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Hydrogen Radicals, Nitrogen Radicals, and the Production of O3 in the Upper Troposphere

The concentrations of the hydrogen radicals OH and HO2 in the middle and upper troposphere were measured simultaneously with those of NO, O3, CO, H2O, CH4, non-methane hydrocarbons, and with the ultraviolet and visible radiation field. The data allow a direct examination of the processes that produce O3, in this region of the atmosphere. Comparison of the measured concentrations of OH and HO2 with calculations based on their production from water vapor, ozone, and methane demonstrate that these sources are insufficient to explain the observed radical concentrations in the upper troposphere. The photolysis of carbonyl and peroxide compounds transported to this region from the lower troposphere may provide the source of HO(x) required to sustain the measured abundances of these radical species. The mechanism by which NO affects the production of 03 is also illustrated by the measurements. In the upper tropospheric air masses sampled, the production rate for ozone (determined from the measured concentrations of HO2 and NO) is calculated to be about 1 part per billion by volume each day.This production rate is faster than previously thought and implies that anthropogenic activities that add NO to the upper troposphere, such as biomass burning and aviation, will lead to production of more 03 than expected.

Wennberg, P. O.↗

A Satellite-Derived Upper-Tropospheric Water Vapor Transport Index for Climate Studies

A new approach is presented to quantify upper-level moisture transport from geostationary satellite data. Daily time sequences of GOES-7 water vapor imagery were used to produce estimates of winds and water vapor mixing ratio in the upper-troposphere sensed by the 6.7-microns water vapor channel. The winds and mixing ratio values were gridded and then combined to produce a parameter called the Water Vapor Transport Index (WVTI) which represents the magnitude of the two dimensional transport of water vapor in the upper troposphere. Daily grids of WVTI, meridional moisture transport, mixing ratio, pressure and other associated parameters were averaged to produce monthly fields for June, July and August of 1987 and 1988 over the Americas and surrounding oceanic regions. The WVTI was used to compare upper-tropospheric moisture transport between the summers of 1987 and 1988, contrasting the latter part of the 1986/87 El Nino event and the La Nina period of 1988. A similar product derived from the NCEP reanalysis was used to help validate the index and understand interannual variability of moisture transport from the modeling perspective. Both datasets showed large upper-level water vapor transport associated with synoptic features over the Americas and with outflow from tropical convective systems. Minimal transport occurred over tropical and subtropical high pressure regions where winds were light. Index values from NCEP were 2-3 times larger than that determined from the GOES satellite This difference resulted from an over estimate of the zonal winds and upper-tropospheric moisture in the reanalysis model. A comparison of the satellite-derived monthly values between the summers of 1987 and 1988 provided some insight into the impact of the ENSO event on upper-level moisture and its transport during the period. During July 1987, a large portion of the tropics in the eastern Pacific Ocean and Caribbean Sea was dominated by strong vapor transport in excess of 5 g/kg/ms with relatively small amounts in the other months. In contrast, JJA 1988 showed an opposite trend with July 1988 being less dominated by tropical water vapor transport. The meridional transport of upper-level water vapor indicated significant poleward transport from the tropics to the higher latitudes. This transport favored the Southern Hemisphere with large transport occurring south of the ITCZ which extended across the eastern Pacific and northern South America. Zonally-averaged monthly transport values were shown to provide a simple way to quantify the monthly and interannual changes in water vapor transport. Zonally-averaged WVTI values peaked in the Southern Hemisphere subtropics during both Austral winters. In the tropics a single more pronounced peak located over the equator and south latitudes occurred in 1988 as opposed to a dual peak in 1987. The second peak around 20 deg.N latitude is consistent with findings of others where upper-tropospheric winds were noted to be stronger in this region during warm ENSO events. Zonally-averaged meridional transport was southward for all summer months and stronger in 1988. The asymmetric nature of the zonally-averaged meridional transport (more southerly water vapor transport) was enhanced during JJA 1998 thus indicating a stronger upper-level branch of the Hadley circulation during this notable strong La Nina period.

