Person:

Jacob, Daniel

Two cold front episodes were sampled during the two flights out of Yokota, Japan, during the Transport and Chemical Evolution Over the Pacific (TRACE-P) experiment during March 2001. The data from these two flights are examined using a mesoscale three-dimensional model. We show how these cyclonic systems have impacted the export of pollution out of the Asian continent. We contrast the relative role of convection and ascent in the warm conveyor belts associated with the cyclone during these two episodes. Although the necessary meteorological conditions for an efficient export of pollution are met during flight 13 (i.e., the occurrences of the warm conveyor belt near the source regions), no significant pollution is simulated in the mid-Pacific in the lower and middle troposphere. The efficient ventilation of the WCB by convection near the coast, the advection by the anticyclonical flow above 700 hPa, and the downward motion associated with the Pacific high in the remote ocean significantly prevent any long-range transport of undiluted pollution in the WCB. During flight 15 the conveyor belts have already moved to the remote ocean. The polluted plume is split by the rising air in the warm conveyor belt which transports CO-poor air northward and by the oceanic convection which transports clean air masses upward. These mechanisms lead to the dilution of Asian pollution in WCB en route to North America and add to the episodic nature of the Asian outflow by fragmenting the pollution plume.

Fossil fuel combustion accounts for >50% of the global atmospheric emission of NOx, but this source is concentrated in the polluted continental boundary layer (CBL) and only a small fraction is exported as NOy (NOx and its oxidation products) to the global troposphere. Better quantification of this export efficiency is needed because of its implications for global tropospheric ozone. A recent Lagrangian analysis of the NOy-CO correlations observed from the North Atlantic Regional Experiment in September 1997 (NARE'97) aircraft campaign downwind of eastern North America (September 1997) indicated a NOy export efficiency of <10%, with <10% of the exported NOy present as NOx. In contrast, previous three-dimensional (3-D) model Eulerian budget analyses for the North American boundary layer indicated NOy export efficiencies of 25–30%, with 30–35% of the exported NOy present as NOx. We investigated this apparent discrepancy by simulating the NARE'97 aircraft observations with a global 3-D model of tropospheric chemistry (GEOS-CHEM) and using the model to calculate the NOy export efficiency both through a Lagrangian analysis of the NOy-CO correlations along the aircraft flight tracks and through an Eulerian budget analysis for the North American boundary layer. The model reproduces the variability and NOy-CO correlations observed in the aircraft data and also at the Harvard Forest surface site in the northeastern United States. We show that the previous Lagrangian analyses of the NOy export efficiency during NARE'97 were probably biased low because of underestimation of the CO background. Correcting for this bias, we find a NOy export efficiency of 17 ± 7% in the model and 15 ± 11% in the observations. A similar NOy export efficiency (20%) in the model is obtained from the Eulerian budget analysis, demonstrating that the Lagrangian and Eulerian approaches are in fact consistent. Export efficiencies of NOy in previous 3-D model Eulerian budget analyses were probably too high because of insufficient scavenging out of the CBL. Model results indicate that only 6% of the exported NOy is present as NOx along the aircraft flight tracks, in agreement with the observations, but that 40% of the NOy export flux is present as NOx, in agreement with the previous 3-D model analyses. This result reflects the fast oxidation of NOx between the point of exit from the CBL and the point of sampling by the aircraft. The eventual ozone production in the global troposphere due to exported NOx and peroxyacetylnitrate (PAN), with equal contributions from each, is comparable in magnitude to the direct export of ozone pollution from the North American boundary layer.

