Person:

Logan, Jennifer

We examine the sources and chemistry affecting nitrogen oxides (NOx = NO + NO2) over the tropical Pacific (30°S–20°N) using observations from the Pacific Exploratory Mission to the Tropics B (PEM-Tropics B) aircraft mission conducted in March–April 1999. A global model of tropospheric chemistry driven by assimilated meteorological data is used to interpret the observations. Median concentrations observed over the South Pacific during PEM-Tropics B were 7 pptv NO, 16 pptv peroxyacetyl nitrate (PAN), and 34 pptv nitric acid (HNO3); the model generally reproduces these observations but overestimates those over the North Pacific. Lightning was the largest source of these species in the equatorial and South Pacific tropospheric column and in the tropical North Pacific upper troposphere. The oceanic source of acetone implied by high observations of acetone concentrations (mean 431 pptv) allows an improved simulation of PAN/NOx chemistry. However, the high acetaldehyde concentrations (mean 78 pptv) measured throughout the troposphere are inconsistent with our understanding of acetaldehyde and PAN chemistry. Simulated concentrations of HNO3 and HNO3/NOx are highly sensitive to the model representation of deep convection and associated HNO3 scavenging. Chemical losses of NOx during PEM-Tropics B exceed chemical sources by a factor of 2 in the South Pacific upper troposphere. The chemical imbalance, also apparent in the low observed HNO3/NOx ratio, is explained by NOx injection from lightning and by frequent convective overturning which depletes HNO3. The observed imbalance was less during the PEM-Tropics A campaign in September 1996, when aged biomass burning effluents over the South Pacific pushed the NOx budget toward chemical steady state.

We define the radiative forcings used in climate simulations with the SI2000 version of the Goddard Institute for Space Studies (GISS) global climate model. These include temporal variations of well-mixed greenhouse gases, stratospheric aerosols, solar irradiance, ozone, stratospheric water vapor, and tropospheric aerosols. Our illustrations focus on the period 1951–2050, but we make the full data sets available for those forcings for which we have earlier data. We illustrate the global response to these forcings for the SI2000 model with specified sea surface temperature and with a simple Q-flux ocean, thus helping to characterize the efficacy of each forcing. The model yields good agreement with observed global temperature change and heat storage in the ocean. This agreement does not yield an improved assessment of climate sensitivity or a confirmation of the net climate forcing because of possible compensations with opposite changes of these quantities. Nevertheless, the results imply that observed global temperature change during the past 50 years is primarily a response to radiative forcings. It is also inferred that the planet is now out of radiation balance by 0.5 to 1 W/m2 and that additional global warming of about 0.5°C is already “in the pipeline.”

We use an inverse model analysis to compare the top-down constraints on Asian sources of carbon monoxide (CO) in spring 2001 from (1) daily MOPITT satellite observations of CO columns over Asia and the neighboring oceans and (2) aircraft observations of CO concentrations in Asian outflow from the TRACE-P aircraft mission over the northwest Pacific. The inversion uses the maximum a posteriori method (MAP) and the GEOS-CHEM chemical transport model (CTM) as the forward model. Detailed error characterization is presented, including spatial correlation of the model transport error. Nighttime MOPITT observations appear to be biased and are excluded from the inverse analysis. We find that MOPITT and TRACE-P observations are independently consistent in the constraints that they provide on Asian CO sources, with the exception of southeast Asia for which the MOPITT observations support a more modest decrease in emissions than suggested by the aircraft observations. Our analysis indicates that the observations do not allow us to differentiate source types (i.e., anthropogenic versus biomass burning) within a region. MOPITT provides ten pieces of information to constrain the geographical distribution of CO sources, while TRACE-P provides only four. The greater information from MOPITT reflects its ability to observe all outflow and source regions. We conducted a number of sensitivity studies for the inverse model analysis using the MOPITT data. Temporal averaging of the MOPITT data (weekly and beyond) degrades the ability to constrain regional sources. Merging source regions beyond what is appropriate after careful selection of the state vector leads to significant aggregation errors. Calculations for an ensemble of realistic assumptions lead to a range of inverse model solutions that has greater uncertainty than the a posteriori errors for the MAP solution. Our best estimate of total Asian CO sources is 361 Tg yr−1, over half of which is attributed to east Asia.

