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Soils have been identified as a major source (~15%) of global nitrogen oxide (NOx) emissions. Parameterizations of soil NOx emissions (SNOx) commonly used in the current generation of chemical transport models were designed to capture mean seasonal behaviour. These parameterizations do not, however, respond quantitatively to the meteorological triggers that are observed to result in pulsed SNOx. Here we present a new parameterization of SNOx implemented within a global chemical transport model (GEOS-Chem). The parameterization represents available nitrogen (N) in soils using biome specific emission factors, online wet- and dry-deposition of N, and fertilizer and manure N derived from a spatially explicit dataset, distributed using seasonality derived from data obtained by the Moderate Resolution Imaging Spectrometer. Moreover, it represents the functional form of emissions derived from point measurements and ecosystem scale experiments including pulsing following soil wetting by rain or irrigation, and emissions that are a smooth function of soil moisture as well as temperature between 0 and 30 °C. This parameterization yields global above-soil SNOx of 10.7 Tg N yr−1, including 1.8 Tg N yr−1 from fertilizer N input (1.5% of applied N) and 0.5 Tg N yr−1 from atmospheric N deposition. Over the United States (US) Great Plains region, SNOx are predicted to comprise 15–40% of the tropospheric NO2 column and increase column variability by a factor of 2–4 during the summer months due to chemical fertilizer application and warm temperatures. SNOx enhancements of 50–80% of the simulated NO2 column are predicted over the African Sahel during the monsoon onset (April–June). In this region the day-to-day variability of column NO2 is increased by a factor of 5 due to pulsed-N emissions. We evaluate the model by comparison with observations of NO2 column density from the Ozone Monitoring Instrument (OMI). We find that the model is able to reproduce the observed interannual variability of NO2 (induced by pulsed-N emissions) over the US Great Plains. We also show that the OMI mean (median) NO2 observed during the overpass following first rainfall over the Sahel is 49% (23%) higher than in the five days preceding. The measured NO2 on the day after rainfall is still 23% (5%) higher, providing a direct measure of the pulse's decay time of 1–2 days. This is consistent with the pulsing representation used in our parameterization and much shorter than 5–14 day pulse decay length used in current models.

Inference of NOx emissions (NO+NO2) from satellite observations of tropospheric NO2 column requires knowledge of NOx lifetime, usually provided by chemical transport models (CTMs). However, it is known that species subject to non-linear sources or sinks, such as ozone, are susceptible to biases in coarse-resolution CTMs. Here we compute the resolution-dependent bias in predicted NO2 column, a quantity relevant to the interpretation of space-based observations. We use 1-D and 2-D models to illustrate the mechanisms responsible for these biases over a range of NO2 concentrations and model resolutions. We find that predicted biases are largest at coarsest model resolutions with negative biases predicted over large sources and positive biases predicted over small sources. As an example, we use WRF-CHEM to illustrate the resolution necessary to predict 10 AM and 1 PM NO2 column to 10 and 25% accuracy over three large sources, the Four Corners power plants in NW New Mexico, Los Angeles, and the San Joaquin Valley in California for a week-long simulation in July 2006. We find that resolution in the range of 4–12 km is sufficient to accurately model nonlinear effects in the NO2 loss rate.

We use recent aircraft measurements of a comprehensive suite of anthropogenic halocarbons, carbon monoxide (CO), and related tracers to place new constraints on North American halocarbon emissions and quantify their global warming potential. Using a chemical transport model (GEOS-Chem) we find that the ensemble of observations are consistent with our prior best estimate of the U.S. anthropogenic CO source, but suggest a 30% underestimate of Mexican emissions. We develop an optimized CO emission inventory on this basis and quantify halocarbon emissions from their measured enhancements relative to CO. Emissions continue for many compounds restricted under the Montreal Protocol, and we show that halocarbons make up an important fraction of the total greenhouse gas source for both countries: our best estimate is 9% (uncertainty range 6-12%) and 32% (21-52%) of equivalent CO2 emissions for the U.S. and Mexico, respectively, on a 20 year time scale. Performance of bottom-up emission inventories is variable, with underestimates for some compounds and overestimates for others. Ongoing methylchloroform emissions are significant in the U.S. (2.8 Gg/y in 2004-2006), in contrast to bottom-up estimates (< 0.05 Gg), with implications for tropospheric OH calculations. Mexican methylchloroform emissions are minor.