Jedlovec, Gary J.↗

An 11-year Solar-Cycle in Tropospheric Ozone from TOMS Measurements

Tropospheric column ozone derived from Nimbus 7 total ozone mapping spectrometer (TOMS) footprint measurements in the tropical western Pacific for 1979-1992 provide the first observational evidence of changes in tropospheric ozone which are out of phase with the stratospheric ozone changes on a time scale of a solar cycle. The estimated changes in tropospheric and stratospheric column ozone over a solar cycle are respectively -2.97 and 8.83 DU (Dobson units) or - 12.7 and 3.7% from the solar minimum to solar maximum. These observations are qualitatively consistent with a modulation effect on tropospheric ozone photochemistry by UV-induced changes in stratospheric ozone. However, in the low NO(x) regime of the marine atmosphere, the observed changes are significantly larger than estimated from a photochemical model. The solar cycle detected in tropospheric ozone is estimated to produce approximately 0.1-0.25 W m(exp -2) anomalous radiative forcing in the tropics. The combination of this with other radiative sources may have substantial influence on both regional and global climate.

Chandra, S.↗

Effects of 1997-1998 El Nino on Tropospheric Ozone and Water Vapor

This paper analyzes the impact of the 1997-1998 El Nino on tropospheric column ozone and tropospheric water vapor derived respectively from the Total Ozone Mapping Spectrometer (TOMS) on Earth Probe and the Microwave Limb Scanning instrument on the Upper Atmosphere Research Satellite. The 1997-1998 El Nino, characterized by an anomalous increase in sea-surface temperature (SST) across the eastern and central tropical Pacific Ocean, is one of the strongest El Nino Southern Oscillation (ENSO) events of the century, comparable in magnitude to the 1982-1983 episode. The major impact of the SST change has been the shift in the convection pattern from the western to the eastern Pacific affecting the response of rain-producing cumulonimbus. As a result, there has been a significant increase in rainfall over the eastern Pacific and a decrease over the western Pacific and Indonesia. The dryness in the Indonesian region has contributed to large-scale burning by uncontrolled wildfires in the tropical rainforests of Sumatra and Borneo. Our study shows that tropospheric column ozone decreased by 4-8 Dobson units (DU) in the eastern Pacific and increased by about 10-20 DU in the western Pacific largely as a result of the eastward shift of the tropical convective activity as inferred from National Oceanic and Atmospheric Administration (NOAA) outgoing longwave radiation (OLR) data. The effect of this shift is also evident in the upper tropospheric water vapor mixing ratio which varies inversely as ozone (O3). These conclusions are qualitatively consistent with the changes in atmospheric circulation derived from zonal and vertical wind data obtained from the Goddard Earth Observing System data assimilation analyses. The changes in tropospheric column O3 during the course of the 1997-1998 El Nino appear to be caused by a combination of large-scale circulation processes associated with the shift in the tropical convection pattern and surface/boundary layer processes associated with forest fires in the Indonesian region.

Chandra, S.↗

Processes Affecting Tropospheric Ozone Inferred from Ozonesonde and Other Tracer Data from the R/V R H Brown Atlantic Cruise (37N-34S) in January-February 1999

During the Aerosols-99 trans-Atlantic cruise from Norfolk, VA, to Cape Town, South Africa, 22 ozonesondes were launched from the NOAA R/V R H Brown between 17 Jan and 6 Feb 1999, with all sondes but one reaching 30 km. A composite of ozone profiles along the transect shows high free tropospheric ozone (up to 100 ppbv at 9 km) between 5N and 20S, a coherent feature straddling either side of the ITCZ. Latitudinal variations of tropospheric ozone are interpreted using correlative measurements of surface ozone, CO, water vapor, and aerosol optical thickness (column absorbance) measured from the ship. Elevated ozone in the lower troposphere results from photochemical reactions of precursors emitted by biomass burning north of the ITCZ. However, the greatest ozone mixing ratios are in the mid-troposphere south of the ITCZ, which gives evidence of interhemispheric transport. Column-integrated tropospheric ozone, 35 DU from 0-16 km, agrees with that derived from the TOMS satellite by the modified-residual method [Thompson and Hudson, 1999]. NCEP wind fields, ship-launched radiosondes and back trajectories are consistent with a picture of recirculating air parcels centered in the tropical Atlantic region which is identified with the maximum wave-one amplitude in total ozone seen in sondes and by satellite.

