We use a global chemical transport model (GEOS-Chem CTM) to interpret observations of black carbon (BC) and organic aerosol (OA) from the NASA ARCTAS aircraft campaign over the North American Arctic in April 2008, as well as longer-term records in surface air and in snow (2007–2009). BC emission inventories for North America, Europe, and Asia in the model are tested by comparison with surface air observations over these source regions. Russian open fires were the dominant source of OA in the Arctic troposphere during ARCTAS but we find that BC was of prevailingly anthropogenic (fossil fuel and biofuel) origin, particularly in surface air. This source attribution is confirmed by correlation of BC and OA with acetonitrile and sulfate in the model and in the observations. Asian emissions are the main anthropogenic source of BC in the free troposphere but European, Russian and North American sources are also important in surface air. Russian anthropogenic emissions appear to dominate the source of BC in Arctic surface air in winter. Model simulations for 2007–2009 (to account for interannual variability of fires) show much higher BC snow content in the Eurasian than the North American Arctic, consistent with the limited observations. We find that anthropogenic sources contribute 90% of BC deposited to Arctic snow in January-March and 60% in April–May 2007–2009. The mean decrease in Arctic snow albedo from BC deposition is estimated to be 0.6% in spring, resulting in a regional surface radiative forcing consistent with previous estimates.

We simulate nitrogen deposition over the US in 2006–2008 by using the GEOS-Chem global chemical transport model at 1/2°×2/3° horizontal resolution over North America and adjacent oceans. US emissions of NO_x and NH₃ in the model are 6.7 and 2.9 Tg N a⁻¹ respectively, including a 20% natural contribution for each. Ammonia emissions are a factor of 3 lower in winter than summer, providing a good match to US network observations of NH_x (≡NH₃ gas + ammonium aerosol) and ammonium wet deposition fluxes. Model comparisons to observed deposition fluxes and surface air concentrations of oxidized nitrogen species (NO_y) show overall good agreement but excessive wintertime HNO₃ production over the US Midwest and Northeast. This suggests a model overestimate N₂O₅ hydrolysis in aerosols, and a possible factor is inhibition by aerosol nitrate. Model results indicate a total nitrogen deposition flux of 6.5 Tg N a⁻¹ over the contiguous US, including 4.2 as NO_y and 2.3 as NH_x. Domestic anthropogenic, foreign anthropogenic, and natural sources contribute respectively 78%, 6%, and 16% of total nitrogen deposition over the contiguous US in the model. The domestic anthropogenic contribution generally exceeds 70% in the east and in populated areas of the west, and is typically 50–70% in remote areas of the west. Total nitrogen deposition in the model exceeds 10 kg N ha⁻¹ a⁻¹ over 35% of the contiguous US.

The recent increase of atmospheric methane is investigated by using two atmospheric inversions to quantify the distribution of sources and sinks for the 2006–2008 period, and a process-based model of methane emissions by natural wetland ecosystems. Methane emissions derived from the two inversions are consistent at a global scale: emissions are decreased in 2006 (−7 Tg) and increased in 2007 (+21 Tg) and 2008 (+18 Tg), as compared to the 1999–2006 period. The agreement on the latitudinal partition of the flux anomalies for the two inversions is fair in 2006, good in 2007, and not good in 2008. In 2007, a positive anomaly of tropical emissions is found to be the main contributor to the global emission anomalies (~60–80%) for both inversions, with a dominant share attributed to natural wetlands (~2/3), and a significant contribution from high latitudes (~25%). The wetland ecosystem model produces smaller and more balanced positive emission anomalies between the tropics and the high latitudes for 2006, 2007 and 2008, mainly due to precipitation changes during these years. At a global scale, the agreement between the ecosystem model and the inversions is good in 2008 but not satisfying in 2006 and 2007. Tropical South America and Boreal Eurasia appear to be major contributors to variations in methane emissions consistently in the inversions and the ecosystem model. Finally, changes in OH radicals during 2006–2008 are found to be less than 1% in inversions, with only a small impact on the inferred methane emissions.

We use observations from the April 2008 NASA ARCTAS aircraft campaign to the North American Arctic, interpreted with a global 3-D chemical transport model (GEOS-Chem), to better understand the sources and cycling of hydrogen oxide radicals (HO_x≡H+OH+peroxy radicals) and their reservoirs (HO_y≡HO_x+peroxides) in the springtime Arctic atmosphere. We find that a standard gas-phase chemical mechanism overestimates the observed HO₂ and H₂O₂ concentrations. Computation of HO_x and HO_y gas-phase chemical budgets on the basis of the aircraft observations also indicates a large missing sink for both. We hypothesize that this could reflect HO₂ uptake by aerosols, favored by low temperatures and relatively high aerosol loadings, through a mechanism that does not produce H₂O₂. We implemented such an uptake of HO₂ by aerosol in the model using a standard reactive uptake coefficient parameterization with γ(HO₂) values ranging from 0.02 at 275 K to 0.5 at 220 K. This successfully reproduces the concentrations and vertical distributions of the different HO_x species and HO_y reservoirs. HO₂ uptake by aerosol is then a major HO_x and HO_y sink, decreasing mean OH and HO₂ concentrations in the Arctic troposphere by 32% and 31% respectively. Better rate and product data for HO₂ uptake by aerosol are needed to understand this role of aerosols in limiting the oxidizing power of the Arctic atmosphere.

We determine enhancement ratios for NO_x, PAN, and other NO_y species from boreal biomass burning using aircraft data obtained during the ARCTAS-B campaign and examine the impact of these emissions on tropospheric ozone in the Arctic. We find an initial emission factor for NO_x of 1.06 g NO per kg dry matter (DM) burned, much lower than previous observations of boreal plumes, and also one third the value recommended for extratropical fires. Our analysis provides the first observational confirmation of rapid PAN formation in a boreal smoke plume, with 40% of the initial NO_x emissions being converted to PAN in the first few hours after emission. We find little clear evidence for ozone formation in the boreal smoke plumes during ARCTAS-B in either aircraft or satellite observations, or in model simulations. Only a third of the smoke plumes observed by the NASA DC8 showed a correlation between ozone and CO, and ozone was depleted in the plumes as often as it was enhanced. Special observations from the Tropospheric Emission Spectrometer (TES) also show little evidence for enhanced ozone in boreal smoke plumes between 15 June and 15 July 2008. Of the 22 plumes observed by TES, only 4 showed ozone increasing within the smoke plumes, and even in those cases it was unclear that the increase was caused by fire emissions. Using the GEOS-Chem atmospheric chemistry model, we show that boreal fires during ARCTAS-B had little impact on the median ozone profile measured over Canada, and had little impact on ozone within the smoke plumes observed by TES.