We estimate future area burned in the Alaskan and Canadian forest by the mid-century (2046–2065) based on the simulated meteorology from 13 climate models under the A1B scenario. We develop ecoregion-dependent regressions using observed relationships between annual total area burned and a suite of meteorological variables and fire weather indices, and apply these regressions to the simulated meteorology. We find that for Alaska and western Canada, almost all models predict significant (p < 0.05) increases in area burned at the mid-century, with median values ranging from 150 to 390 %, depending on the ecoregion. Such changes are attributed to the higher surface air temperatures and 500 hPa geopotential heights relative to present day, which together lead to favorable conditions for wildfire spread. Elsewhere the model predictions are not as robust. For the central and southern Canadian ecoregions, the models predict increases in area burned of 45–90 %. Except for the Taiga Plain, where area burned decreases by 50 %, no robust trends are found in northern Canada, due to the competing effects of hotter weather and wetter conditions there. Using the GEOS-Chem chemical transport model, we find that changes in wildfire emissions alone increase mean summertime surface ozone levels by 5 ppbv for Alaska, 3 ppbv for Canada, and 1 ppbv for the western US by the mid-century. In the northwestern US states, local wildfire emissions at the mid-century enhance surface ozone by an average of 1 ppbv, while transport of boreal fire pollution further degrades ozone air quality by an additional 0.5 ppbv. The projected changes in wildfire activity increase daily summertime surface ozone above the 95th percentile by 1 ppbv in the northwestern US, 5 ppbv in the high latitudes of Canada, and 15 ppbv in Alaska, suggesting a greater frequency of pollution episodes in the future atmosphere.

[1] Nitrogen oxides (NOx ≡ NO + NO2) produced by lightning make a major contribution to the global production of tropospheric ozone and OH. Lightning distributions inferred from standard convective parameterizations in global chemical transport models (CTMs) fail to reproduce observations from the Lightning Imaging Sensor (LIS) and the Optical Transient Detector (OTD) satellite instruments. We present an optimal regional scaling algorithm for CTMs to fit the lightning NOxsource to the satellite lightning data in a way that preserves the coupling to deep convective transport. We show that applying monthly scaling factors over ∼37 regions globally significantly improves the tropical ozone simulation in the GEOS-Chem CTM as compared to a simulation unconstrained by the satellite data and performs equally well to a simulation with local scaling. The coarse regional scaling preserves sufficient statistics in the satellite data to constrain the interannual variability (IAV) of lightning. After processing the LIS data to remove their diurnal sampling bias, we construct a monthly time series of lightning flash rates for 1998–2010 and 35°S–35°N. We find a correlation of IAV in total tropical lightning with El Nino but not with the solar cycle or the quasi-biennial oscillation. The global lightning NOxsource ± IAV standard deviation in GEOS-Chem is 6.0 ± 0.5 Tg N yr−1, compared to 5.5 ± 0.8 Tg N yr−1 for the biomass burning source. Lightning NOx could have a large influence on the IAV of tropospheric ozone because it is released in the upper troposphere where ozone production is most efficient.

Prediction of ozone production, a photochemically non-linear process, is known to be biased in coarse-resolution chemical transport models (CTM). Other species subject to non-linear sources or sinks are also susceptible. Here we compute the resolution-dependent bias in predicted NO2 column, a quantity relevant to the interpretation of space-based observations. We use 1-D and 2-D models to illustrate the mechanisms responsible for these biases over a range of NO2 concentrations and model resolutions. We find that the behavior of calculated biases in NO2 depends on the magnitude and spatial extent of the NO2 source. We use WRF-CHEM to determine the resolution necessary to predict column NO2 to 10 % and 25 % over the Four Corners power plants in NW New Mexico, Los Angeles, and the San Joaquin Valley in California.