Aircraft observations of Asian outflow from the Transport and Chemical Evolution Over the Pacific (TRACE-P) aircraft mission over the NW Pacific (March and April 2001) show large CH4 enhancements relative to background, as well as strong CH4-C2H6-CO correlations that provide signatures of regional sources. We apply a global chemical transport model simulation of the CH4-C2H6-CO system for the TRACE-P period to interpret these observations in terms of CH4 sources and to explore in particular the unique constraints from the CH4-C2H6-CO correlations. We use as a priori a global CH4 source inventory constrained with National Oceanic and Atmospheric Administration (NOAA) Climate Monitoring and Diagnostics Laboratory (CMDL) surface observations [Wang et al., 2004]. We find that the observed CH4 concentration enhancements and CH4-C2H6-CO correlations in Asian outflow in TRACE-P are determined mainly by anthropogenic emissions from China and Eurasia (defined here as Europe and eastern Russia), with only little contribution from tropical sources (wetlands and biomass burning). The a priori inventory overestimates the observed CH4 enhancements and shows regionally variable biases for the CH4/C2H6 slope. The CH4/CO slopes are simulated without significant bias. Matching both the observed CH4 enhancements and the CH4-C2H6-CO slopes in Asian outflow requires increasing the east Asian anthropogenic source of CH4, and decreasing the Eurasian anthropogenic source, by at least 30% for both. The need to increase the east Asian source is driven by the underestimate of the CH4/C2H6 slope in boundary layer Chinese outflow. The Streets et al. [2003] anthropogenic emission inventory for east Asia fits this constraint by increasing CH4 emissions from that region by 40% relative to the a priori, largely because of higher livestock and landfill source estimates. Eurasian sources (mostly European) then need to be reduced by 30–50% from the a priori value of 68 Tg yr−1. The decrease of European sources could result in part from recent mitigation of emissions from coal mining and landfills.

We use observed CO2:CO correlations in Asian outflow from the TRACE-P aircraft campaign (February–April 2001), together with a three-dimensional global chemical transport model (GEOS-CHEM), to constrain specific components of the east Asian CO2 budget including, in particular, Chinese emissions. The CO2/CO emission ratio varies with the source of CO2 (different combustion types versus the terrestrial biosphere) and provides a characteristic signature of source regions and source type. Observed CO2/CO correlation slopes in east Asian boundary layer outflow display distinct regional signatures ranging from 10–20 mol/mol (outflow from northeast China) to 80 mol/mol (over Japan). Model simulations using best a priori estimates of regional CO2 and CO sources from Streets et al. [2003] (anthropogenic), the CASA model (biospheric), and Duncan et al. [2003] (biomass burning) overestimate CO2 concentrations and CO2/CO slopes in the boundary layer outflow. Constraints from the CO2/CO slopes indicate that this must arise from an overestimate of the modeled regional net biospheric CO2 flux. Our corrected best estimate of the net biospheric source of CO2 from China for March–April 2001 is 3200 Gg C/d, which represents a 45% reduction of the net flux from the CASA model. Previous analyses of the TRACE-P data had found that anthropogenic Chinese CO emissions must be ∼50% higher than in Streets et al.'s [2003] inventory. We find that such an adjustment improves the simulation of the CO2/CO slopes and that it likely represents both an underreporting of sector activity (domestic and industrial combustion) and an underestimate of CO emission factors. Increases in sector activity would imply increases in Chinese anthropogenic CO2 emissions and would also imply a further reduction of the Chinese biospheric CO2 source to reconcile simulated and observed CO2 concentrations.

