Upper tropospheric nitrogen oxides measured by solar absorption spectrometry
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Photolysis of nitrogen oxide, nitrogen oxide/ nitrogen mixtures, and nitrogen olefin mixtures
The preliminary results from a three-dimensional dynamic-chemical model applied to the SST-NOx (NO + NO2) problem are reported. Simulations indicate that a depletion of about 12 per cent in total stratospheric O3 would be realized for a continuous NOx injection rate of 1.8 x 10 to the sixth power metric tons per year from a hypothetical fleet of SST's flying at an altitude of 20 km in the midlatitudes of the Northern Hemisphere. Sixteen per cent of the existing O3 would be destroyed on an annual basis. The model assumes a fleet of about 500 aircraft of the now-canceled American Boeing 2707 type; if only present Anglo-French and Russian SST models, which fly at lower, less harmful altitudes, are built, it will take a fleet of a few thousand such craft to attain an effective injection rate equal to the one above.
In the study of fuel consumption rate by stratospheric aircraft, the range of nitric oxide injection is interpreted as an eightfold range of emission index (5-40) with both the one- and the two-dimensional models. Possible effects of future aircraft NO(x) emissions on stratospheric ozone are considered for a broad range in magnitude, altitude, and latitude of the assumed NO(x) emissions. Results of the sensitivity studies using both models are discussed. Large ozone reductions are found to be outside the expected range of validity of these models and are to be anticipated if there should be a large fleet of stratospheric aircraft with NO(x) emission characteristics of current commercial aircraft. Under the test conditions, a global ozone reduction of about 9 percent is estimated for a jet engine emission index of 15 in both models. If engines are redesigned to reduce the emission index to the NASA goal of 5, global average ozone reductions are between 2 and 3 percent, and those of the Northern Hemisphere are about 4 percent. The effects of stratospheric aircraft on ozone could be further reduced through operation at lower altitudes, reduction of aircraft, and efficient fuel consumption.
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.
In the framework of the project POLINAT 2 (Pollution in the North Atlantic Flight Corridor) we measured NO(x) (NO and NO2) and ozone on 98 flights through the North Atlantic Flight Corridor (NAFC) with a fully automated system permanently installed aboard an in-service Swissair B-747 airliner in the period of August to November 1997. The averaged NO, concentrations both in the NAFC and at the U.S. east coast were similar to that measured in autumn 1995 with the same system. The patchy occurrence of NO(x), enhancements up to 3000 pptv over several hundred kilometers (plumes), predominately found over the U.S. east coast lead to a log-normal NO(x) probability density function. In three case-studies we examine the origins of such plumes by combining back-trajectories with brightness temperature enhanced (IR) satellite imagery, with lightning observations from the U.S. National Lightning Detection Network (NLDN) or with the Optical Transient Detector (OTD) satellite. For frontal activity above the continental U.S., we demonstrate that the location of NO(x) plumes can be well explained with maps of convective influence. For another case we show that the number of lightning flashes in a cluster of marine thunderstorms is proportional to the NO(x) concentrations observed several hundred kilometers downwind of the anvil outflows and suggest that lightning was the dominant source. From the fact that in autumn the NO, maximum was found several hundred kilometers off the U.S. east coast, it can be inferred that thunderstorms triggered over the warm Gulf Stream current are an important source for the regional upper tropospheric NO(x) budget in autumn.
This report addresses the Tropospheric Trace Gas and Airborne Measurements (TTGAMG) endeavors to further downsize and stabilize the Georgia Institute of Technology's Airborne Laser Induced Fluorescence Experiment (GITALIFE). It will mainly address the TTGAMG successes and failures as participants in the summer 1998 Wallops Island test flights on board the P3-B. Due to the restructuring and reorganization of the TTGAMG since the original funding of this grant, some of the objectives and time lines of the deliverables have been changed. Most of these changes have been covered in the preceding annual report. We are anticipating getting back on track with the original proposal's downsizing effort this summer, culminating in the GITALIFE no longer occupying a high bay rack and the loss of several hundred pounds.