Thompson, Anne M.↗

A Satellite-Derived Upper-Tropospheric Water Vapor Transport Index for Climate Studies

A new approach is presented to quantify upper-level moisture transport from geostationary satellite data. Daily time sequences of Geostationary Operational Environmental Satellite GOES-7 water vapor imagery were used to produce estimates of winds and water vapor mixing ratio in the cloud-free region of the upper troposphere sensed by the 6.7- microns water vapor channel. The winds and mixing ratio values were gridded and then combined to produce a parameter called the water vapor transport index (WVTI), which represents the magnitude of the two-dimensional transport of water vapor in the upper troposphere. Daily grids of WVTI, meridional moisture transport, mixing ratio, pressure, and other associated parameters were averaged to produce monthly fields for June, July, and August (JJA) of 1987 and 1988 over the Americas and surrounding oceanic regions, The WVTI was used to compare upper-tropospheric moisture transport between the summers of 1987 and 1988, contrasting the latter part of the 1986/87 El Nino event and the La Nina period of 1988. A similar product derived from the National Centers for Environmental Prediction (NCEP)-National Center for Atmospheric Research (NCAR) 40-Year Reanalysis Project was used to help to validate the index. Although the goal of this research was to describe the formulation and utility of the WVTI, considerable insight was obtained into the interannual variability of upper-level water vapor transport. Both datasets showed large upper-level water vapor transport associated with synoptic features over the Americas and with outflow from tropical convective systems. Minimal transport occurred over tropical and subtropical high pressure regions where winds were light. Index values from NCEP-NCAR were 2-3 times larger than that determined from GOES. This difference resulted from large zonal wind differences and an apparent overestimate of upper-tropospheric moisture in the reanalysis model. A comparison of the satellite-derived monthly values between the summers of 1987 and 1988 provided some insight into the impact of the ENSO event on upper-level moisture and its transport during the period. During July 1987, a large portion of the Tropics in the eastern Pacific Ocean and Caribbean Sea was dominated by strong vapor transport in excess of 4.0 g/kg m/s, with relatively small amounts in the other months. JJA 1988 transport values reached similar magnitude and showed similar patterns for all three months. The meridional transport of upper-level water vapor indicated large poleward transport from the Tropics to the higher latitudes. This transport favored the Southern Hemisphere, with large transport occurring south of the ITCZ, which extended across the eastern Pacific and northern South America. Zonally averaged monthly transport values were shown to provide a simple way to quantify the monthly and interannual changes in water vapor transport. Zonally averaged WVTI values peaked in the Southern Hemisphere subtropics during both austral winters. In the Tropics, a single, more- pronounced peak located over the equator and south latitudes occurred in 1988 as opposed to a dual peak in 1987. The second peak around 20'N latitude is consistent with findings of others in which upper-tropospheric winds were noted to be stronger in this region during warm ENSO events. Zonally averaged meridional transport was southward for all summer months and was stronger in 1988. The asymmetric nature of the zonally averaged meridional transport (more southerly water vapor transport) was enhanced during JJA 1988, thus indicating a stronger upper- level branch of the Hadley circulation during this notably strong La Nina period.

Jedlovec, Gray J.↗

Elevated Tropospheric Ozone Over the South Tropical Atlantic in January-February 1999: An Ozone Paradox Due to Interhemispheric Transport, Lightning, or Stratospheric Exchange?

On this first North American to southern African oceanographic cruise with ozonesonde launches (January and February 1999 on board the NOAA Research Vessel Ronald H Brown between Norfolk, VA, and Cape Town, South Africa) we found: (1) high ozone, CO, and aerosols off northern equatorial Africa from biomass burning, but even higher ozone concentrations off southern Africa which was not burning - an "ozone paradox"; (2) TOMS satellite evidence that south Atlantic elevated ozone in January-February 1999 was a regional feature similar in extent to the well-known September-October ozone maximum. Several mechanisms are considered to explain the "ozone paradox." Convection transporting air from the lower troposphere rich in ozone and/or ozone precursors to the upper troposphere through the ITCZ (intertropical Convergence Zone) may lead to cross-hemisphere transport of pollution. This is supported by trajectory linkage of lower-tropospheric ozone maxima with smoke seen by the TOMS satellite. Lightning-generated NO (nitric oxide) leading to ozone peaks of > 100 ppbv observed at 7-10 km altitude is another explanation. The TRMM (Tropical Rainfall Measuring Mission) Lightning Imaging Sounder shows many lightning flashes over southern Africa, which trajectories link to the high-ozone layers south of the ITCZ. The highest ozone peaks in the middle troposphere correspond to very low water vapor, which may point to photochemical destruction of ozone or subsidence from the upper troposphere which had interacted with stratospheric ozone.

