Biomass burning (BB) is a large source of primary and secondary organic aerosols (POA and SOA). This study addresses the physical and chemical evolution of BB organic aerosols. Firstly, the evolution and lifetime of BB POA and SOA signatures observed with the Aerodyne Aerosol Mass Spectrometer are investigated, focusing on measurements at high-latitudes acquired during the 2008 NASA ARCTAS mission, in comparison to data from other field studies and from laboratory aging experiments. The parameter f₆₀, the ratio of the integrated signal at m/z 60 to the total signal in the organic component mass spectrum, is used as a marker to study the rate of oxidation and fate of the BB POA. A background level of f₆₀~0.3% ± 0.06% for SOA-dominated ambient OA is shown to be an appropriate background level for this tracer. Using also f₄₄ as a tracer for SOA and aged POA and a surrogate of organic O:C, a novel graphical method is presented to characterise the aging of BB plumes. Similar trends of decreasing f₆₀ and increasing f₄₄ with aging are observed in most field and lab studies. At least some very aged BB plumes retain a clear f₆₀ signature. A statistically significant difference in f₆₀ between highly-oxygenated OA of BB and non-BB origin is observed using this tracer, consistent with a substantial contribution of BBOA to the springtime Arctic aerosol burden in 2008. Secondly, a summary is presented of results on the net enhancement of OA with aging of BB plumes, which shows large variability. The estimates of net OA gain range from ΔOA/ΔCO(mass) = −0.01 to ~0.05, with a mean ΔOA/POA ~19%. With these ratios and global inventories of BB CO and POA a global net OA source due to aging of BB plumes of ~8 ± 7 Tg OA yr⁻¹ is estimated, of the order of 5 % of recent total OA source estimates. Further field data following BB plume advection should be a focus of future research in order to better constrain this potentially important contribution to the OA burden.

Ozone pollution in the Southeast US involves complex chemistry driven by emissions of anthropogenic nitrogen oxide radicals (NO_x ≡ NO + NO₂) and biogenic isoprene. Model estimates of surface ozone concentrations tend to be biased high in the region and this is of concern for designing effective emission control strategies to meet air quality standards. We use detailed chemical observations from the SEAC⁴RS aircraft campaign in August and September 2013, interpreted with the GEOS-Chem chemical transport model at 0.25° × 0.3125° horizontal resolution, to better understand the factors controlling surface ozone in the Southeast US. We find that the National Emission Inventory (NEI) for NO_x from the US Environmental Protection Agency (EPA) is too high. This finding is based on SEAC⁴RS observations of NO_x and its oxidation products, surface network observations of nitrate wet deposition fluxes, and OMI satellite observations of tropospheric NO₂ columns. Our results indicate that NEI NO_x emissions from mobile and industrial sources must be reduced by 30–60 %, dependent on the assumption of the contribution by soil NO_x emissions. Upper-tropospheric NO₂ from lightning makes a large contribution to satellite observations of tropospheric NO₂ that must be accounted for when using these data to estimate surface NO_x emissions. We find that only half of isoprene oxidation proceeds by the high-NO_x pathway to produce ozone; this fraction is only moderately sensitive to changes in NO_x emissions because isoprene and NO_x emissions are spatially segregated. GEOS-Chem with reduced NO_x emissions provides an unbiased simulation of ozone observations from the aircraft and reproduces the observed ozone production efficiency in the boundary layer as derived from a regression of ozone and NO_x oxidation products. However, the model is still biased high by 6 ± 14 ppb relative to observed surface ozone in the Southeast US. Ozonesondes launched during midday hours show a 7 ppb ozone decrease from 1.5 km to the surface that GEOS-Chem does not capture. This bias may reflect a combination of excessive vertical mixing and net ozone production in the model boundary layer.

Atmospheric deposition of Hg(II) represents a major input of mercury to surface environments. The phase of Hg(II) (gas or particle) has important implications for deposition. We use long-term observations of reactive gaseous mercury (RGM, the gaseous component of Hg(II)), particle-bound mercury (PBM, the particulate component of Hg(II)), fine particulate matter (PM_2.5), and temperature (T) at five sites in North America to derive an empirical gas-particle partitioning relationship log₁₀(K⁻¹) = (10±1)–(2500±300)/T where K = (PBM/PM_2.5)/RGM with PBM and RGM in common mixing ratio units, PM_2.5 in μg m⁻³, and T in K. This relationship is within the range of previous work but is based on far more extensive data from multiple sites. We implement this empirical relationship in the GEOS-Chem global 3-D Hg model to partition Hg(II) between the gas and particle phases. The resulting gas-phase fraction of Hg(II) ranges from over 90 % in warm air with little aerosol to less than 10 % in cold air with high aerosol. Hg deposition to high latitudes increases because of more efficient scavenging of particulate Hg(II) by precipitating snow. Model comparison to Hg observations at the North American surface sites suggests that subsidence from the free troposphere (warm air, low aerosol) is a major factor driving the seasonality of RGM, while elevated PBM is mostly associated with high aerosol loads. Simulation of RGM and PBM at these sites is improved by including fast in-plume reduction of Hg(II) emitted from coal combustion and by assuming that anthropogenic particulate Hg(p) behaves as semi-volatile Hg(II) rather than as a refractory particulate component. We improve the simulation of Hg wet deposition fluxes in the US relative to a previous version of GEOS-Chem; this largely reflects independent improvement of the washout algorithm. The observed wintertime minimum in wet deposition fluxes is attributed to inefficient snow scavenging of gas-phase Hg(II).

