In contrast with the textbook view of remote chemistry where HNO 3 formation is the primary sink of nitrogen oxides, recent theoretical analyses show that formation of RONO2 (ΣANs) from isoprene and other terpene precursors is the primary net chemical loss of nitrogen oxides over the remote continents where the concentration of nitrogen oxides is low. This then increases the prominence of questions concerning the chemical lifetime and ultimate fate of ΣANs. We present observations of nitrogen oxides and organic molecules collected over the Canadian boreal forest during the summer which show that ΣANs account for ∼20% of total oxidized nitrogen and that their instantaneous production rate is larger than that of HNO3. This confirms the primary role of reactions producing ΣANs as a control over the lifetime of NOx (NOx =NO+NO2) in remote, continental environments. However, HNO 3 is generally present in larger concentrations than ΣANs indicating that the atmospheric lifetime of ΣANs is shorter than the HNO3 lifetime. We in-vestigate a range of proposed loss mechanisms that would explain the inferred lifetime of ΣANs finding that in combination with deposition, two processes are consistent with the observations: (1) rapid ozonolysis of isoprene nitrates where at least ∼40% of the ozonolysis producs t ts release NOx from the carbon backbone and/or (2) hydrolysis of particulate organic nitrates with HNO3 as a product. Implications of these ideas for our understanding of NOx and NOy budget in remote and rural locations are discussed. © Author(s) 2013.

We evaluate the impact of transport from midlatitudes on aerosol number concentrations in the accumulation mode (light-scattering particles (LSP) with diameters >180 nm) in the Arctic during the Arctic Research of the Composition of the Troposphere from Aircraft and Satellites (ARCTAS) campaign. We focus on transport from the Asian continent. We find marked contrasts in the number concentration (NLSP), transport efficiency (TE N-LSP, the fraction transported from sources to the Arctic), size distribution, and the chemical composition of aerosols between air parcels from anthropogenic sources in East Asia (Asian AN) and biomass burning sources in Russia and Kazakhstan (Russian BB). Asian AN air had lower NLSP and TEN-LSP (25 cm^-3 and 18% in spring and 6.2 cm^-3 and 3.0% in summer) than Russian BB air (280 cm^-3 and 97% in spring and 36 cm^-3 and 7.6% in summer) due to more efficient wet scavenging during transport from East Asia. Russian BB in this spring is the most important source of accumulation-mode aerosols over the Arctic, and BB emissions are found to be the primary source of aerosols within all the data in spring during ARCTAS. On the other hand, the contribution of Asian AN transport had a negligible effect on the accumulation-mode aerosol number concentration in the Arctic during ARCTAS. Compared with background air, NLSP was 2.3-4.7 times greater for Russian BB air but 2.4-2.6 times less for Asian AN air in both spring and summer. This result shows that the transport of Asian AN air decreases aerosol number concentrations in the Arctic, despite the large emissions of aerosols in East Asia. The very low aerosol number concentrations in Asian AN air were caused by wet removal during vertical transport in association with warm conveyor belts (WCBs). Therefore, this cleansing effect will be prominent for air transported via WCBs from other midlatitude regions and seasons. The inflow of clean midlatitude air can potentially have an important impact on accumulation-mode aerosol number concentrations in the Arctic. Copyright 2011 by the American Geophysical Union.