Thompson, Anne M.↗

Tropospheric Ozone Pollution Transport Traced from the TOMS (Total Ozone Mapping Spectrometer) Instrument During the Nashville-1999 Campaign

Over the past several years, we have developed two new tropospheric ozone retrievals from the TOMS (Total Ozone Mapping Spectrometer) satellite instrument that are of sufficient resolution to follow pollution episodes. The modified-residual technique [Hudson and Thompson, 1998; Thompson and Hudson, 1999] uses v. 7 TOMS total ozone and is applicable to tropical regimes in which the wave-one pattern in total ozone is observed. The TOMS-direct method [("TDOT" = TOMS Direct Ozone in the Troposphere; Frolov et al., 2000] represents a new algorithm that uses TOMS radiances directly (i.e., not previously processed for TOMS ozone) to extract tropospheric ozone in regions of constant stratospheric ozone and tropospheric ozone displaying high mixing ratios and variability characteristic of pollution. These events tend to occur in certain meteorological regimes. For example, mid-latitude pollution usually occurs on the backside of subtropical fronts, as low pv, usually moist air intrudes to the extra-tropics. July 1999 was a month characterized by robust pollution in the eastern US, with high ozone, as detected by TOMS, originating over south central states and moving up the Atlantic seaboard. This corresponds to 50-80 DU in tropospheric ozone column depth. In most cases, further transport occurred to the North Atlantic, with ozone plumes traveling to western Europe in 4-5 days. Examples of high ozone and transit across boundaries within the US, as well as US->Europe, give a regional context for model results and field measurements taken in the SE US during the Nashville-1999 campaign period. Validation of the TDOT maps is made with ozonesondes taken during that time. TDOT maps also show ozone pollution from Asia traveling to the western US in July 1999.

Thompson, Anne M.↗

Tropospheric Delay Signal in SAR Interferogram and its Correction for Precise Surface Change Detection

Synthetic Aperture Radar (SAR) interferometry has become an important tool for measuring the surface deformation and mapping topography. The largest error source of the SAR interferometry measurements is differential atmospheric delay of water vapor. It reflects detailed distribution of water vapor in troposphere at data acquisition. We found phase difference associated with atmospheric waves and severe local atmospheric phenomena in interferograms. To distinguish phase difference associated with surface deformation from tropospheric effect, we need several SAR interferograms including the time period of the deformation. Averaging the interferograms is an effective way to reduce the tropospheric delay from horizontal inhomogeneity of the water vapor distribution. Apart from the tropospheric delay of the horizontal water vapor inhomogeneity, we often find the differential phase correlated to the topography (elevation) in interferograms, which might cause error in interpretation of surface deformation. This phase is due to the differential tropospheric delay caused by the topography and vertical change of water vapor between two images in different atmospheric condition. Theoretical calculation shows that the phase difference can be approximated by linear expression of the elevation. We applied a simple and effective correction method that the error is removed by subtracting the DEM (Digital Elevation Model) multiplied a coefficient.

Fujiwara, Satoshi↗

Measurements of Oxygenated Organic Chemicals In the Pacific Troposphere During TRACE-P: Higher Aldehydes (less than C(sub 1)), Their Sources, and Potential Role In Atmospheric Oxidation

Airborne measurements of a large number of oxygenated organics were carried out in the Pacific troposphere (to 12 km) in the Spring of 2001 (Feb. 24-April 10). Specifically these measurements included acetaldehyde, propanaldehyde, acetone, methylethyl ketone, methanol, ethanol, PAM and organic nitrates. Independent measurements of formaldehyde, peroxides, and tracers were also available. Highly polluted as well as pristine air masses were sampled. Oxygenated organics were abundant in the clean In troposphere and were greatly enhanced in the outflow regions from Asia. Extremely high concentrations of aldehydes could be measured in the troposphere. It is not possible to explain the large abundances of aldehydes in the background troposphere without invoking significant oceanic sources. A strong correlation between the observed mixing ratios of formaldehyde and acetaldehyde is present. We infer that higher aldehydes (such as acetaldehyde and propanaldehyde) may provide a large source of formaldehyde and sequester Cox throughout the troposphere. The atmospheric behavior of acetone, methylethyl ketone, and methanol is generally indicative of their common terrestrial sources with a Image contribution from biomass/biofuel burning. A vast body of data has been collected and it is being analyzed both statistically and with the help of models to better understand the role that oxygenated organics play in the atmosphere and to unravel their sources and sinks. These results will be presented.