We use observations of fire radiative power (FRP) from the Moderate Resolution Imaging Spectroradiometer~(MODIS) and tropospheric NO2 column measurements from the Ozone Monitoring Instrument (OMI) to derive NO2 wildfire emission coefficients (g MJ−1) for three land types over California and Nevada. Retrieved emission coefficients were 0.279±0.077, 0.342±0.053, and 0.696±0.088 g MJ−1 NO2 for forest, grass and shrub fuels, respectively. These emission coefficients reproduce ratios of emissions with fuel type reported previously using independent methods. However, the magnitude of these coefficients is lower than prior estimates. While it is possible that a negative bias in the OMI NO2 retrieval over regions of active fire emissions is partly responsible, comparison with several other studies of fire emissions using satellite platforms indicates that current emission factors may overestimate the contributions of flaming combustion and underestimate the contributions of smoldering combustion to total fire emissions. Our results indicate that satellite data can provide an extensive characterization of the variability in fire NOx emissions; 67 % of the variability in emissions in this region can be accounted for using an FRP-based parameterization.

[1] We investigate the impact of climate change on wildfire activity and carbonaceous aerosol concentrations in the western United States. We regress observed area burned onto observed meteorological fields and fire indices from the Canadian Fire Weather Index system and find that May–October mean temperature and fuel moisture explain 24–57% of the variance in annual area burned in this region. Applying meteorological fields calculated by a general circulation model (GCM) to our regression model, we show that increases in temperature cause annual mean area burned in the western United States to increase by 54% by the 2050s relative to the present day. Changes in area burned are ecosystem dependent, with the forests of the Pacific Northwest and Rocky Mountains experiencing the greatest increases of 78 and 175%, respectively. Increased area burned results in near doubling of wildfire carbonaceous aerosol emissions by midcentury. Using a chemical transport model driven by meteorology from the same GCM, we calculate that climate change will increase summertime organic carbon (OC) aerosol concentrations over the western United States by 40% and elemental carbon (EC) concentrations by 20% from 2000 to 2050. Most of this increase (75% for OC and 95% for EC) is caused by larger wildfire emissions with the rest caused by changes in meteorology and for OC by increased monoterpene emissions in a warmer climate. Such an increase in carbonaceous aerosol would have important consequences for western U.S. air quality and visibility.

[1] We use observations from the International Consortium for Atmospheric Research on Transport and Transformation (ICARTT) campaign over eastern North America in summer 2004, interpreted with a global 3-D model of tropospheric chemistry (GEOS-Chem), to improve and update estimates of North American influence on global tropospheric ozone and the effect of recent U.S. anthropogenic reductions on surface ozone pollution. We find that the 50% decrease in U.S. stationary NOx sources since 1999 has decreased mean U.S. boundary layer ozone concentrations by 6–8 ppbv in the southeast and 4–6 ppbv in the Midwest. The observed dO3/dCO molar enhancement ratio in the U.S. boundary layer during ICARTT was 0.46 mol mol−1, larger than the range of 0.3–0.4 from studies in the early 1990s, possibly reflecting the decrease in the NOx/CO emission ratio as well as an increase in the ozone production efficiency per unit NOx. North American NOx emissions during summer 2004 as constrained by the ICARTT observations (0.72 Tg N fossil fuel, 0.11 Tg N biomass burning, 0.28 Tg N lightning for 1 July to 15 August) enhanced the hemispheric tropospheric ozone burden by 12.4%, with comparable contributions from fossil fuel and lightning (5–6%), but only 1% from biomass burning emissions despite 2004 being a record fire year over Alaska and western Canada.

International audience; Carbon monoxide (CO) total column observations from the Scanning Imaging Absorption Spectrometer for Atmospheric Cartography (SCIAMACHY) on board Envisat-1 are assimilated into the Global Modeling and Assimilation Office constituent assimilation system for the period 1 April to 20 December 2004. The impact of the assimilation on CO distribution is evaluated using independent surface flask observations from the National Oceanic and Atmospheric Administration (NOAA)/ESRL global cooperative air sampling network and Measurement of Ozone and Water Vapor by Airbus In-Service Aircraft (MOZAIC) in situ CO profiles. Assimilation of SCIAMACHY data improves agreement of CO assimilation with both of these data sets on both global and regional scales compared to the free-running model. Regional comparisons with MOZAIC profiles made in western Europe, the northeastern United States, and the Arabian Peninsula show improvements at all three locations in the free troposphere and into the boundary layer over Arabia and the northeastern United States. Comparisons with NOAA Earth System Research Laboratory data improve at about two thirds of the surface observation sites. The systematic model errors related to the uncertainty of CO surface sources and the chemistry of CO losses are investigated through experiments with increased surface CO emissions over the Arabian Peninsula and/or globally reduced hydroxyl radical (OH) concentrations. Both model changes decrease mean CO errors at all altitudes in comparison to MOZAIC data over Dubai and Abu Dhabi. In contrast, errors in the assimilated CO are reduced by the increased emissions for pressures ≥800 hPa and by the reduced OH for pressures ≤600 hPa. Our analysis suggests that CO emissions over Dubai in 2004 are more than double those in the 1998 emissions inventory.

