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The role of anthropogenic NOx emissions in secondary organic aerosol (SOA) production is not fully understood but is important for understanding the contribution of emissions to air quality. Here, we examine the role of organic nitrates (RONO2) in SOA formation over the Korean Peninsula during the Korea-United States Air Quality field study in Spring 2016 as a model for RONO2 aerosol in cities worldwide. We use aircraft-based measurements of the particle phase and total (gas + particle) RONO2 to explore RONO2 phase partitioning. These measurements show that, on average, one-fourth of RONO2 are in the condensed phase, and we estimate that ≈15% of the organic aerosol (OA) mass can be attributed to RONO2. Furthermore, we observe that the fraction of RONO2 in the condensed phase increases with OA concentration, evidencing that equilibrium absorptive partitioning controls the RONO2 phase distribution. Lastly, we model RONO2 chemistry and phase partitioning in the Community Multiscale Air Quality modeling system. We find that known chemistry can account for one-third of the observed RONO2, but there is a large missing source of semivolatile, anthropogenically derived RONO2. We propose that this missing source may result from the oxidation of semi- and intermediate-volatility organic compounds and/or from anthropogenic molecules that undergo autoxidation or multiple generations of OH-initiated oxidation.

A better understanding of the chemistry of nitrogen oxides (NOx) is crucial to effectively reducing air pollution and predicting future air quality. The response of NOx lifetime to perturbations in emissions or in the climate system is set in large part by whether NOx loss occurs primarily by the direct formation of HNO3 or through the formation of alkyl and multifunctional nitrates (RONO2). Using 15 years of detailed in situ observations, we show that in the summer daytime continental boundary layer the relative importance of these two pathways can be well approximated by the relative likelihood that OH will react with NO2 or instead with a volatile organic compound (VOC). Over the past decades, changes in anthropogenic emissions of both NOx and VOCs have led to a significant increase in the overall importance of RONO2 chemistry to NOx loss. We find that this shift is associated with a decreased effectiveness of NOx emissions reductions on ozone production in polluted areas and increased transport of NOx from source to receptor regions. This change in chemistry, combined with changes in the spatial pattern of NOx emissions, is observed to be leading to a flatter distribution of NO2 across the United States, potentially transforming ozone air pollution from a local issue into a regional one.

Retrievals of tropospheric NO2 columns from UV–visible observations of reflected sunlight require a priori vertical profiles to account for the variation in sensitivity of the observations to NO2 at different altitudes. These profiles vary in space and time but are usually approximated using models that do not resolve the full details of this variation. Currently, no operational retrieval simulates these a priori profiles at both high spatial and high temporal resolution. Here we examine the additional benefits of daily variations in a priori profiles for retrievals already simulating a priori NO2 profiles at sufficiently high spatial resolution to identify variations of NO2 within urban plumes. We show the effects of introducing daily variation into a priori profiles can be as large as 40 % and 3 × 1015 molec. cm−2 for an individual day and lead to corrections as large as −13 % for a monthly average in a case study of Atlanta, GA, USA. Additionally, we show that NOx emissions estimated from space-based remote sensing using daily, high-spatial-resolution a priori profiles are ∼ 100 % greater than those of a retrieval using spatially coarse a priori profiles, and 26–40 % less than those of a retrieval using monthly averaged high-spatial-resolution profiles.

Organic nitrates contribute significantly to the total organic aerosol burden. However, the formation and loss mechanisms of particulate organic nitrates (PONs) remain poorly understood. In this study, with the CMAQ modeling system, we implement a detailed biogenic volatile organic carbon gas phase oxidation mechanism and an explicit representation of multiphase organic nitrate formation and loss, including both aqueous-phase uptake and vapor-pressure driven partitioning into organic aerosol as well as condensed-phase reactions. We find vapor-pressure dependent partitioning is the leading mechanism for formation of PONs and hydrolysis is a major loss mechanism for PON resulting in substantial amounts of organic aerosol that originate as an organic nitrate. Partitioning and hydrolysis together can produce high concentrations (up to 5 μg/m(3)) of PON-derived aerosols over the southeast United States. The main source of PON-derived aerosols is monoterpene nitrates that have been chemically processed to lose their nitrate functionality through aqueous chemistry. In contrast, the major portion of aqueous aerosol and in-cloud PON, which retains its nitrate moiety, are soluble isoprene nitrates. We evaluate the model using the observations from the Southern Oxidant and Aerosol Study (SOAS) campaign in the Southeast US in summer 2013 and show implementing aerosol-phase pathways for organic nitrates dramatically improves the magnitude of total alkyl nitrates (ANs) in CMAQ. The contribution of PONs to the total ANs at the SOAS site is estimated to be ~20%, a value in the range of the measurements. The predicted AN composition is shifted from monoterpene to isoprene and anthropogenic organic nitrates.