In the framework of the project POLINAT 2 (Pollution in the North Atlantic Flight Corridor) we measured NO(x) (NO and NO2) and ozone on 85 flights through the North Atlantic Flight Corridor (NAFC) with a fully automated system permanently installed aboard an in-service Swissair B-747 airliner in the period of August to November 1997. The averaged NO(x) concentrations both in the NAFC and at the U.S. east coast were similar to that measured in autumn 1995 with the same system. The patchy occurrence of NO(x) enhancements up to 3000 pptv over several hundred kilometers (plumes), predominately found over the U.S. east coast lead to a log-normal NO(x) probability density function. In three case studies we examine the origins of such plumes by combining back-trajectories with brightness temperature enhanced (IR) satellite imagery, lightning observations from the U.S. National Lightning Detection Network (NLDN) and the Optical Transient Detector (OTD) satellite. We demonstrate that the location of NO(x) plumes can be well explained with maps of convective influence. We show that the number of lightning flashes in cluster of marine thunderstorms is proportional to the NO(x) concentrations observed several hundred kilometers downwind of the anvil outflows. From the fact that in autumn the NO(x) maximum was found several hundred kilometers off the U.S. east coast, it can be inferred that thunderstorms triggered over the warm Gulf Stream current are major sources for the regional upper tropospheric NO(x) budget in autumn.
This final report follows closely on our 1998 Annual Progress Report which was forwarded to NASA on November 19, 1998. Rather than reiterate the material therein we note here the continuation of the various items covered. SONEX has proN,Ided a number of opportunities to learn more about the fine-scale structure of the atmosphere. Coupled with the MOZAIC work on layers we can synthesize a new 3-D view of the fine scales that influence atmospheric chemistry. As a side issue we are also relating the features to clear air turbulence which would be, we think, a useful connection for commercial aviation.
Measurements of NO(x) and ozone performed during the NOXAR project are compared with results from the coupled chemistry-climate models ECHAM4.L39(DLR)/CHEM and GISS-model. The measurements are based on flights between Europe and the East coast of America and between Europe and the Far East in the latitude range 40 deg N to 65 deg N. The comparison concentrates on tropopause altitudes and reveals strong longitudinal variations of seasonal mean NO,, of 200 pptv. Either model reproduced strong variations 3 km below but not at the tropopause, indicating a strong missing NO(x) or NO(y) sink over remote areas, e.g. NO(x) to HNO3 conversion by OH from additional OH sources or HNO3 wash-out. Vertical profiles show maximum NO(x) values 2-3 km below the tropopause with a strong seasonal cycle. ECHAM4.L39(DLR)/CHEM reproduces a maximum, although located at the tropopause with a less pronounced seasonal cycle, whereas the GISS model reproduces the seasonal cycle but not the profile's shape due to its coarser vertical resolution. A comparison of NO(x) frequency distributions reveals that both models are capable of reproducing the observed variability, except that ECHAM4.L39(DLR)/CHEM shows no very high NO(x) mixing ratios. Ozone mean values, vertical profiles and frequency distributions are much better reproduced in either model, indicating that the NO(x) frequency distribution, namely the most frequent NO(x) mixing ratio, is more important for the tropospheric photochemical ozone production than its mean value. Both models show that among all sources, NO(x) from lightning contributes most to the seasonal cycle of NO(x) at tropopause altitudes. The impact of lightning in the upper troposphere on NO(x) does not vary strongly with altitude, whereas the impact of surface emissions decreases with altitude. However, the models show significant differences in lightning induced NO(x) concentrations, especially in winter, which may be related to the different treatment of the lower stratospheric coupling between dynamics and chemistry.
Fabrication of the University of Michigan Multichannel Chemiluminescence Instrument (UMMCI) was completed in early 1996 and the instrument participated in test flights on the NASA P3B at Wallops Island prior to integration and deployment for the PEM- Tropics A Mission. The UMMCI consists of 4 channels for simultaneous measurements of ozone and NO with the option for measurements of NO2 and NOy (total reactive nitrogen) when converters are placed upstream of the NO channels. Each NO channel consists of a zeroing volume and reaction vessel, while the ozone channel consists of an ozone catalyst (or scrubber) trap that is not in line with the reaction vessel. The detectors in all for channels are Hamamatsu photomultiplier tubes, which are followed by pulse amplifier discriminators on the NO channels and an electrometer on the ozone channel. Schematics of the Detector Module and NOx/03 Probe Insert and Diagrams of the Control and Data System, the Power and Ground System, the Gas Flow System, and the Calibration System Flow are attached. Intercomparisons were conducted with G. Gregory, NASA/Langley, during the test flights (following prior calibration of the ozone generator/calibrators at the Wallops Long-Path Absorption facility). Initial test results appeared to be reasonable, and instrument characterization studies proceeded for the ozone channel and the 3 NO channels until deployment for integration for the PEM-Tropics Mission. Ozone data was obtained for Flights #4, and 6-2 1, and