[1] We use a 3-D chemical transport model (the GEOS-Chem CTM) to evaluate a global emission inventory for ethane (C2H6), with a best estimate for the global source of 13 Tg yr−1, 8.0 Tg yr−1 from fossil fuel production, 2.6 Tg yr−1 from biofuel, and 2.4 Tg yr−1 from biomass burning. About 80% of the source is emitted in the Northern Hemisphere. The model generally provides a reasonable and unbiased simulation of surface air observations, column measurements, and aircraft profiles worldwide, including patterns of geographical and seasonal variability. The main bias is a 20%–30% overestimate at European surface sites. Propagation of the C2H6 seasonal signal from northern midlatitudes to the equatorial western Pacific and the southern tropics demonstrates the dominance of northern midlatitudes as a source of C2H6 worldwide. Interhemispheric transport provides the largest C2H6 source to the Southern Hemisphere (1.7 Tg yr−1), and southern biomass burning provides the other major source (1.0 Tg yr−1). The C2H6 emission inventory for the United States from the Environmental Protection Agency (0.6 Tg yr−1) is considerably lower than our estimate constrained by extensive aircraft observations in the continental boundary layer (2.4 Tg yr−1). This appears to reflect a factor 7 underestimate in the fossil fuel source over the south-central United States. Our estimate of C2H6 emissions, together with observed ratios of CH4:C2H6, suggests that CH4 emissions from energy production in the U.S. may be underestimated by as much as 50%–100%.

Aircraft observations of carbon monoxide (CO) from the ICARTT campaign over the eastern United States in summer 2004 (July 1–August 15), interpreted with a global 3-D model of tropospheric chemistry (GEOS-Chem), show that the national anthropogenic emission inventory from the U.S. Environmental Protection Agency (93 Tg CO y−1) is too high by 60% in summer. Our best estimate of the CO anthropogenic source for the ICARTT period is 6.4 Tg CO, including 4.6 Tg from direct emission and 1.8 Tg CO from oxidation of anthropogenic volatile organic compounds (VOCs). The biogenic CO source for the same period from the oxidation of isoprene and other biogenic VOCs is 8.3 Tg CO, and is independently constrained by ICARTT observations of formaldehyde (HCHO). Anthropogenic emissions of CO in the U.S. have decreased to the point that they are now lower than the biogenic source in summer.

Retrievals from the Microwave Limb Sounder (MLS) and the Ozone Monitoring Instrument (OMI) on EOS-Aura were included in the Goddard Earth Observing System version 4 (GEOS-4) ozone data assimilation system. The distribution and daily to seasonal evolution of ozone in the stratosphere and troposphere during 2005 are investigated. In the lower stratosphere, where dynamical processes dominate, comparisons with independent ozonesonde and Measurement of Ozone and Water Vapour by Airbus In-Service Aircraft (MOZAIC) data indicate mean agreement within 10%. In the troposphere, OMI and MLS provide constraints on the ozone column, but the ozone profile shape results from the parameterized ozone chemistry and the resolved and parameterized transport. Assimilation of OMI and MLS data improves tropospheric column estimates in the Atlantic region but leads to an overestimation in the tropical Pacific and an underestimation in the northern high and middle latitudes in winter and spring. Transport and data biases are considered in order to understand these discrepancies. Comparisons of assimilated tropospheric ozone columns with ozonesonde data reveal root-mean-square (RMS) differences of 2.9-7.2 Dobson units (DU), which are smaller than the model-sonde RMS differences of 3.2-8.7 DU. Four different definitions of the tropopause using temperature lapse rate, potential vorticity (PV), and isentropic surfaces or ozone isosurfaces are compared with respect to their global impact on the estimated tropospheric ozone column. The largest sensitivity in the tropospheric ozone column is found near the subtropical jet, where the ozone- or PV-determined tropopause typically lies below the lapse rate tropopause. Copyright 2008 by the American Geophysical Union. U7 - Export Date: 2 August 2010 U7 - Source: Scopus U7 - Art. No.: D16S32