A better understanding of the chemistry of nitrogen oxides (NONOx) is crucial to effectively reducing air pollution and predicting future air quality. The response of NOx lifetime to perturbations in emissions or in the climate system is set in large part by whether NOx loss occurs primarily by the direct formation of HNO3 or through the formation of alkyl and multifunctional nitrates (RONO2). Using 15 years of detailed in situ observations, we show that in the summertime continental boundary layer the relative importance of these two pathways can be well approximated by the relative likelihood that OH will react with NO2 or instead with a volatile organic compound (VOC). Over the past decades, changes in anthropogenic emissions of both NONOx and VOCs have led to a significant increase in the overall importance of RONO2 chemistry to NONOx loss. We find that this shift is associated with a decreased effectiveness of NONOx emissions reductions on ozone production in polluted areas and increased transport of NONOx from source to receptor regions. This change in chemistry, combined with changes in the spatial pattern of NONOx emissions, is observed to be leading to a flatter distribution of NO2 across the United States, potentially transforming ozone air pollution from a local issue into a regional one.

Accurate estimates of emissions from natural sources are needed for reliable predictions of ozone and fine particulate matter (PM2.5) using air quality models. In this study, the large-scale atmospheric chemistry transport model, DEHM (the Danish Eulerian Hemispheric Model) is further developed, evaluated and applied to study and quantify the contributions of natural emissions of VOCs, NOx, NH3, SO2, CH4, PM, CO and sea salt to the concentration of ozone and formation of PM2.5 for the year 2006. Natural source categories adopted in the recent model are vegetation, lightning, soils, wild animals and oceans. In this study, the model has been further developed to include more Biogenic Volatile Organic Compounds (BVOCs) and to implement a scheme for secondary organic aerosols as well as an updated description of sea-salt emissions. Our simulations indicate that in the Northern Hemisphere the contribution from natural emissions to the average annual ozone mixing ratios over land is between 4–30 ppbV. Among the natural emissions, BVOCs are found to be the most significant contributors to ozone formation in 2006, enhancing the average ozone mixing ratio by about 11% over the land areas of the Northern Hemisphere. The relative contribution of all the natural emissions to ozone is found to be highest in the northern part of South America by about 42%. Similarly, the highest contribution of all the natural sources to total fine particles over land is found to be in South America by about 74% and sea-salt aerosols demonstrated to play the most important role. However, over the rest of the regions in the model domain the largest contribution from the natural sources to PM2.5 in the specific year 2006 is due to wildfires. The contribution from natural emissions to the mean PM2.5 concentration over the land areas in the model domain is about 34%.

Anthropogenic emissions of sulfur dioxide (SO2) and nitrogen oxides (NOx) may affect concentration levels and composition of biogenic secondary organic aerosols (BSOA) through photochemical reactions with biogenic organic precursors to form organosulfates and nitrooxy organosulfates. We investigated this influence in a field study from 19 May to 22 June, 2011 at two sampling sites in Denmark. Within the study, we identified a substantial number of organic acids, organosulfates and nitrooxy organosulfates in the ambient urban curbside and semi-rural background air. A high degree of correlation in concentrations was found among a group of specific organic acids, organosulfates and nitrooxy organosulfates, which may originate from various precursors, suggesting a common mechanism or factor affecting their concentration levels at the sites. It was proposed that the formation of those species most likely occurred on a larger spatial scale, with the compounds being long-range transported to the sites on the days with the highest concentrations. The origin of the long-range transported aerosols was investigated using the Hybrid Single Particle Lagrangian Integrated Trajectory (HYSPLIT) model in addition to modeled emissions of related precursors, including isoprene and monoterpenes using the global Model of Emissions of Gases and Aerosols from Nature (MEGAN) and SO2 emissions using the European Monitoring and Evaluation Program (EMEP) database. The local impacts were also studied by examining the correlation between selected species, which showed significantly enhanced concentrations at the urban curbside site and the local concentrations of various gases, including SO2, ozone (O3), NOx, aerosol acidity and other meteorological conditions. This investigation showed that an inter-play of the local parameters such as the aerosol acidity, NOx, SO2, relative humidity (RH), temperature and global radiation seemed to affect the concentration level of those species, suggesting the influence of aqueous aerosol chemistry. The local impacts, however, seemed minor compared to the regional impacts. The total concentrations of organosulfates and nitrooxy organosulfates, on average, contributed to approximately 0.5–0.8% of PM1 mass at the two sampling sites.