We construct global atmospheric budgets of HCN and CH3CN through a three-dimensional (3-D) model simulation of the HCN-CH3CN-CO system constrained and evaluated with aircraft observations from the Transport and Chemical Evolution Over the Pacific (TRACE-P) mission over the NW Pacific in February–April 2001. Observed background vertical gradients of HCN and CH3CN imply a dominant ocean sink for both gases, with deposition velocity of 0.13 cm s−1 for both and saturation ratios of 0.79 for HCN and 0.88 for CH3CN. Observations for both gases in the free troposphere imply a dominant source from biomass burning. Enhancement of HCN observed in Chinese urban plumes is attributed tentatively to residential coal burning. Biomass burning and residential coal burning emission ratios relative to CO of 0.27% and 1.6%, respectively, for HCN, and of 0.20% and 0.25%, respectively, for CH3CN, are consistent with observations in biomass burning and Chinese urban plumes. They provide the best model simulation of the ensemble of TRACE-P observations including vertical profiles and HCN-CH3CN-CO correlations. They also allow successful simulation of the long-term observations of HCN columns at sites in the Northern Hemisphere, and of the CH3CN vertical distribution observed over the northern Indian Ocean. Global biomass burning and Asian residential coal burning sources in the model are 0.63 and 0.2 Tg N yr−1, respectively, for HCN and 0.47 and 0.03 Tg N yr−1, respectively, for CH3CN. Ocean uptake is the dominant sink for both gases, with oxidation by OH representing an additional minor sink. The resulting tropospheric lifetimes are 5.3 months for HCN and 5.8 months for CH3CN. The model predicts very low HCN and CH3CN concentrations at high southern latitudes, reflecting the assumption of a uniform saturation ratio for ocean uptake; observations in that region are needed. In the free troposphere, the dominance of biomass burning sources (70–85% for HCN and 90–95% for CH3CN) implies that both gases can be used as biomass burning tracers. In the boundary layer, CH3CN appears to be a better biomass burning tracer. More work is needed to identify the origin of the Chinese urban source of HCN.

We develop a daily-resolved global emission inventory for biomass burning using AVHRR satellite observations of fire activity corrected for data gaps and scan angle biases. We implemented this inventory in a global three-dimensional model (GEOS-CHEM) to simulate aircraft CO observations during the TRACE-P mission over the NW Pacific in February–April 2001. Seasonal biomass burning in SE Asia was a major contributor to the outflow of Asian pollution observed in TRACE-P and shows large day-to-day fluctuations that vary depending on location. Three simulations were conducted with the same 3-month total (February–April) emissions but different temporal distributions: 2001 daily resolved, 2001 monthly resolved, and climatological monthly resolved. The effect of daily resolved versus monthly resolved 2001 emissions in the simulation of CO is less than 8 ppbv in Asian outflow over the NW Pacific but can exceed 100 ppbv over source regions. The relatively small effect in Asian outflow reflects spatial and temporal averaging of emissions during ageing in the continental boundary layer. Significant improvement in the simulation of TRACE-P observations (as diagnosed by the resolved variance) is found when using 2001 monthly versus climatological monthly emissions, but using 2001 daily emissions does not offer further improvement.

We examine the transatlantic transport of anthropogenic ozone and its impact on surface ozone in Europe and North America by using a 5-year (1993–1997) simulation with the GEOS-CHEM global three-dimensional model of tropospheric chemistry. Long-term time series of ozone and CO at Mace Head (Ireland) and Sable Island (Canada) are used to evaluate transatlantic transport in the model. North American anthropogenic emissions contribute on average 5 ppbv to surface ozone at Mace Head, and up to 10–20 ppbv during transatlantic transport events, which are forerunners of broader events in Europe. These events are associated with low-level westerly flow driven by an intense Icelandic low between Iceland and the British Isles. North American influence on ozone at Mace Head is strongly correlated with the North Atlantic Oscillation (NAO), implying that the NAO index can be used to forecast transatlantic transport of North American pollution to Europe. European anthropogenic emissions contribute on average less than 2 ppbv to surface ozone at Sable Island but up to 5–10 ppbv during transatlantic transport events. These events are associated with low-level easterly flow established by anomalous low pressure at 45°N over the North Atlantic. North American anthropogenic emissions enhance surface ozone in continental Europe by 2–4 ppbv on average in summer and by 5–10 ppbv during transatlantic transport events; transport in the boundary layer and subsidence from the free troposphere are both important mechanisms. We find in the model that 20% of the violations of the European Council ozone standard (55 ppbv, 8-hour average) in the summer of 1997 over Europe would not have occurred in the absence of anthropogenic emissions from North America. North American influence on surface ozone in Europe is particularly strong at the thresholds used for the European standards (55–65 ppbv).

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.