Four global scale and three regional scale chemical transport models are intercompared and evaluated during NASA's Transport and Chemical Evolution over the Pacific (TRACE-P) experiment. Model simulated and measured CO are statistically analyzed along aircraft flight tracks. Results for the combination of 11 flights show an overall negative bias in simulated CO. Biases are most pronounced during large CO events. Statistical agreements vary greatly among the individual flights. Those flights with the greatest range of CO values tend to be the worst simulated. However, for each given flight, the models generally provide similar relative results. The models exhibit difficulties simulating intense CO plumes. CO error is found to be greatest in the lower troposphere. Convective mass flux is shown to be very important, particularly near emissions source regions. Occasionally meteorological lift associated with excessive model-calculated mass fluxes leads to an overestimation of middle and upper tropospheric mixing ratios. Planetary Boundary Layer (PBL) depth is found to play an important role in simulating intense CO plumes. PBL depth is shown to cap plumes, confining heavy pollution to the very lowest levels.

We interpret the distribution of tropical tropospheric ozone columns (TTOCs) from the Total Ozone Mapping Spectrometer (TOMS) by using a global three-dimensional model of tropospheric chemistry (GEOS-CHEM) and additional information from in situ observations. The GEOS-CHEM TTOCs capture 44% of the variance of monthly mean TOMS TTOCs from the convective cloud differential method (CCD) with no global bias. Major discrepancies are found over northern Africa and south Asia where the TOMS TTOCs do not capture the seasonal enhancements from biomass burning found in the model and in aircraft observations. A characteristic feature of these northern tropical enhancements, in contrast to southern tropical enhancements, is that they are driven by the lower troposphere where the sensitivity of TOMS is poor due to Rayleigh scattering. We develop an efficiency correction to the TOMS retrieval algorithm that accounts for the variability of ozone in the lower troposphere. This efficiency correction increases TTOCs over biomass burning regions by 3–5 Dobson units (DU) and decreases them by 2–5 DU over oceanic regions, improving the agreement between CCD TTOCs and in situ observations. Applying the correction to CCD TTOCs reduces by ∼5 DU the magnitude of the “tropical Atlantic paradox” [Thompson et al., 2000], i.e. the presence of a TTOC enhancement over the southern tropical Atlantic during the northern African biomass burning season in December–February. We reproduce the remainder of the paradox in the model and explain it by the combination of upper tropospheric ozone production from lightning NOx, persistent subsidence over the southern tropical Atlantic as part of the Walker circulation, and cross-equatorial transport of upper tropospheric ozone from northern midlatitudes in the African “westerly duct.” These processes in the model can also account for the observed 13–17 DU persistent wave-1 pattern in TTOCs with a maximum over the tropical Atlantic and a minimum over the tropical Pacific during all seasons. The photochemical effects of mineral dust have only a minor role on the modeled distribution of TTOCs, including over northern Africa, due to multiple competing effects. The photochemical effects of mineral dust globally decrease annual mean OH concentrations by 9%. A global lightning NOx source of 6 Tg N yr−1 in the model produces a simulation that is most consistent with TOMS and in situ observations.

The Tropospheric Emission Spectrometer (TES) on board NASA's Aura satellite (to be launched in 2004) will provide measurements of global distributions of ozone, CO, and other key chemical species in the troposphere. In order for TES to meet a design lifetime of 5 years, it has been determined that a global survey strategy with ∼50% duty cycle must be identified. In this study, simulated concentrations of ozone and CO from the GEOS-CHEM global three-dimensional (3-D) model of troposphere chemistry are used as a time-varying synthetic atmosphere for demonstrating and assessing the capabilities of TES nadir observations. Autocorrelation analyses of the model species fields for different time lags identify a significant 1-day correlation and support a 1-day-on/1-day-off observation strategy. Three major steps are then taken to demonstrate and evaluate TES products: (1) species profiles along the TES orbit track are sampled from the model 3-D time-varying fields with cloudy scenes (50-60% of total scenes) removed; (2) nadir-retrieved profiles (“level 2 products”) are obtained from these “true” synthetic profiles using TES retrieval characteristic functions; (3) interpolated daily global maps (“level 3 products”) are generated to compare with the original model fields. The latter comparison indicates that the error in the level 3 products relative to the true fields for ozone and CO is <10% in ∼70% of cases and <20% in 80–90% of cases. The three major sources of error lie in the asynoptic orbital sampling, the retrieval, and the level 3 global mapping.

