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Refractory black carbon (rBC), a primary aerosol material, is radiatively significant and a uniquely useful tracer of aerosol processes. Here we present analyses of open‐burning generated rBC size distributions observed both from a research aircraft and from ground‐based sampling. The aircraft sampled fresh smoke generated by 14 different western wildfires and 80 agricultural/prescribed fires, providing sufficient data for statistical analysis of rBC size. The ground‐based observations represent a narrower range of smoke sources, but provide a constraint on contributions to total rBC concentrations from larger particles than those quantified from the aircraft. The range of rBC mass median diameter observed in log‐normal fits was 0.11–0.2 μm volume‐equivalent diameter, with geometric standard deviations ranging from 1.25 to 1.5. rBC size showed a dependence on fuel type. We hypothesize that fuel density and structure significantly influence rBC size in open burning emissions via their influence on the physical conditions of open burning.

Nitrogen oxides (NOx) have fallen steadily across the US over the last 15 years. At the same time, NOx concentrations decrease on weekends relative to weekdays, largely without co-occurring changes in other gas-phase emissions, due to patterns of diesel truck activities. These trends taken together provide two independent constraints on the role of NOx in the nonlinear chemistry of atmospheric oxidation. In this context, we interpret interannual trends in wintertime ammonium nitrate (NH4NO3) in the San Joaquin Valley of California, a location with the worst aerosol pollution in the US and where a large portion of aerosol mass is NH4NO3. Here, we show that NOx reductions have simultaneously decreased nighttime and increased daytime NH4NO3 production over the last decade. We find a substantial decrease in NH4NO3 since 2000 and conclude that this decrease is due to reduced nitrate radical-initiated production at night in residual layers that are decoupled from fresh emissions at the surface. Further reductions in NOx are imminent in California, and nationwide, and we make a quantitative prediction of the response of NH4NO3. We show that the combination of rapid chemical production and efficient NH4NO3 loss via deposition of gas-phase nitric acid implies that high aerosol days in cities in the San Joaquin Valley air basin are responsive to local changes in NOx within those individual cities. Our calculations indicate that large decreases in NOx in the future will not only lower wintertime NH4NO3 concentrations but also cause a transition in the dominant NH4NO3 source from nighttime to daytime chemistry.

Limited availability of ammonia (NH3) observations is currently a barrier for effective monitoring of the nitrogen cycle. It prevents a full understanding of the atmospheric processes in which this trace gas is involved and therefore impedes determining its related budgets. Since the end of 2007, the Infrared Atmospheric Sounding Interferometer (IASI) satellite has been observing NH3 from space at a high spatio-temporal resolution. This valuable data set, already used by models, still needs validation. We present here a first attempt to validate IASI-NH3 measurements using existing independent ground-based and airborne data sets. The yearly distributions reveal similar patterns between ground-based and space-borne observations and highlight the scarcity of local NH3 measurements as well as their spatial heterogeneity and lack of representativity. By comparison with monthly resolved data sets in Europe, China and Africa, we show that IASI-NH3 observations are in fair agreement, but they are characterized by a smaller variation in concentrations. The use of hourly and airborne data sets to compare with IASI individual observations allows investigations of the impact of averaging as well as the representativity of independent observations for the satellite footprint. The importance of considering the latter and the added value of densely located airborne measurements at various altitudes to validate IASI-NH3 columns are discussed. Perspectives and guidelines for future validation work on NH3 satellite observations are presented.

The fate of deepwater releases of gas and oil mixtures is initially determined by solubility and volatility of individual hydrocarbon species; these attributes determine partitioning between air and water. Quantifying this partitioning is necessary to constrain simulations of gas and oil transport, to predict marine bioavailability of different fractions of the gas‐oil mixture, and to develop a comprehensive picture of the fate of leaked hydrocarbons in the marine environment. Analysis of airborne atmospheric data shows massive amounts (∼258,000 kg/day) of hydrocarbons evaporating promptly from the Deepwater Horizon spill; these data collected during two research flights constrain air‐water partitioning, thus bioavailability and fate, of the leaked fluid. This analysis quantifies the fraction of surfacing hydrocarbons that dissolves in the water column (∼33% by mass), the fraction that does not dissolve, and the fraction that evaporates promptly after surfacing (∼14% by mass). We do not quantify the leaked fraction lacking a surface expression; therefore, calculation of atmospheric mass fluxes provides a lower limit to the total hydrocarbon leak rate of 32,600 to 47,700 barrels of fluid per day, depending on reservoir fluid composition information. This study demonstrates a new approach for rapid‐response airborne assessment of future oil spills. Key Points Atmospheric hydrocarbon data define air‐water partitioning of marine oil spills Air‐water partitioning determines oil fate and extent in the marine environment These data permit a unique and robust calculation of oil leak rate