Knowledge about isoprene emissions and concentration distribution is important for chemistry transport models (CTMs), because isoprene acts as a precursor for tropospheric ozone and subsequently affects the atmospheric concentrations of many other atmospheric compounds. Isoprene has a short lifetime, and hence it is very difficult to evaluate its emission estimates against measurements. For this reason, we coupled two isoprene emission models with the Danish Eulerian Hemispheric Model (DEHM), and evaluated the simulated background ozone concentrations based on different models for isoprene emissions. In this research, results of using the two global biogenic emission models; GEIA (Global Emissions Inventory Activity) and MEGAN (the global Model of Emissions of Gases and Aerosols from Nature) are compared and evaluated. The total annual emissions of isoprene for the year 2006 estimated by using MEGAN is 592 Tg yr−1 for an extended area of the Northern Hemisphere, which is 21% higher than that estimated by using GEIA. The overall feature of the emissions from the two models is quite similar, but differences are found mainly in Africa's savannah and in the southern part of North America. Differences in spatial distribution of emission factors are found to be a key source of these discrepancies. In spite of the short life-time of isoprene, a direct evaluation of isoprene concentrations using the two biogenic emission models in DEHM has been made against available measurements in Europe. Results show an agreement between two models simulations and the measurements in general and that the CTM is able to simulate isoprene concentrations. Additionally, investigation of ozone concentrations resulting from the two biogenic emission models show that isoprene simulated by MEGAN strongly affects the ozone production in the African savannah; the effect is up to 10% more than that obtained using GEIA. In contrast, the impact of using GEIA is higher in the Amazon region with more than 8% higher ozone concentrations compared to that of using MEGAN. Comparing the ozone concentrations obtained by DEHM using the two different isoprene models with measurements from Europe and North America, show an agreement on the hourly, mean daily and daily maximum values. However, the average of ozone daily maximum value simulated by using MEGAN is slightly closer to the measured value for the average of all measuring sites in Europe.

The Danish Eulerian Hemispheric Model (DEHM) is a 3D long-range atmospheric chemistry-transport model with a horizontal domain covering the Northern Hemisphere. For the AQMEII (Air Quality Modelling Evaluation International Initiative) inter-comparison exercise, the model was set up with two two-way nested domains simultaneously – one covering Europe and one covering North America. In this paper, the model configuration used in AQMEII will be described, including a discussion of model results and evaluation for the year 2006 against available measurements in Europe for different chemical species. The evaluation of DEHM for Europe shows that the model gives satisfying results for species such as ozone, nitrogen-dioxide, sulphur-dioxide and secondary inorganic aerosols. The evaluation also points to certain processes where DEHM can be improved, such as biogenic emissions of isoprene, mass closure for particulate matter, wet deposition, and description of vertical mixing during winter. Furthermore, special attention is given to the intercontinental transport of air pollution between North America (NA) and Europe (EU). We estimate the contributions to the total air pollution levels at continental scale from the anthropogenic emissions in the two areas, with a focus on ozone and particulate matter using a tagging method, taking into account the non-linear effects of atmospheric chemistry. We conclude that for this specific year, the intercontinental transport between NA and EU is small for the annual or seasonal mean values – for ozone the contributions are typically around 3% (∼1 ppb) from NA to EU and around 1% (∼0.3 ppb) from EU to NA. For particles the contributions from NA to EU is around 0.9% (∼0.05 μg m −3 ) and from EU to NA around 1.4% (∼0.05 μg m −3 ).

The ozone chemistry in four decades (1890s, 1990s, 2090s and 2190s) representing the changes over three centuries has been simulated using the chemistry version of the atmospheric long-range transport model: the Danish Eulerian Hemispheric Model (DEHM) forced with meteorology projected by theECHAM5/MPI-OM coupled Atmosphere-Ocean General Circulation Model. The largest changes in meteorology, ozone and its precursors are found in the 21st century, however, also significant changes are found in the 22nd century. At surface level the ozone concentration is projected to increase due to climate change in the areas where substantial amounts of ozone precursors are emitted. Elsewhere a significant decrease is projected at the surface. In the free troposphere a general increase is found in the entire Northern Hemisphere except in the tropics, where the ozone concentration is decreasing. In the Arctic the ozone concentration will increase in the entire air column, which most likely is due to changes in atmospheric transport. Changes in temperature, humidity and the naturally emitted Volatile Organic Compounds (VOCs) are governing the changes in ozone both in the past, present and future century.