A global three-dimensional model of tropospheric chemistry driven by reanalyzed European Centre for Medium-Range Weather Forecasts meteorological data is used to examine the sources of O3, CO, and nitrogen oxides (NOx = NO + NO2) in the South Pacific troposphere during the NASA Pacific Exploratory Mission to the Tropics (PEM-Tropics A) in September–October 1996. Aircraft observations up to 12 km during that mission revealed considerable biomass burning influence on O3 and CO in terms of elevated pollution layers and regional enhancements. The model reproduces the long-range transport of biomass burning effluents from southern Africa and South America in the westerly subtropical flow over the South Pacific. Meteorological conditions in 1996 were particularly favorable for this transport. Africa and South America make comparable contributions to the biomass burning pollution over the South Pacific; the contribution from Australia and Indonesia is much less. Biomass burning dominates the supply of NOx in the lower troposphere over the South Pacific (through long-range transport and decomposition of peroxyacetylnitrate), but lightning dominates in the upper troposphere. Observations in PEM-Tropics A and elsewhere indicate low HNO3/NOx concentration ratios and an imbalance in the chemical budget of NOx in the upper troposphere. We reproduce these observations in our model and show that they reflect the subsidence of primary NOx injected by lightning into the uppermost troposphere, rather than any fast chemistry recycling HNO3 to NOx. We find that biomass burning and lightning made similar contributions to O3 production over the South Pacific during PEM-Tropics A. Biomass burning plumes sampled in PEM-Tropics A contained little NOx, and the O3 enhancements observed in these plumes originated from production over the source continents rather than over the South Pacific.

We analyze the Asian outflow of CO, ozone, and nitrogen oxides (NOx) to the Pacific in spring by using the GEOS-CHEM global three-dimensional model of tropospheric chemistry and simulating the Pacific Exploratory Mission-West (PEM-West B) aircraft mission in February–March 1994. The GEOS-CHEM model uses assimilated meteorological fields from the NASA Goddard Earth Observing System (GEOS). It reproduces relatively well the main features of tropospheric ozone, CO, and reactive nitrogen species observed in PEM-West B, including latitudinal and vertical gradients of the Asian pollution outflow over the western Pacific although simulated concentrations of CO tend to be too low (possibly because biogenic sources are underestimated). We use CO as a long-lived tracer to diagnose the processes contributing to the outflow. The highest concentrations in the outflow are in the boundary layer (0–2 km), but the strongest outflow fluxes are in the lower free troposphere (2–5 km) and reflect episodic lifting of pollution over central and eastern China ahead of eastward moving cold fronts. This frontal lifting, followed by westerly transport in the lower free troposphere, is the principal process responsible for export of both anthropogenic and biomass burning pollution from Asia. Anthropogenic emissions from Europe and biomass burning emissions from Africa make also major contributions to the Asian outflow over the western Pacific; European sources dominate in the lower troposphere north of 40°N, while African sources are important in the upper troposphere at low latitudes. For the period of PEM-West B (February–March) we estimate that fossil fuel combustion and biomass burning make comparable contributions to the budgets of CO, ozone, and NOx. in the Asian outflow. We find that 13% of NOx emitted in Asia is exported as NOx or PAN, a smaller fraction than for the United States because of higher aerosol concentrations that promote heterogeneous conversion of NOx to HNO3. Production and export of ozone from Asia in spring is much greater than from the United States because of the higher photochemical activity.