International audience; We analyze aircraft observations obtained during INTEX-A (1 July to 14 August 2004) to examine the summertime influence of Asian pollution in the free troposphere over North America. By applying correlation analysis and principal component analysis (PCA) to the observations between 6 and 12 km, we find dominant influences from recent convection and lightning (13% of observations), Asia (7%), the lower stratosphere (7%), and boreal forest fires (2%), with the remaining 71% assigned to background. Asian air masses are marked by high levels of CO, O3, HCN, PAN, C2H2, C6H6, methanol, and SO42-. The partitioning of NOy species in the Asian plumes is dominated by PAN (∼600 pptv), with varying NOx/HNO3 ratios in individual plumes, consistent with individual transit times of 3-9 days. Export of Asian pollution occurred in warm conveyor belts of midlatitude cyclones, deep convection, and in typhoons. Compared to Asian outflow measurements during spring, INTEX-A observations display lower levels of anthropogenic pollutants (CO, C3H8, C2H6, C6H6) due to shorter summer lifetimes; higher levels of biogenic tracers (methanol and acetone) because of a more active biosphere; and higher levels of PAN, NOx, HNO3, and O3 reflecting active photochemistry, possibly enhanced by efficient NOy export and lightning. The high ΔO3/ΔCO ratio (0.76 mol/mol) in Asian plumes during INTEX-A is due to strong photochemical production and, in some cases, mixing with stratospheric air along isentropic surfaces. The GEOS-Chem global model captures the timing and location of the Asian plumes. However, it significantly underestimates the magnitude of observed enhancements in CO, O3, PAN and NOx.

We use observations from two aircraft during the International Consortium for Atmospheric Research on Transport and Transformation (ICARTT) campaign over the eastern United States and North Atlantic during summer 2004, interpreted with a global 3-D model of tropospheric chemistry (GEOS-Chem) to test current understanding of the regional sources, chemical evolution, and export of nitrogen oxides. The boundary layer NO(x) data provide top-down verification of a 50% decrease in power plant and industry NO(x) emissions over the eastern United States between 1999 and 2004. Observed 8-12 8 km NO(x) concentrations in ICARTT were 0.55 +/- 36 ppbv, much larger than in previous United States aircraft campaigns (ELCHEM, SUCCESS, SONEX). We show that regional lightning was the dominant source of this NO(x) and increased upper tropospheric ozone by 10 ppbv. Simulating the ICARTT upper tropospheric NO(x) observations with GEOS-Chem require a factor of 4 increase in the model NO(x) yield per flash (to 500 mol/flash). Observed OH concentrations were a factor of 2 lower than can be explained from current photochemical models, and if correct would imply a broader lightning influence in the upper troposphere than presently thought.An NO(y)-CO correlation analysis of the fraction f of North American NO(x) emissions vented to the free troposphere as NO(y) (sum of NO(x) and its oxidation products PAN and HNO3) s shows observed f=16+/-10 percent and modeled f=14 +/- 8 percent, consistent with previous studies. Export to the lower free troposphere is mostly HNO3 but at higher altitudes is mostly PAN. The model successfully simulates NO(y) export efficiency and speciation, supporting previous model estimates of a large U.S. contribution to tropospheric ozone through NO(x) and PAN export.