finalized data was submitted to the PEM-Tropics Data Archive and to the Science Team during the April 1997 Data Workshop. Although it initially appeared that the instrument sensitivity varied, subsequent tests showed that this was the fault of a leak in the ozone calibrator. In fact; the instrument sensitivity has not been observed to vary in a large number of tests over the years since the PEM-Tropics mission. We have, therefore, a very high degree of confidence in the O3 data that we submitted. NO data was obtained for all flights except the mission out of Christmas Island and the subsequent return to Hawaii, during which time the NO channels were contaminated with back-flushing pure NO from the O3 channel. The NO channels were found to suffer from a varying artifact (7 - 22 pptv) which made the instrument's results unreliable for the marine boundary layer portions of the missions (where conditions were extremely clean with NO typically < 2 pptv and O3 only 8 ppbv). Nonetheless, the NO values were an upper limit and were quite useful in identifying pollution layers and outflow from the Latin American Continent. NO data was submitted to the archive for all flights during which data was obtained. Ozone data from the P3B was among the results presented in several peer-reviewed publications. Notably, the ozone data supported the first published finding of evidence for the occurrence of aerosol nucleation in the marine boundary layer. As well, the ozone data was utilized in a treatment of the wavenumber spectra of winds, temperature and trace gases and to demonstrate the occurrence of layering as observed by the P3B during PEM-Tropics A . O3 and NO data were used in an assessment of the impact of southern hemispheric biomass burning, and in the role of NOx and O3 in HOx photochemistry during the PEM Tropics A mission. These data, along with other species measured during PEM-Tropics A, have also been employed in the generation of climatologies for tropospheric ozone and its precursors by the PI's research group.
Woody encroachment has contributed to documented changes world-wide and locally in the southwestern U.S. Specifically, in North Texas rangelands encroaching mesquite (Prosopis glandulosa var. glandulosa) a known N-fixing species has caused changes in aboveground biomass. While measurements of aboveground plant production are relatively common, measures of soil N availability are scarce and vary widely. N trace gas emissions (nitric and nitrous oxide) flom soils reflect patterns in current N cycling rates and availability as they are stimulated by inputs of organic and inorganic N. Quantification of N oxide emissions from savanna soils may depend upon the spatial distribution of woody plant canopies, and specifically upon the changes in N availability and cycling and subsequent N trace gas production as influenced by the shift from herbaceous to woody vegetation type. The main goal of this research was to determine whether remotely sensible parameters of vegetation structure and soil type could be used to quantify biogeochemical changes in N at local, landscape and regional scales. To accomplish this goal, field-based measurements of N trace gases were carried out between 2000-2001, encompassing the acquisition of imaging spectrometer data from the NASA Airborne Visible and Infrared Imaging Spectrometer (AVIRIS) on September 29, 2001. Both biotic (vegetation type and soil organic N) and abiotic (soil type, soil pH, temperature, soil moisture, and soil inorganic N) controls were analyzed for their contributions to observed spatial and temporal variation in soil N gas fluxes. These plot level studies were used to develop relationships between spatially extensive, field-based measurements of N oxide fluxes and remotely sensible aboveground vegetation and soil properties, and to evaluate the short-term controls over N oxide emissions through intensive field wetting experiments. The relationship between N oxide emissions, remotely-sensed parameters (vegetation cover, and soil type), and physical controls (soil moisture, and temperature) permitted the regional scale quantification of soil N oxides emissions. Landscape scale analysis linking N oxide emissions with cover change revealed an alleviation from N limitation following mesquite invasion. This study demonstrated the advantage of using N trace gases as a measure of ecosystem N availability combined with remote sensing to characterize the spatial heterogeneity in ecosystem parameters at a scale commensurate with field-based measurements of these properties. Woody vegetation encroachment provided an opportunity to capitalize on detection of the remotely-sensible parameter of woody cover as it relates to belowground biogeochemical processes that determine N trace gas production. The first spatially-explicit estimates of NO flux were calculated based on Prosopis fractional cover derived from high resolution remote sensing estimates of fractional woody cover (< 4 m) for a 120 sq km region of North Texas. An assessment of both N stocks and fluxes from the study revealed an alleviation of N limitation at this site experiencing recent woody encroachment. Many arid and semi-arid regions of the world are experiencing woody invasions, often of N-fixing species. The issue of woody encroachment is in the center of an ecological and political debate. Improving the links between biogeochemical processes and remote sensing of ecosystem properties will improve our understanding of biogeochemical processes at the regional scale, thus providing a means to address issues of land-use and land-cover change.
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