We present an overview of the background, scientific goals, and execution of the Aerosol, Radiation, and Cloud Processes affecting Arctic Climate (ARCPAC) project of April 2008. We then summarize airborne measurements, made in the troposphere of the Alaskan Arctic, of aerosol particle size distributions, composition, and optical properties and discuss the sources and transport of the aerosols. The aerosol data were grouped into four categories based on gas-phase composition. First, the background troposphere contained a relatively diffuse, sulfate-rich aerosol extending from the top of the sea-ice inversion layer to 7.4 km altitude. Second, a region of depleted (relative to the background) aerosol was present within the surface inversion layer over sea-ice. Third, layers of dense, organic-rich smoke from open biomass fires in southern Russia and southeastern Siberia were frequently encountered at all altitudes from the top of the inversion layer to 7.1 km. Finally, some aerosol layers were dominated by components originating from fossil fuel combustion. Of these four categories measured during ARCPAC, the diffuse background aerosol was most similar to the average springtime aerosol properties observed at a long-term monitoring site at Barrow, Alaska. The biomass burning (BB) and fossil fuel layers were present above the sea-ice inversion layer and did not reach the sea-ice surface during the course of the ARCPAC measurements. The BB aerosol layers were highly scattering and were moderately hygroscopic. On average, the layers produced a noontime net heating of ~0.1 K day−1 between 3 and 7 km and a slight cooling at the surface. The ratios of particle mass to carbon monoxide (CO) in the BB plumes, which had been transported over distances >5000 km, were comparable to the high end of literature values derived from previous measurements in wildfire smoke. These ratios suggest minimal precipitation scavenging and removal of the BB particles between the time they were emitted and the time they were observed in dense layers above the sea-ice inversion layer.

Observations from the NOAA WP‐3D aircraft during CalNex in May and June 2010 are used to quantify ammonia (NH3) emissions from automobiles and dairy facilities in the California South Coast Air Basin (SoCAB) and assess their impact on particulate ammonium nitrate (NH4NO3) formation. These airborne measurements in the SoCAB are used to estimate automobile NH3 emissions, 62 ± 24 metric tons day−1, and dairy facility NH3 emissions, 33 ± 16 to 176 ± 88 metric tons day−1. Emission inventories agree with the observed automobile NH3:CO emission ratio, but substantially underpredict dairy facility NH3 emissions. Conditions observed downwind of the dairy facilities were always thermodynamically favorable for NH4NO3 formation due to high NH3 mixing ratios from the concentrated sources. Although automobile emissions generated lower NH3 mixing ratios, they also can thermodynamically favor NH4NO3 formation. As an aerosol control strategy, addressing the dairy NH3 source would have the larger impact on reducing SoCAB NH4NO3 formation. Key Points Mass of SoCAB ammonia emissions is similar from automobile and dairy sources SoCAB dairy ammonia emissions are underrepresented in inventories Dairy ammonia emissions have larger impact on SoCAB ammonium nitrate formation

Analysis of in situ airborne measurements from the CalNex 2010 field experiment (Research at the Nexus of Air Quality and Climate Change) show that ozone in the boundary layer over Southern California was increased by downward mixing of air from the free troposphere (FT). The chemical composition, origin, and transport of air upwind and over Los Angeles, California, were studied using measurements of carbon monoxide (CO), ozone, reactive nitrogen species, and meteorological parameters from the National Oceanic and Atmospheric Administration WP‐3D aircraft on 18 research flights in California in May and June 2010. On six flights, multiple vertical profiles from 0.2–3.5 km above ground level were conducted throughout the Los Angeles (LA) basin and over the Pacific Ocean. Gas phase compounds measured in 32 vertical profiles are used to characterize air masses in the FT over the LA basin, with the aim of determining the source of increased ozone observed above the planetary boundary layer (PBL). Four primary air mass influences were observed regularly in the FT between approximately 1 and 3.5 km altitude: upper tropospheric air, long‐range transport of emissions, aged regional emissions, and marine air. The first three air mass types accounted for 89% of the FT observations. Ozone averaged 71 ppbv in air influenced by the upper troposphere, 69 ppbv in air containing emissions transported long distances, and 65 ppbv in air with aged regional emissions. Correlations between ozone and CO, and ozone and nitric acid, demonstrate entrainment of ozone from the FT into the LA PBL. Downward transport of ozone‐rich air from the FT into the PBL contributes to the ozone burden at the surface in this region and makes compliance with air quality standards challenging. Key Points Air mass chemical composition over Los Angeles Basin measured from aircraft Upper tropospheric influence increased ozone in the lower free troposphere Downward mixing of ozone‐rich air increased ozone in California