A comprehensive group of reactive nitrogen species (NO, NO2, HNO3, HO2NO2, PANs, alkyl nitrates, and aerosol-NO3) were measured in the troposphere and lowermost stratosphere over North America and the Atlantic during July/August 2004 (INTEX-A) from the NASA DC-8 platform (0.1-12 km). Less reactive nitrogen species (HCN and CH3CN), that are also unique tracers of biomass combustion, were also measured along with a host of other gaseous (CO, VOC, OVOC, halocarbon) and aerosol tracers. Clean background air as well as air with influences from biogenic emissions, anthropogenic pollution, biomass combustion, and stratosphere was sampled both over continental U. S., Atlantic and Pacific. The North American upper troposphere was found to be greatly influenced by both lightning NO(x) and surface pollution lofted via convection and contained elevated concentrations of PAN, ozone, hydrocarbons, and NO(x). Under polluted conditions PAN was a dominant carrier of reactive nitrogen in the upper troposphere while nitric acid dominated in the lower troposphere. Peroxynitric acid (HO2NO2) was present in sizable concentrations always peaking at around 8 km. Aerosol nitrate appeared to be mostly contained in large soil based particles in the lower troposphere. Plumes from Alaskan fires contained large amounts of PAN and very little enhancement in ozone. Observational data suggest that lightning was a far greater contributor to NO(x) in the upper troposphere than previously believed. NO(x) and NO(y) reservoir appeared to be in steady state only in the middle troposphere where NO(x)/NO(y) was independent of air mass age. A first comparison of observed data with simulations from four 3-D models shows significant differences between observations and models as well as among models. These uncertainties likely propagate themselves in satellites derived NOx data. Observed data are interpreted to suggest that soil sinks of HCN/CH3CN are at best very small. We investigate the partitioning and interplay of the reactive nitrogen species within characteristic air masses and further examine their role in ozone formation.

The summer of 2004 was one of the largest fire seasons on record for Alaska and western Canada. We construct a daily bottom-up fire emission inventory for that season, including consideration of peat burning and high-altitude (buoyant) injection, and evaluate it in a global chemical transport model (the GEOS-Chem CTM) simulation of CO through comparison with MOPITT satellite and ICARTT aircraft observations. The inventory is constructed by combining daily area burned reports and MODIS fire hot spots with estimates of fuel consumption and emission factors based on ecosystem type. We estimate the contribution from peat burning using drainage and peat distribution maps for Alaska and Canada; 17% of the reported 5.1 × 106 ha burned were located in peatlands in 2004. Our total estimate of North American fire emissions during the summer of 2004 is 30 Tg CO, including 11 Tg from peat. Including peat burning in the GEOS-Chem simulation improves agreement with MOPITT observations. The long-range transport of fire plumes observed by MOPITT suggests that the largest fires injected a significant fraction of their emissions in the upper troposphere.

0.4– 1.0 mol mol � 1 and consistent with ICARTT data. The GEOS-Chem model reproduces the O3-CO enhancement ratios observed in continental outflow, but model correlations are stronger and more extensive. We show that the discrepancy can be explained by spectral measurement errors in the TES data. These errors will decrease in future data releases, which should enable TES to provide better information on O3-CO correlations. Citation: Zhang, L., et al. (2006), Ozone-CO correlations determined by the TES satellite instrument in continental outflow regions, Geophys. Res. Lett., 33, L18804, doi:10.1029/2006GL026399.

[1] We present a factor analysis-based method for differentiating air masses on the basis of source influence and apply the method to a broad suite of trace gas and aerosol measurements collected at Chebogue Point, Nova Scotia, during the summer of 2004 to characterize the chemical composition of atmospheric outflow from eastern North America. CO, ozone, and aerosol mass were elevated by 30%, 56%, and more than 300% at Chebogue Point during U.S. outflow periods. Organic aerosol mass was highest during U.S. pollution events, but made up the largest fraction (70%) of the total aerosol during periods of primary and especially secondary biogenic influence, indicating the importance of both anthropogenic and biogenic organic aerosol. Anthropogenic and oxygenated volatile organic compounds account for the bulk of the gas-phase organic carbon under most conditions; however, biogenic compounds are important in terms of chemical reactivity. Biogenic emissions thus have a significant impact on the chemistry of air masses downwind of the polluted northeastern United States. Using output from a global 3-D model of atmospheric composition (GEOS-Chem), we estimate that CO directly emitted from U.S. pollution sources makes up 28% of the total CO observed at Chebogue Point during U.S. outflow events and 19% at other times, although more work is needed to improve U.S. emission estimates for CO and other pollutants. We conclude that the effects of North American pollution on the chemistry of the western North Atlantic boundary layer are pervasive and not restricted to particular events.