Reliable assessment of the impact of aerosols emitted from boreal forest fires on the Arctic climate necessitates improved understanding of emissions and the microphysical properties of carbonaceous (black carbon (BC) and organic aerosols (OA)) and inorganic aerosols. The size distributions of BC were measured by an SP2 based on the laser-induced incandescence technique on board the DC-8 aircraft during the NASA ARCTAS campaign. Aircraft sampling was made in fresh plumes strongly impacted by wildfires in North America (Canada and California) in summer 2008 and in those transported from Asia (Siberia in Russia and Kazakhstan) in spring 2008. We extracted biomass burning plumes using particle and tracer (CO, CH3CN, and CH2Cl2) data. OA constituted the dominant fraction of aerosols mass in the submicron range. The large majority of the emitted particles did not contain BC. We related the combustion phase of the fire as represented by the modified combustion efficiency (MCE) to the emission ratios between BC and other species. In particular, we derived the average emission ratios of BC/CO = 2.3 ± 2.2 and 8.5 ± 5.4 ng m^-3/ppbv for BB in North America and Asia, respectively. The difference in the BC/CO emission ratios is likely due to the difference in MCE. The count median diameters and geometric standard deviations of the lognormal size distribution of BC in the BB plumes were 136-141 nm and 1.32-1.36, respectively, and depended little on MCE. These BC particles were thickly coated, with shell/core ratios of 1.3-1.6. These parameters can be used directly for improving model estimates of the impact of BB in the Arctic. Copyright 2011 by the American Geophysical Union.

Recent laboratory and field studies have indicated that glyoxal is a potentially large contributor to secondary organic aerosol mass. We present in situ glyoxal measurements acquired with a recently developed, high sensitivity spectroscopic instrument during the CalNex 2010 field campaign in Pasadena, California. We use three methods to quantify the production and loss of glyoxal in Los Angeles and its contribution to organic aerosol. First, we calculate the difference between steady state sources and sinks of glyoxal at the Pasadena site, assuming that the remainder is available for aerosol uptake. Second, we use the Master Chemical Mechanism to construct a two-dimensional model for gas-phase glyoxal chemistry in Los Angeles, assuming that the difference between the modeled and measured glyoxal concentration is available for aerosol uptake. Third, we examine the nighttime loss of glyoxal in the absence of its photochemical sources and sinks. Using these methods we constrain the glyoxal loss to aerosol to be 0-5 × 10^-5 s^-1 during clear days and (1 ± 0.3) × 10^-5 s^-1 at night. Between 07:00-15:00 local time, the diurnally averaged secondary organic aerosol mass increases from 3.2 μg m^-3 to a maximum of 8.8 μg m ^-3. The constraints on the glyoxal budget from this analysis indicate that it contributes 0-0.2 μg m^-3 or 0-4% of the secondary organic aerosol mass. Copyright 2011 by the American Geophysical Union.

We determine enhancement ratios for NOx, 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 NOx 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. © 2010 Author(s).

Organic aerosols (OA) in Pasadena are characterized using multiple measurements from the California Research at the Nexus of Air Quality and Climate Change (CalNex) campaign. Five OA components are identified using positive matrix factorization including hydrocarbon-like OA (HOA) and two types of oxygenated OA (OOA). The Pasadena OA elemental composition when plotted as H:C versus O:C follows a line less steep than that observed for Riverside, CA. The OOA components from both locations follow a common line, however, indicating similar secondary organic aerosol (SOA) oxidation chemistry at the two sites such as fragmentation reactions leading to acid formation. In addition to the similar evolution of elemental composition, the dependence of SOA concentration on photochemical age displays quantitatively the same trends across several North American urban sites. First, the OA/ΔCO values for Pasadena increase with photochemical age exhibiting a slope identical to or slightly higher than those for Mexico City and the northeastern United States. Second, the ratios of OOA to odd-oxygen (a photochemical oxidation marker) for Pasadena, Mexico City, and Riverside are similar, suggesting a proportional relationship between SOA and odd-oxygen formation rates. Weekly cycles of the OA components are examined as well. HOA exhibits lower concentrations on Sundays versus weekdays, and the decrease in HOA matches that predicted for primary vehicle emissions using fuel sales data, traffic counts, and vehicle emission ratios. OOA does not display a weekly cycle - after accounting for differences in photochemical aging - which suggests the dominance of gasoline emissions in SOA formation under the assumption that most urban SOA precursors are from motor vehicles. © 2013. Her Majesty the Queen in Right of Canada. American Geophysical Union.