Abstract. A new aerosol dynamics model (DMANx) has been developed that simulates aerosol size/composition distribution and includes the condensation of organic vapors on nanoparticles through the implementation of the recently developed volatility basis set framework. Simulations were performed for Hyytiälä (Finland) and Finokalia (Greece), two locations with different organic sources where detailed measurements were available to constrain the new model. We investigate the effect of condensation of organics and chemical aging reactions of secondary organic aerosol (SOA) precursors on ultrafine particle growth and particle number concentration during a typical springtime nucleation event in both locations. This work highlights the importance of the pathways of oxidation of biogenic volatile organic compounds and the production of extremely low volatility organics. At Hyytiälä, organic condensation dominates the growth process of new particles. The low-volatility SOA contributes to particle growth during the early growth stage, but after a few hours most of the growth is due to semi-volatile SOA. At Finokalia, simulations show that organics have a complementary role in new particle growth, contributing 45% to the total mass of new particles. Condensation of organics increases the number concentration of particles that can act as CCN (cloud condensation nuclei) (N100) by 13% at Finokalia and 25% at Hyytiälä during a typical spring day with nucleation. The sensitivity of our results to the surface tension used is discussed.
Abstract. Emissions of biogenic volatile organic compounds (BVOC) have changed in the past millennium due to changes in land use, temperature and CO2 concentrations. Recent model reconstructions of BVOC emissions over the past millennium predicted changes in dominant secondary organic aerosol (SOA) producing BVOC classes (isoprene, monoterpenes and sesquiterpenes). The reconstructions predicted that global isoprene emissions have decreased (land-use changes to crop/grazing land dominate the reduction), while monoterpene and sesquiterpene emissions have increased (temperature increases dominate the increases); however, all three show regional variability due to competition between the various influencing factors. These BVOC changes have largely been anthropogenic in nature, and land-use change was shown to have the most dramatic effect by decreasing isoprene emissions. In this work, we use two modeled estimates of BVOC emissions from the years 1000 to 2000 to test the effect of anthropogenic changes to BVOC emissions on SOA formation, global aerosol size distributions, and radiative effects using the GEOS-Chem-TOMAS global aerosol microphysics model. With anthropogenic emissions (e.g. SO2, NOx, primary aerosols) held at present day values and BVOC emissions changed from year 1000 to year 2000 values, decreases in the number concentration of particles of size Dp > 80 nm (N80) of >25% in year 2000 relative to year 1000 were predicted in regions with extensive land-use changes since year 1000 which led to regional increases in direct plus indirect aerosol radiative effect of >0.5 W m−2 in these regions. We test the sensitivity of our results to BVOC emissions inventory, SOA yields and the presence of anthropogenic emissions; however, the qualitative response of the model to historic BVOC changes remains the same in all cases. Accounting for these uncertainties, we estimate millennial changes in BVOC emissions cause a global mean direct effect of between +0.022 and +0.163 W m−2 and the global mean cloud-albedo aerosol indirect effect of between −0.008 and −0.056 W m−2. This change in aerosols, and the associated radiative forcing, could be a~largely overlooked and important anthropogenic aerosol effect on regional climates.
The growth or evaporation of droplets or crystals in a gas mixture is controlled by the balance of mass and heat transfer. The nature of the condensing vapor and above all its relative abundance in the atmosphere plays a major role in the mass transfer processes. We investigate the influence of molecular diffusion, thermal diffusion or Soret effect (mass transfer), and Dufour effect (heat transfer), with previous work done by Kulmala and Vesala (1991) as a starting point (hereafter KV91) and extending it to the case of high relative abundances of the condensing vapor.
We analyzed size distributions measured continuously at a boreal forest measurement site at Hyytiaelae, Finland between 1996 and 2003. From the eight-year data we identified days when new aerosol particle formation was taking place as well as days when no formation was detected, removing days with ambiguous status. The event days were then classified based on whether it was possible to determine formation and growth rates of new particles. These characteristics were then calculated. We found that new particle formation happens frequently in the boreal forest boundary layer, with at least 24% of days containing an event. Events are more probable during spring and autumn than during other times of the year. The average formation rate of particles larger than 3 nm was 0.8 cm{sup -3} s{sup -1}, with enhanced rates during spring and autumn. The mean growth rate was 3.0 nm h{sup -1}, peaking in summer. The created event database is valuable for future studies of reasons leading to new particle formation in the atmosphere. (orig.)