The NASA Arctic Research of the Composition of the Troposphere from Aircraft and Satellites (ARCTAS) mission was conducted in two 3-week deployments based in Alaska (April 2008) and western Canada (June–July 2008). Its goal was to better understand the factors driving current changes in Arctic atmospheric composition and climate, including (1) influx of mid-latitude pollution, (2) boreal forest fires, (3) aerosol radiative forcing, and (4) chemical processes. The June–July deployment was preceded by one week of flights over California (ARCTAS-CARB) focused on (1) improving state emission inventories for greenhouse gases and aerosols, (2) providing observations to test and improve models of ozone and aerosol pollution. ARCTAS involved three aircraft: a DC-8 with a detailed chemical payload, a P-3 with an extensive aerosol and radiometric payload, and a B-200 with aerosol remote sensing instrumentation. The aircraft data augmented satellite observations of Arctic atmospheric composition, in particular from the NASA A-Train. The spring phase (ARCTAS-A) revealed pervasive Asian pollution throughout the Arctic as well as significant European pollution below 2 km. Unusually large Siberian fires in April 2008 caused high concentrations of carbonaceous aerosols and also affected ozone. Satellite observations of BrO column hotspots were found not to be related to Arctic boundary layer events but instead to tropopause depressions, suggesting the presence of elevated inorganic bromine (5–10 pptv) in the lower stratosphere. Fresh fire plumes from Canada and California sampled during the summer phase (ARCTAS-B) indicated low NO_x emission factors from the fires, rapid conversion of NO_x to PAN, no significant secondary aerosol production, and no significant ozone enhancements except when mixed with urban pollution.

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.

Isoprene emitted by vegetation is an important precursor of secondary organic aerosol (SOA), but the mechanism and yields are uncertain. Aerosol is prevailingly aqueous under the humid conditions typical of isoprene-emitting regions. Here we develop an aqueous-phase mechanism for isoprene SOA formation coupled to a detailed gas-phase isoprene oxidation scheme. The mechanism is based on aerosol reactive uptake coefficients (γ) for water-soluble isoprene oxidation products, including sensitivity to aerosol acidity and nucleophile concentrations. We apply this mechanism to simulation of aircraft (SEAC⁴RS) and ground-based (SOAS) observations over the southeast US in summer 2013 using the GEOS-Chem chemical transport model. Emissions of nitrogen oxides (NO_x ≡ NO + NO₂) over the southeast US are such that the peroxy radicals produced from isoprene oxidation (ISOPO₂) react significantly with both NO (high-NO_x pathway) and HO₂ (low-NO_x pathway), leading to different suites of isoprene SOA precursors. We find a mean SOA mass yield of 3.3 % from isoprene oxidation, consistent with the observed relationship of total fine organic aerosol (OA) and formaldehyde (a product of isoprene oxidation). Isoprene SOA production is mainly contributed by two immediate gas-phase precursors, isoprene epoxydiols (IEPOX, 58 % of isoprene SOA) from the low-NO_x pathway and glyoxal (28 %) from both low- and high-NO_x pathways. This speciation is consistent with observations of IEPOX SOA from SOAS and SEAC⁴RS. Observations show a strong relationship between IEPOX SOA and sulfate aerosol that we explain as due to the effect of sulfate on aerosol acidity and volume. Isoprene SOA concentrations increase as NO_x emissions decrease (favoring the low-NO_x pathway for isoprene oxidation), but decrease more strongly as SO₂ emissions decrease (due to the effect of sulfate on aerosol acidity and volume). The US Environmental Protection Agency (EPA) projects 2013–2025 decreases in anthropogenic emissions of 34 % for NO_x (leading to a 7 % increase in isoprene SOA) and 48 % for SO₂ (35 % decrease in isoprene SOA). Reducing SO₂ emissions decreases sulfate and isoprene SOA by a similar magnitude, representing a factor of 2 co-benefit for PM_2.5 from SO₂ emission controls.