In the atmosphere nighttime removal of volatile organic compounds is initiated to a large extent by reaction with the nitrate radical (NO3) forming organic nitrates which partition between gas and particulate phase. Here we show based on particle phase measurements performed at a suburban site in the Netherlands that organic nitrates contribute substantially to particulate nitrate and organic mass. Comparisons with a chemistry transport model indicate that most of the measured particulate organic nitrates are formed by NO3 oxidation. Using aerosol composition data from three intensive observation periods at numerous measurement sites across Europe, we conclude that organic nitrates are a considerable fraction of fine particulate matter (PM1) at the continental scale. Organic nitrates represent 34% to 44% of measured submicron aerosol nitrate and are found at all urban and rural sites, implying a substantial potential of PM reduction by NOx emission control.

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Here, we present a new automated instrument for semicontinuous gradient measurements of water-soluble reactive trace gas species (NH3, HNO3, HONO, HCl, and SO2) and their related aerosol compounds (NH4+, NO3-, Cl-, SO4(2-)). Gas and aerosol samples are collected simultaneously at two heights using rotating wet-annular denuders and steam-jet aerosol collectors, respectively. Online (real-time) analysis using ion chromatography (IC) for anions and flow injection analysis (FIA) for NH4+ and NH3 provide a half-hourly averaged gas and aerosol gradients within each hour. Through the use of syringe pumps, IC preconcentration columns, and high-quality purified water, the system achieves detection limits (3sigma-definition) under field conditions of typically: 136/207,135/114, 29/ 22,119/92, and 189/159 ng m(-3) for NH3/NH4+, HNO3/NO3-, HONO/ NO2-, HCl/Cl- and SO2/SO4(2-), respectively. The instrument demonstrates very good linearity and accuracy for liquid and selected gas phase calibrations over typical ambient concentration ranges. As shown by examples from field experiments, the instrument provides sufficient precision (3-9%), even at low ambient concentrations, to resolve vertical gradients and calculate surface-atmosphere exchange fluxes undertypical meteorological conditions of the atmospheric surface layer using the aerodynamic gradient technique.

Abstract. In some regions, reducing aerosol ammonium nitrate (NH4NO3) concentrations may substantially improve air quality. This can be accomplished by reductions in precursor emissions, such as nitrogen oxides (NOx) to lower nitric acid (HNO3) that partitions to the aerosol, or reductions in ammonia (NH3) to lower particle pH and keep HNO3 in the gas phase. Using the ISORROPIA-II thermodynamic aerosol model and detailed observational data sets, we explore the sensitivity of aerosol NH4NO3 to gas-phase NH3 and NOx controls for a number of contrasting locations, including Europe, the United States, and China. NOx control is always effective, whereas the aerosol response to NH3 control is highly nonlinear and only becomes effective at a thermodynamic sweet spot. The analysis provides a conceptual framework and fundamental evaluation on the relative value of NOx versus NH3 control and demonstrates the relevance of pH as an air quality parameter. We find that, regardless of the locations examined, it is only when ambient particle pH drops below an approximate critical value of 3 (slightly higher in warm and slightly lower in cold seasons) that NH3 reduction leads to an effective response in PM2.5 mass. The required amount of NH3 reduction to reach the critical pH and efficiently decrease NH4NO3 at different sites is assessed. Owing to the linkage between NH3 emissions and agricultural productivity, the substantial NH3 reduction required in some locations may not be feasible. Finally, controlling NH3 emissions to increase aerosol acidity and evaporate NH4NO3 will have other effects, beyond reduction of PM2.5 NH4NO3, such as increasing aerosol toxicity and potentially altering the deposition patterns of nitrogen and trace nutrients.