Singh, Hanwant B.↗

Tropospheric Ozone during the TRACE-P Mission: Comparison between TOMS Satellite Retrievals and Aircraft Lidar Data, March 2001

Over the past several years, we have developed two new tropospheric ozone retrievals from the TOMS (Total Ozone Mapping Spectrometer) satellite instrument that are of sufficient resolution to follow pollution episodes. The modified-residual technique uses v. 7 TOMS total ozone and is applicable to tropical regimes in which the wave-one pattern in total ozone is observed. The TOMS-direct method ('TDOT' = TOMS Direct Ozone in the Troposphere) represents a new algorithm that uses TOMS radiances directly to extract tropospheric ozone in regions of constant stratospheric ozone. It is not geographically restricted, using meteorological regimes as the basis for classifying TOMS radiances and for selecting appropriate comparison data. TDOT is useful where tropospheric ozone displays high mixing ratios and variability characteristic of pollution. Some of these episodes were observed downwind of Asian biomass burning during the TRACE-P (Transport and Atmospheric Chemical Evolution-Pacific) field experiment in March 2001. This paper features comparisons among TDOT tropospheric ozone column depth, integrated uv-DIAL measurements made from NASA's DC-8, and ozonesonde data.

Frolov, A. D.↗

Tropospheric Trace Gas Interactions with Aerosols

Tropospheric aerosols are of considerable environmental importance. They modify the radiative budget of Earth by scattering and absorbing radiation, and by providing nuclei for cloud formation. Additionally, they provide surfaces for heterogeneous and multiphase reactions that affect tropospheric chemistry. For example, Dentener and Crutzen (1993) showed that reactions of N2O5 and NO3 with sulfate aerosols may significantly alter the tropospheric concentrations of NO(x), O3, and OH by converting NOx to HNO3 which is rapidly removed by precipitation. Zhang et al. (1994) assumed these same reactions would occur on dust aerosols and showed that dust outbreaks may reduce NO(x) levels by up to 50%. Dentener et al. (1996) studied the possible effect of reactions on dust on sulfate, nitrate, and O3 concentration. Heterogeneous and multiphase reactions on aerosols may also perturb the sulfur cycle the chlorine cycle and the bromine cycle. Because these reactions can release free chlorine and free bromine they might lead to the destruction of ozone in the marine boundary layer that may be important to include in models of tropospheric chemistry. The goal of our proposed work is to examine the role of heterogeneous and multiphase reactions in the tropospheric cycles of reactive nitrogen and sulfur.

Penner, Joyce E.↗

Chemistry-Transport Modeling of the Satellite Observed Distribution of Tropical Tropospheric Ozone

We have compared the 14-year record of satellite derived tropical tropospheric ozone columns (TTOC) from the NIMBUS-7 Total Ozone Mapping Spectrometer (TOMS) to TTOC calculated by a chemistry-transport model (CTM). An objective measure of error, based on the zonal distribution of TTOC in the tropics, is applied to perform this comparison systematically. In addition, the sensitivity of the model to several key processes in the tropics is quantified to select directions for future improvements. The comparisons indicate a widespread, systematic (20%) discrepancy over the tropical Atlantic Ocean, which maximizes during austral Spring. Although independent evidence from ozonesondes shows that some of the disagreement is due to satellite over-estimate of TTOC, the Atlantic mismatch is largely due to a misrepresentation of seasonally recurring processes in the model. Only minor differences between the model and observations over the Pacific occur, mostly due to interannual variability not captured by the model. Although chemical processes determine the TTOC extent, dynamical processes dominate the TTOC distribution, as the use of actual meteorology pertaining to the year of observations always leads to a better agreement with TTOC observations than using a random year or a climatology. The modeled TTOC is remarkably insensitive to many model parameters due to efficient feedbacks in the ozone budget. Nevertheless, the simulations would profit from an improved biomass burning calendar, as well as from an increase in NOX abundances in free tropospheric biomass burning plumes. The model showed the largest response to lightning NOX emissions, but systematic improvements could not be found. The use of multi-year satellite derived tropospheric data to systematically test and improve a CTM is a promising new addition to existing methods of model validation, and is a first step to integrating tropospheric satellite observations into global ozone modeling studies. Conversely,the CTM may suggest improvements to evolving satellite retrievals for tropospheric ozone.