Formaldehyde (HCHO) columns measured from space provide constraints on emissions of volatile organic compounds (VOCs). Quantitative interpretation requires characterization of errors in HCHO column retrievals and relating these columns to VOC emissions. Retrieval error is mainly in the air mass factor (AMF) which relates fitted backscattered radiances to vertical columns and requires external information on HCHO, aerosols, and clouds. Here we use aircraft data collected over North America and the Atlantic to determine the local relationships between HCHO columns and VOC emissions, calculate AMFs for HCHO retrievals, assess the errors in deriving AMFs with a chemical transport model (GEOS-Chem), and draw conclusions regarding space-based mapping of VOC emissions. We show that isoprene drives observed HCHO column variability over North America; HCHO column data from space can thus be used effectively as a proxy for isoprene emission. From observed HCHO and isoprene profiles we find an HCHO molar yield from isoprene oxidation of 1.6 +/- 0.5, consistent with current chemical mechanisms. Clouds are the primary error source in the AMF calculation; errors in the HCHO vertical profile and aerosols have comparatively little effect. The mean bias and 1Q uncertainty in the GEOS-Chem AMF calculation increase from

[1] We examine the major outflow pathways for North American pollution to the Atlantic in summer by conducting a 4-year simulation with the GEOS-CHEM global chemical transport model, including a coupled ozone-aerosol simulation with 1° × 1° horizontal resolution for summer 2000. The outflow is driven principally by cyclones tracking eastward across North America at 45–55°N, every 5 days on average. Anthropogenic and fire effluents from western North America are mostly transported north and east, eventually merging with the eastern U.S. pollution outflow to the Atlantic. A semipermanent upper-level anticyclone traps the convective outflow and allows it to age in the upper troposphere over the United States for several days. Rapid ozone production takes place in this outflow, driven in part by anthropogenic and lightning NOx and in part by HOx radicals produced from convectively lifted CH2O that originates from biogenic isoprene. This mechanism could explain ozonesonde observations of elevated ozone in the upper troposphere over the southeastern United States. Asian and European pollution influences in the North American outflow to the Atlantic are found to be dispersed into the background and do not generate distinct plumes. Satellite observations of CO columns from MOPITT and of aerosol optical depths (AODs) from MODIS provide useful mapping of outflow events, despite their restriction to clear-sky scenes.

[1] We examine the ozone production efficiency in transpacific Asian pollution plumes, and the implications for ozone air quality in California, by using aircraft and surface observations in April–May 2002 from the Intercontinental Transport and Chemical Transformation 2002 (ITCT 2K2) campaign off the California coast and the Pacific Exploration of Asian Continental Emission–B (PEACE-B) campaign over the northwest Pacific. The observations are interpreted with a global three-dimensional chemical transport model (GEOS-CHEM). The model reproduces the mean features observed for CO, reactive nitrogen oxides (NOy), and ozone but underestimates the strong (20 ppbv) stratospheric contribution to ozone in the middle troposphere. The ITCT 2K2 aircraft sampled two major transpacific Asian pollution plumes, one on 5 May at 5–8 km altitude with CO up to 275 ppbv but no elevated ozone and one on 17 May at 2.5–4 km altitude with CO up to 225 ppbv and ozone up to 90 ppbv. We show that the elevated ozone in the latter plume is consistent with production from peroxyacetylnitrate (PAN) decomposition during subsidence of the plume over the northeast Pacific. This production is particularly efficient because of the strong radiation and low humidity of the subsiding environment. We argue that such PAN decomposition represents a major and possibly dominant component of the ozone enhancement in transpacific Asian pollution plumes. Strong dilution of Asian pollution plumes takes place during entrainment in the U.S. boundary layer, greatly reducing their impact at U.S. surface sites. California mountain sites are more sensitive to Asian pollution because of their exposure to the free troposphere. Model results indicate a mean Asian pollution enhancement of 7 ppbv ozone at Sequoia National Park in May 2002 on those days when the 8-hour average ozone concentration exceeded 80 ppbv. INDEX TERMS: 0368 Atmospheric Composition and Structure: Troposphere—constituent transport and chemistry; 0365 Atmospheric Composition and Structure: Troposphere—composition and chemistry; 0345 Atmospheric Composition and Structure: Pollution—urban and regional (0305); KEYWORDS: ozone, Asian pollution, ITCT 2K2, PEACE-B, transpacific transport