Night-time reactions of biogenic volatile organic compounds (BVOCs) and nitrate radicals (NO3) can lead to the formation of secondary organic aerosol (BSOANO3). Here we firstly present the chemical composition and volatility of BSOANO3 formed in the dark from three precursors (isoprene, α-pinene, and β-caryophyllene) in atmospheric simulation chamber experiments (Wu et al., 2021; Bell et al., 2022; Graham et al., 2022). The chemical composition of particle-phase compounds was measured with a chemical ionization mass spectrometer with a filter inlet for gases and aerosols (FIGAERO-CIMS) and an extractive electrospray ionization time-of-flight mass spectrometer (EESI-TOF). The volatility information of BSOANO3 was derived from isothermal evaporation chambers, temperature-dependent evaporation in a volatility tandem differential mobility analyzer (VTDMA), and thermal desorption in the FIGAERO-CIMS. In addition, the molecular composition of particulate compounds was used in volatility parametrizations to calculate the compounds’ saturation vapor pressures and to establish volatility basis sets (VBS, Donahue et al., 2011) for the bulk aerosol. Four different parametrizations were tested for reproducing the observed evaporation in a kinetic modeling framework (Riipinen et al., 2010). Here, we compare the different methods for particle volatility determination and discuss the limitation of the parameterizations.Our results suggest the BSOANO3 from α-pinene and isoprene be dominated by low-volatility organic compounds (LVOC) and semi-volatile organic compounds (SVOC), while the corresponding BSOANO3 from β-caryophyllene consists primarily of extremely low-volatility organic compounds (ELVOC) and LVOC. The parameterizations yielded variable results in terms of reproducing the observed evaporation, and generally the comparisons pointed to a need for re-evaluating the treatment of the nitrate group in such parameterizations.Furthermore, we link the lab experiments to field observations of secondary organic aerosols and organic nitrates from a boreal forest (ICOS Norunda, Sweden), which is dominated by monoterpene emissions and includes also isoprene and sesquiterpene emissions. We will show the chemical composition and volatility of the particles detected with a FIGAERO-CIMS, compare them to the lab results, and discuss how nitrate-initiated nighttime oxidation of different precursors contribute to the total particle formation and growth. References:Wu, C. et al., Atmos. Chem. Phys., 21, 14907–14925, 2021Bell, D. et al., Atmos. Chem. Phys., 22, 13167–13182, 2022Graham, E. and Wu, C. et al, EGUsphere [preprint], https://doi.org/10.5194/egusphere-2022-1043, 2022Donahue, N. M. et al., Atmos. Chem. Phys., 11, 3303–3318, 2011Riipinen, I. et al., Atmos. Environ., 44-5, 597-607, 2010 
Equipment consisting of annular denuders, a filter, and a polyurethane foam adsorbent was used for sampling 15 PAHs from the diluted emission from a heat-storing masonry heater. The denuder method was compared to the ISO 11338 method which was used for the sampling from hot and undiluted exhaust gas. The denuder method used with the exhaust dilution gave a realistic gas–particle distribution of PAHs in more atmospheric-like conditions compared to the sampling from undiluted exhaust gas where PAHs were almost totally in the gas phase. The results gained with the denuder method from the diluted exhaust are more relevant, e.g., from exposure and atmospheric processes point of view. The emissions from smoldering combustion conditions (SC) were compared with the emissions from normal combustion conditions (NC). The emission of each PAH was 7 to 14 times higher from SC than from NC, and the gas–particle distribution was shifted towards the particle phase due to increased condensation of PAHs. The PAHs could be divided into three groups based on their phase distributions. In the first group, PAHs existed mostly in the gas phase in both combustion cases; the vapor pressures of PAHs were lower than the saturation vapor pressures. In the second group, the gas phase was saturated and the concentration was almost the same in both combustion cases, whereas the particle phase concentration was higher in SC. In the third group, PAHs were mostly in the particle phase where the concentration was higher in SC.
Abstract. Particle–water interactions of completely soluble or insoluble particles are fairly well understood but less is known of aerosols consisting of mixtures of soluble and insoluble components. In this study, laboratory measurements were performed to investigate cloud condensation nuclei (CCN) activity of silica particles mixed with ammonium sulfate (a salt), sucrose (a sugar) and bovine serum albumin known as BSA (a protein). The agglomerated structure of the silica particles was investigated using measurements with a differential mobility analyser (DMA) and an aerosol particle mass analyser (APM). Based on these data, the particles were assumed to be compact agglomerates when studying their CCN activation capabilities. Furthermore, the critical supersaturations of particles consisting of pure and mixed soluble and insoluble compounds were explored using existing theoretical frameworks. These results showed that the CCN activation of single-component particles was in good agreement with Köhler- and adsorption theory based models when the agglomerated structure was accounted for. For mixed particles the CCN activation was governed by the soluble components, and the soluble fraction varied considerably with particle size for our wet-generated aerosols. Our results confirm the hypothesis that knowing the soluble fraction is the key parameter needed for describing the CCN activation of mixed aerosols, and highlight the importance of controlled coating techniques for acquiring a detailed understanding of the CCN activation of atmospheric insoluble particles mixed with soluble pollutants.
Abstract. In this study we investigated the impact of water uptake by aerosol particles in ambient atmosphere on their optical properties and their direct radiative effect (ADRE, W m−2) in the Arctic at Ny-Ålesund, Svalbard, during 2008. To achieve this, we combined three models, a hygroscopic growth model, a Mie model and a radiative transfer model, with an extensive set of observational data. We found that the seasonal variation of dry aerosol scattering coefficients showed minimum values during the summer season and the beginning of fall (July-August-September), when small particles (< 100 nm in diameter) dominate the aerosol number size distribution. The maximum scattering by dry particles was observed during the Arctic haze period (March-April-May) when the average size of the particles was larger. Considering the hygroscopic growth of aerosol particles in the ambient atmosphere had a significant impact on the aerosol scattering coefficients: the aerosol scattering coefficients were enhanced by on average a factor of 4.30 ± 2.26 (mean ± standard deviation), with lower values during the haze period (March-April-May) as compared to summer and fall. Hygroscopic growth of aerosol particles was found to cause 1.6 to 3.7 times more negative ADRE at the surface, with the smallest effect during the haze period (March-April-May) and the highest during late summer and beginning of fall (July-August-September).