Peters, Wouter↗

Tropospheric Chemistry Studies using Observations from GOME and TOMS

Studies to quantitatively determine trace gas and aerosol amounts from the Global Ozone Monitoring Experiment (GOME) and the Total Ozone Monitoring Experiment (TOMS) and to perform chemical modeling studies which utilize these results are given. This includes: 1. Analysis of measurements from the GOME and TOMS instruments for troposphere distributions of O3 and HCHO; troposphere enhancements of SO2, NO2 and aerosols associated with major sources; and springtime events of elevated BrO in the lower Arctic troposphere. 2. Application of a global 3-dimensional model of troposphere chemistry to interpret the GOME observations in terms of the factors controlling the abundances of troposphere ozone and OH.

Chance, Kelly↗

Discoveries about Tropical Tropospheric Ozone from Satellite and SHADOZ (Southern Hemisphere Additional Ozonesondes) and a Future Perspective on NASA's Ozone Sensors

We have been producing near-real tropical tropospheric ozone ('TTO') data from TOMS since 1997 with Prof. Hudson and students at the University of Maryland. Maps for 1996-2000 for the operational Earth-Probe instrument reside at: . We also have archived 'TTO' data from the Nimbus 7/TOMS satellite (1979-1992). The tropics is a region strongly influenced by natural variability and anthropogenic activity and the satellite data have been used to track biomass burning pollution and to detect interannual variability and climate signals in ozone. We look forward to future ozone sensors from NASA; four will be launched in 2004 as part of the EOS AURA Mission. The satellite view of chemical-dynamical interactions in tropospheric ozone is not adequate to capture vertical variability. Thus, in 1998, NASA's Goddard Space Flight Center, NOAA's Climate Monitoring and Diagnostics Laboratory (CMDL) and a team of international sponsors established the SHADOZ (Southern Hemisphere ADditional OZonesondes) project to address the gap in tropical ozone soundings. SHADOZ augments launches at selected sites and provides a public archive of ozonesonde data from twelve tropical and subtropical stations at http://croc.nsfc.nasa.gov/shadoz. The stations are: Ascension Island; Nairobi, Kenya; Irene, South Africa; R,union Island; Watukosek, Java; Fiji; Tahiti; American Samoa; San Cristobal, Galapagos; Natal, Brazil, Malindi, Kenya; Paramaribo, Surinam. From the first 3-4 years of data (presently greater than 1700 sondes), the following features emerge: (a) highly variable tropospheric ozone; (b) a zonal wave-one pattern in tropospheric column ozone; (c) tropospheric ozone variability over the Indian and Pacific Ocean displays strong convective signatures.

Thompson, Anne↗

Laser Sounder for Global Measurement of CO2 Concentrations in the Troposphere from Space: Progress

