughly balanced, much more atmospheric and source data, especially from the southern hemisphere, are needed to reliably quantify the atmospheric budget of acetone.

Description: Biomass-burning impacted air masses sampled over central and eastern Canada during the summer of 1990 as part of ABLE 3B contained enhanced mixing ratios of gaseous HNO3, HCOOH, CH3COOH, and what appears to be (COOH)2. These aircraft-based samples were collected from a variety of fresh burning plumes and more aged haze layers from different source regions. Values of the enhancement factor, delta X/delta CO, where X represents an acidic gas, for combustion-impacted air masses sampled both near and farther away from the fires, were relatively uniform. However, comparison of carboxylic acid emission ratios measured in laboratory fires to field plume enhancement factors indicates significant in-plume production of HCOOH. Biomass-burning appears to be an important source of HNO3, HCOOH, and CH3COOH to the troposphere over subarctic Canada.

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: We report here large-scale features of the distribution of NO(x), HNO3, PAN, particle NO3, and NO(y) in the troposphere from 0.15 to 6 km altitude over central Canada. These measurements were conducted in July - August 1990 from the NASA Wallops Electra aircraft as part of the joint United States-Canadian Arctic Boundary Layer Expedition (ABLE) 3B-Northern Wetlands Study. Our findings show that this region is generally NO(x) limited, with NO(x) mixing ratios typically 20-30 parts per trillion by volume (pptv). We found little direct evidence for anthropogenic enhancement of mixing ratios of reactive odd nitrogen species and NO(y) above those in 'background' air. Instead, it appears that enhancements in the mixing ratios of these species were primarily due to emissions from several day old or CO-rich-NO(x)-poor smoldering local biomass-burning fires. NO(x) mixing ratios in biomass-burning impacted air masses were usually less than 50 pptv, but those of HNO3 and PAN were typically 100-300 pptv representing a twofold-threefold enhancement over 'background' air. During our study period, inputs of what appeared to be aged tropical air were a major factor influencing the distribution of reactive odd nitrogen in the midtroposphere over northeastern North America. These air masses were quite depleted in NO(y) (generally less than 150 pptv), and a frequent summertime occurrence of such air masses over this region would imply a significant influence on the reactive odd nitrogen budget. Our findings show that the chemical composition of aged air masses over subarctic Canada and those documented in the Arctic during ABLE 3A have strikingly similar chemistries, suggesting large-scale connection between the air masses influencing these regions.

Description: Aircraft measurements of key reactive nitrogen species (NO, NO2, HNO3, PAN, PPN, NO3(-), NO(y)), C1 to C6 hydrocarbons, acetone, O3, chemical tracers (C2Cl4, CO), and important meteorological parameters were performed over eastern Canada during July to August 1990 at altitudes between 0 and 6 km as part of an Arctic Boundary Layer Expedition (ABLE3B). In the free troposphere, PAN was found to be the single most abundant reactive nitrogen species constituting a major fraction of NO(y) and was significantly more abundant than NO(x) and HNO3. PAN and O3 were well correlated both in their fine and gross structures. Compared to data previously collected in the Arctic/subarctic atmosphere over Alaska (ABLE3A), the lower troposphere (0-4 km) over eastern Canada was found to contain larger reactive nitrogen and anthropogenic tracer concentrations. At higher altitudes (4-6 km) the atmospheric composition was in many ways similar to what was seen over Alaska and supports the view that a large-scale reservoir of PAN (and NO(y)) is present in the upper troposphere over the entire Arctic/subarctic region. The reactive nitrogen budget based on missions conducted from the North Bay site (missions 2-10) showed a small shortfall, whereas the budget for data collected from the Goose Bay operation (missions 11-19) showed essential balance. It is calculated that 15-20 ppt of the observed NO(x) may find its source from the available PAN reservoir. Meteorological considerations as well as relationships between reactive nitrogen and tracer species suggest that the atmosphere over eastern Canada during summer is greatly influenced by forest fires and transported industrial pollution.