[1] Field measurements of a wide suite of trace gases and aerosols were carried out during April and May 2002, along with extensive chemical transport modeling, as part of the NOAA Intercontinental Transport and Chemical Transformation study. Here, we use a combination of in-situ ground-based measurements from Trinidad Head, CA, chemical transport modeling, and backward trajectory analysis to examine the impact of long-range transport from Asia on the composition of air masses arriving at the California coast at the surface. The impact of Asian emissions is explored in terms of both episodic enhancements and contribution to background concentrations. We find that variability in CO concentrations at the ground site was largely driven by North American emissions, and that individual Asian plumes did not cause any observable pollution enhancement episodes at Trinidad Head. Despite this, model simulations suggest that Asian emissions were responsible for 33% of the CO observed at Trinidad Head, providing a larger mean contribution than direct emissions from any other region of the globe. Surface ozone levels were found to depend primarily on local atmospheric mixing, with surface deposition leading to low concentrations under stagnant conditions. Model simulations suggested that on average 4 ± 1 ppb of ozone (10% of observed) at Trinidad Head was transported from Asia.

Received 19 June 2002; revised 13 September 2002; accepted 11 November 2002; published 8 April 2003. [1] We report results of a cloud chemistry numerical modeling intercomparison, which shows good agreement among gas-aqueous photochemistry box models that are being used in the community. For the case studied, cloud chemistry depleted concentrations of CH2O, CH3OOH, HNO3, and O3, while H2O2 (in the absence of sulfur chemistry), NO, and NO2 increased. Because parcels of air usually flow in and out of cloud in a matter of minutes rather than remain in cloud for an hour, an optional simulation was performed in which frequent brief cloud encounters were represented. Representing a cloud intermittently rather than continuously does not alter the total concentration of many of the species. However CH2O and HCOOH concentrations are decreased and increased, respectively, because of the timing of the CH2O production during clear-sky intervals and its destruction during cloudy intervals. Further differences between a continuous cloud simulation and an intermittent cloud simulation are expected if pH is allowed to vary during the cloud periods. Simulating an intermittent cloud brought out the importance of using a chemistry time step that is a multiple of the cloud time step because deviations of results from a simulation in which the chemistry time step did not coincide with the appearance and disappearance of cloud were quite large. To better quantify the effect of cloud on HOx photochemistry, future investigations should include nonmethane hydrocarbon and sulfur chemistry. Future cloud chemistry modeling intercomparisons should bring in cloud physical and chemical measurements so that the models can be evaluated with observations. INDEX TERMS: 0320 Atmospheric Composition and Structure: Cloud physics and chemistry; 0365 Atmospheric Composition and Structure: Troposphere—composition and chemistry; 0399 Atmospheric Composition and Structure: General or miscellaneous; KEYWORDS: cloud chemistry, photochemical models, tropospheric chemistry

We analyze the North American budget for carbon monoxide using data for CO and formaldehyde concentrations from tall towers and aircraft in a model-data assimilation framework. The Stochastic Time-Inverted Lagrangian Transport model for CO (STILT-CO) determines local to regional-scale CO contributions associated with production from fossil fuel combustion, biomass burning, and oxidation of volatile organic compounds (VOCs) using an ensemble of Lagrangian particles driven by high resolution assimilated meteorology. In many cases, the model demonstrates high fidelity simulations of hourly surface data from tall towers and point measurements from aircraft, with somewhat less satisfactory performance in coastal regions and when CO from large biomass fires in Alaska and the Yukon Territory influence the continental US. Inversions of STILT-CO simulations for CO and formaldehyde show that current inventories of CO emissions from fossil fuel combustion are significantly too high, by almost a factor of three in summer and a factor two in early spring, consistent with recent analyses of data from the INTEX-A aircraft program. Formaldehyde data help to show that sources of CO from oxidation of CH4 and other VOCs represent the dominant sources of CO over North America in summer.