Anthropogenic emissions of NOx (nitric oxide (NO) + nitrogen dioxide (NO2)), which in sunlight can be oxidized to form nitric acid (HNO3), can react with ammonia (NH3) to form ammonium nitrate particles. Ammonium nitrate formation was observed from the NOAA WP‐3D aircraft over Houston during the 2006 Texas Air Quality Study with fast‐response measurements of NH3, HNO3, particle composition, and particle size distribution. Typically, NH3 mixing ratios over the urban area ranged from 0.2 to 3 ppbv and were predominantly from area sources. No NH3 enhancements were observed in emission plumes from power plants. The few plumes with high NH3 levels from point source emissions that were sampled are analyzed in detail. While the paucity of NH3 data in emission inventories made point source identification difficult, one plume was traced to NH3 release from an industrial accident. NH3 mixing ratios in these plumes ranged from 5 to 80 ppbv. In these plumes, the NH3 enhancement correlated with a decrease in HNO3 mixing ratio and an increase in particulate NO3− concentration indicating ammonium nitrate formation. The ammonium nitrate aerosol mass budget in the plumes was analyzed to assess the quantitative agreement between the gas and aerosol phase measurements. The thermodynamic equilibrium between the gas and aerosol phase was examined for one flight by comparing the modeled dissociation constant for ammonium nitrate with NH3 and HNO3 measurements. The high levels of NH3 in these plumes shifted the equilibrium toward favorable thermodynamic conditions for the condensation of ammonium nitrate onto particles.

New-particle formation in the plumes of coal-fired power plants and other anthropogenic sulfur sources may be an important source of particles in the atmosphere. It remains unclear, however, how best to reproduce this formation in global and regional aerosol models with grid-box lengths that are 10s of kilometers and larger. The predictive power of these models is thus limited by the resultant uncertainties in aerosol size distributions. In this paper, we focus on sub-grid sulfate aerosol processes within coal-fired power plant plumes: the sub-grid oxidation of SO2 with condensation of H2SO4 onto newly-formed and pre-existing particles. We have developed a modeling framework with aerosol microphysics in the System for Atmospheric Modelling (SAM), a Large-Eddy Simulation/Cloud-Resolving Model (LES/CRM). The model is evaluated against aircraft observations of new-particle formation in two different power-plant plumes and reproduces the major features of the observations. We show how the downwind plume aerosols can be greatly modified by both meteorological and background aerosol conditions. In general, new-particle formation and growth is greatly reduced during polluted conditions due to the large pre-existing aerosol surface area for H2SO4 condensation and particle coagulation. The new-particle formation and growth rates are also a strong function of the amount of sunlight and NOx since both control OH concentrations. The results of this study highlight the importance for improved sub-grid particle formation schemes in regional and global aerosol models.

Inorganic bromine plays a critical role in ozone and mercury depletions events (ODEs and MDEs) in the Arctic marine boundary layer. Direct observations of bromine species other than bromine oxide (BrO) during ODEs are very limited. Here we report the first direct measurements of hypobromous acid (HOBr) as well as observations of BrO and molecular bromine (Br2) by chemical ionization mass spectrometry at Barrow, Alaska in spring 2009 during the Ocean‐Atmospheric‐Sea Ice‐Snowpack (OASIS) campaign. Diurnal profiles of HOBr with maximum concentrations near local noon and no significant concentrations at night were observed. The measured average daytime HOBr mixing ratio was 10 pptv with a maximum value of 26 pptv. The observed HOBr was reasonably well correlated (R2 = 0.57) with predictions from a simple steady state photochemical model constrained to observed BrO and HO2 at wind speeds <6 m s−1. However, predicted HOBr levels were considerably higher than observations at higher wind speeds. This may be due to enhanced heterogeneous loss of HOBr on blowing snow coincident with higher wind speeds. BrO levels were also found to be higher at elevated wind speeds. Br2 was observed in significant mixing ratios (maximum = 46 pptv; average = 13 pptv) at night and was strongly anti‐correlated with ozone. The diurnal speciation of observed gas phase inorganic bromine species can be predicted by a time‐dependent box model that includes efficient heterogeneous recycling of HOBr, hydrogen bromide (HBr), and bromine nitrate (BrONO2) back to more reactive forms of bromine. Key Points First observations of HOBr are presented Direct evidence for high winds activating bromine HOBr can be reproduced with model including aerosol uptake