We describe progress toward developing a laser-based technique for the remote measurement of the tropospheric CO2 concentrations from orbit. Our goal is to demonstrate a lidar technique and instrument technology that will permit measurements of the CO2 column abundance in the lower troposphere from aircraft at the few ppm level, with a capability of scaling to permit global CO2 measurements from orbit. Accurate measurements of the tropospheric CO2 mixing ratio from space are challenging due to the many potential error sources. These include possible interference from other trace gas species, the effects of temperature, clouds, aerosols & turbulence in the path, changes in surface reflectivity, and variability in dry air density caused by changes in atmospheric pressure, water vapor and topographic height. Some potential instrumental errors include frequency drifts in the transmitter, small transmission and sensitivity drifts in the instrument. High signal-to-noise ratios and measurement stability are needed for mixing ratio estimates at the few ppm level. We have been developing a laser sounder approach as a candidate for a future space mission. It utilizes multiple different laser transmitters to permit simultaneous measurement of CO2 and O2 extinction, and aerosol backscatter in the same measurement path. It directs the narrow co-aligned laser beams from the instrument's fiber lasers toward nadir, and measures the energy of the strong laser echoes reflected from the Earth's land and water surfaces. During the measurement its narrow linewidth lasers are rapidly tuned on- and off- selected CO2 line near 1572 nm and an O2 absorption line near 770 nm. The receiver measures the energies of the laser echoes from the surface and any clouds and aerosols in the path with photon counting detectors. Ratioing the on- to off-line echo pulse energies for each gas permits the column extinction and column densities of CO2 and O2 to be estimated simultaneously via the differential absorption lidar technique. For the on-line wavelengths, the side of the selected absorption lines are used, which due to pressure broadening, weights the measurements to the lower troposphere, where CO2 variations caused by surface sources and sinks are largest. Simultaneous measurements of O2 column abundance are made using an identical approach using an O2 line. The laser backscatter profiles from clouds and aerosols are measured with other lidar channels, which permits identifying measurements influenced by clouds and/or aerosol scattering in the path. For space use, our lidar would continuously measure at nadir in near polar circular orbit. Using dawn and dusk measurements made over the same region will make it possible to sample the diurnal variations in CO2 mixing ratios. A 1-m diameter telescope is used for the receiver for all wavelengths. When averaging over 50 seconds, our calculations show a SNR of approximately 1500 is achievable for each gas at each on- and off-line measurement. Measurements from such a mission can be used to generate monthly global maps of the lower tropospheric CO2 column abundance. Our calculations show global coverage with an accuracy of a few ppm with a spatial resolution of approximately 50,000 sq. km are achievable each month. We have demonstrated some key elements of the laser, detector and receiver approaches in the laboratory and with measurements over a 206 m horizontal path. These include stable measurements of CO2 line shapes in an absorption cell using a fiber laser amplifier seeded by a tunable diode laser, measurement of small amplitude changes at low optical signal levels with the PMT receiver, and comparison of the horizontal path measurements of CO2 against those from an in-situ instrument.

Abshire, J. B.↗

Halogens and the Chemistry of the Free Troposphere

The role of halogens in both the marine boundary layer and the stratosphere has long been recognized, while their role in the free troposphere is often not considered in global chemical models. However, a careful examination of free-tropospheric chemistry constrained by observations using a full chemical data assimilation system shows that halogens do play a significant role in the free troposphere. In particular, the chlorine initiation of methane oxidation in the free troposphere can contribute more than 10%, and in some regions up to 50%, of the total rate of initiation. The initiation of methane oxidation by chlorine is particularly important below the polar vortex and in northern mid-latitudes. Likewise, the hydrolysis of BrONO2 alone can contribute more than 35% of the HNO3 production rate in the free-troposphere.

Lary, David John↗

Oxygenated Organic Chemicals in the Pacific Troposphere: Distribution, Sources and Chemistry

Airborne measurements of a large number of oxygenated organic chemicals (Oxorgs) were carried out in the Pacific troposphere (0.1-12 km) in the Spring of 2001 (Feb. 24-April 10). Specifically these measuremen ts included acetone, methylethyl ketone (MEK), methanol, ethanol, ace taldehyde, propionaldehyde, PANS, and organic nitrates. Complementary measurements of formaldehyde, organic peroxides, and tracers were al so available. Ox-orgs were abundant in the clean troposphere and were greatly enhanced in the outflow regions from Asia. Their mixing ratios were typically highest in the lower troposphere and declined toward s the upper troposphere and the lowermost stratosphere. Their total a bundance (Ox-orgs) significantly exceeded that of NMHC (C2-C8 NMHC). A comparison of these data with observations collected some seven yea rs earlier (Feb.-March, 1994), did not reveal any significant changes . Throughout the troposphere mixing ratios of Ox-orgs were strongly c orrelated with each other as well as with tracers of fossil and bioma sshiof'uel combustion. Analysis of the relative enhancement of selected Oxorgs with respect to CH3Cl and CO in twelve sampled plumes, origi nating from fires, is used to assess their primary and secondary sour ces from biomass combustion. The composition of these plumes also ind icates a large shift of reactive nitrogen into the PAN reservoir ther eby limiting ozone formation. The Harvard 3-D photochemical model, th at uses state of the art chemistry and source information, is used to compare simulated and observed mixing ratios of selected species. A 1 -D model is used to explore the chemistry of aldehydes. These results will be presented.

Singh, Hanwant B.↗