Measurements of the reactive uptake coefficient for N 2 O 5 hydrolysis, g m , on sub-micron organic aerosols were performed in an entrained aerosol flow tube as a function of relative humidity (RH), aerosol phase, N 2 O 5 partial pressure, and mean aerosol size. Aerosol phase and relative humidity were determined simultaneously, and chemical ionization mass spectrometry was used to detect the decay rate of N 2 O 5 in the presence of malonic acid or azelaic acid aerosol. The g m on solid malonic acid was determined to be less than 0.001 (RH ¼ 10-50%), and on solid azelaic acid, g m was 0.0005 AE 0.0003. Aqueous malonic acid aerosol yielded g m ¼ 0.0020 AE 0.0005 at 10% RH and increased with RH to $0.03 at RH ¼ 50-70%. We report the first evidence of an inverse dependence of the g m on the initial partial pressure of N 2 O 5 in the flow reactor, and a dependence on particle size for aerosol with surface area-weighted radii less than $100 nm at 50% RH. We find that the super-saturated malonic acid aerosol results are consistent with N 2 O 5 hydrolysis being both aerosol volume-limited where, for RH < 50%, water is the limiting reagent, and also with a surface-specific process.

International audienceExisting descriptions of bi-directional ammonia (NH3) land-atmosphere exchange incorporate temperature and moisture controls, and are beginning to be used in regional chemical transport models. However, such models have typically applied simpler emission factors to upscale the main NH3 emission terms. While this approach has successfully simulated the main spatial patterns on local to global scales, it fails to address the environment- and climate-dependence of emissions. To handle these issues, we outline the basis for a new modelling paradigm where both NH3 emissions and deposition are calculated online according to diurnal, seasonal and spatial differences in meteorology. We show how measurements reveal a strong, but complex pattern of climatic dependence, which is increasingly being characterized using ground-based NH3 monitoring and satellite observations, while advances in process-based modelling are illustrated for agricultural and natural sources, including a global application for seabird colonies. A future architecture for NH3 emission-deposition modelling is proposed that integrates the spatio-temporal interactions, and provides the necessary foundation to assess the consequences of climate change. Based on available measurements, a first empirical estimate suggests that 5°C warming would increase emissions by 42 per cent (28-67%). Together with increased anthropogenic activity, global NH3 emissions may increase from 65 (45-85) Tg N in 2008 to reach 132 (89-179) Tg by 2100

Abstract. Eleven instruments for the measurement of ambient concentrations of atmospheric ammonia gas (NH3), based on eight different measurement methods were inter-compared above an intensively managed agricultural field in late summer 2008 in Southern Scotland. To test the instruments over a wide range of concentrations, the field was fertilised with urea midway through the experiment, leading to an increase in the average concentration from 10 to 100 ppbv. The instruments deployed included three wet-chemistry systems, one with offline analysis (annular rotating batch denuder, RBD) and two with online-analysis (Annular Denuder sampling with online Analysis, AMANDA; AiRRmonia), two Quantum Cascade Laser Absorption Spectrometers (a large-cell dual system; DUAL-QCLAS, and a compact system; c-QCLAS), two photo-acoustic spectrometers (WaSul-Flux; Nitrolux-100), a Cavity Ring Down Spectrosmeter (CRDS), a Chemical Ionisation Mass Spectrometer (CIMS), an ion mobility spectrometer (IMS) and an Open-Path Fourier Transform Infra-Red (OP-FTIR) Spectrometer. The instruments were compared with each other and with the average concentration of all instruments. An overall good agreement of hourly average concentrations between the instruments (R2>0.84), was observed for NH3 concentrations at the field of up to 120 ppbv with the slopes against the average ranging from 0.67 (DUAL-QCLAS) to 1.13 (AiRRmonia) with intercepts of −0.74 ppbv (RBD) to +2.69 ppbv (CIMS). More variability was found for performance for lower concentrations (<10 ppbv). Here the main factors affecting measurement precision are (a) the inlet design, (b) the state of inlet filters (where applicable), and (c) the quality of gas-phase standards (where applicable). By reference to the fast (1 Hz) instruments deployed during the study, it was possible to characterize the response times of the slower instruments.

Atmospheric aerosol has been shown to contain an organic component that includes a significant fraction of small dicarboxylic acids, particularly in the urban environment. As an initial step toward understanding the phase in which particles may exist, a detailed study into the phase transitions of malonic and oxalic acid aerosols has been carried out. Both the aerosol phase transitions (deliquescence and efflorescence) and bulk solution properties (equilibrium water vapor pressure and the solubility and freezing curves of the aqueous solutions) are reported. An aerosol flow tube-FTIR and a static mode chamber-FTIR have been used to identify particulate phase transitions. In the latter the particles can be observed under ice-supersaturated conditions, allowing investigation of behavior at subeutectic temperatures. We report that both malonic and oxalic acid aerosols sustain a substantial level of solute supersaturation before efflorescence occurs, whereas deliquescence occurs at the thermodynamically predicted relative humidity. At room temperature, malonic acid efflorescence is observed at RH = 6% ± 3% and oxalic acid efflorescence occurs at RH ≤ 5%. Malonic acid particles deliquesce between 69% and 91% RH over the temperature range 293−252 K, and for oxalic acid conditions close to 100% RH are required. We report the first observation of the phase transition of oxalic acid between the anhydrous and dihydrate form and discuss our results in the context of recently published data.

Adverse health effects from exposure to air pollution are a global challenge and of widespread concern. Recent high ambient concentration episodes of air pollutants in European cities highlighted the dynamic nature of human exposure and the gaps in data and knowledge about exposure patterns. In order to support health impact assessment it is essential to develop a better understanding of individual exposure pathways in people's everyday lives by taking account of all environments in which people spend time. Here we describe the development, validation and results of an exposure method applied in a study conducted in Scotland. A low-cost particle counter based on light-scattering technology - the Dylos 1700 was used. Its performance was validated in comparison with equivalent instruments (TEOM-FDMS) at two national monitoring network sites (R(2)=0.9 at a rural background site, R(2)=0.7 at an urban background site). This validation also provided two functions to convert measured PNCs into calculated particle mass concentrations for direct comparison of concentrations with equivalent monitoring instruments and air quality limit values. This study also used contextual and time-based activity data to define six microenvironments (MEs) to assess everyday exposure of individuals to short-term PM2.5 concentrations. The Dylos was combined with a GPS receiver to track movement and exposure of individuals across the MEs. Seventeen volunteers collected 35 profiles. Profiles may have a different overall duration and structure with respect to times spent in different MEs and activities undertaken. Results indicate that due to the substantial variability across and between MEs, it is essential to measure near-complete exposure pathways to allow for a comprehensive assessment of the exposure risk a person encounters on a daily basis. Taking into account the information gained through personal exposure measurements, this work demonstrates the added value of data generated by the application of low-cost monitors.