During the CARRIBA (Cloud, Aerosol, Radiation and tuRbulence in the trade wInd regime over BArbados) campaign, the interaction between aerosol particles and cloud microphysical properties was ...investigated in detail, which also includes the influence of clouds on the aerosol formation. During two intensive campaigns in 2010 and 2011, helicopter-borne measurement flights were performed to investigate the thermodynamic, turbulent, microphysical, and radiative properties of trade-wind cumuli over Barbados. During these flights, 91 cases with increased aerosol particle number concentrations near clouds were detected. The majority of these cases are also correlated with enhanced irradiance in the ultraviolet (UV) spectral wavelength range. This enhancement reaches values up to a factor of 3.3 greater compared to background values. Thus, cloud boundaries provide a perfect environment for the production of precursor gases for new particle formation. Another feature of cloud edges is an increased turbulence, which may also enhance nucleation and particle growth. The observed events have a mean length of 100 m, corresponding to a lifetime of less than 300 s. This implies that particles with diameters of at least 7 nm grew several nanometers per minute, which corresponds to the upper end of values in the literature (Kulmala et al., 2004). Such high values cannot be explained by sulfuric acid alone; thus extremely low volatility organic compounds (ELVOCs) are probably involved here.
The global environment is changing rapidly due to anthropogenic emissions and actions. Such activities modify aerosol and greenhouse gas concentrations in the atmosphere, leading to regional and ...global climate change and affecting, e.g., food and fresh-water security, sustainable use of natural resources and even demography. Here we present a conceptual design of a global, hierarchical observation network that can provide tools and increased understanding to tackle the inter-connected environmental and societal challenges that we will face in the coming decades. The philosophy behind the conceptual design relies on physical conservation laws of mass, energy and momentum, as well as on concentration gradients that act as driving forces for the atmosphere-biosphere exchange. The network is composed of standard, flux and/or advanced and flagship stations, each of which having specific and identified tasks. Each ecosystem type on the globe has its own characteristic features that have to be taken into consideration. The hierarchical network as a whole is able to tackle problems related to large spatial scales, heterogeneity of ecosystems and their complexity. The most comprehensive observations are envisioned to occur in flagship stations, with which the process-level understanding can be expanded to continental and global scales together with advanced data analysis, Earth system modelling and satellite remote sensing. The denser network of the flux and standard stations allows application and up-scaling of the results obtained from flagship stations to the global level.
The effect of increased reaction rates of stabilized Criegee intermediates (sCIs) with SO2 to produce sulfuric acid is investigated using data from two different locations, SMEAR II, Hyytiälä, ...Finland, and Hohenpeissenberg, Germany. Results from MALTE, a zero-dimensional model, show that using previous values for the rate coefficients of sCI + SO2, the model underestimates gas phase H2SO4 by up to a factor of two when compared to measurements. Using the rate coefficients recently calculated by Mauldin et al. (2012) increases sulfuric acid by 30–40%. Increasing the rate coefficient for formaldehyde oxide (CH2OO) with SO2 according to the values recommended by Welz et al. (2012) increases the H2SO4 yield by 3–6%. Taken together, these increases lead to the conclusion that, depending on their concentrations, the reaction of stabilized Criegee intermediates with SO2 could contribute as much as 33–46% to atmospheric sulfuric acid gas phase concentrations at ground level. Using the SMEAR II data, results from SOSA, a one-dimensional model, show that the contribution from sCI reactions to sulfuric acid production is most important in the canopy, where the concentrations of organic compounds are the highest, but can have significant effects on sulfuric acid concentrations up to 100 m. The recent findings that the reaction of sCI + SO2 is much faster than previously thought together with these results show that the inclusion of this new oxidation mechanism could be crucial in regional as well as global models.
The Antarctic near-coastal sub-micrometre aerosol particle features in summer were characterised based on measured data on aerosol hygroscopicity, size distributions, volatility and chemical ion and ...organic carbon mass concentrations. Hysplit model was used to calculate the history of the air masses to predict the particle origin. Additional measurements of meteorological parameters were utilised. The hygroscopic properties of particles mostly resembled those of marine aerosols. The measurements took place at 130 km from the Southern Ocean, which was the most significant factor affecting the particle properties. This is explained by the lack of additional sources on the continent of Antarctica. The Southern Ocean was thus a likely source of the particles and nucleating and condensing vapours. The particles were very hygroscopic (HGF 1.75 at 90 nm) and very volatile. Most of the sub-100 nm particle volume volatilised below 100 °C. Based on chemical data, particle hygroscopic and volatile properties were explained by a large fraction of non-neutralised sulphuric acid together with organic material. The hygroscopic growth factors assessed from chemical data were similar to measured. Hygroscopicity was higher in dry continental air masses compared with the moist marine air masses. This was explained by the aging of the marine organic species and lower methanesulphonic acid volume fraction together with the changes in the inorganic aerosol chemistry as the aerosol had travelled long time over the continental Antarctica. Special focus was directed in detailed examination of the observed new particle formation events. Indications of the preference of negative over positive ions in nucleation could be detected. However, in a detailed case study, the neutral particles dominated the particle formation process. Freshly nucleated particles had the smallest hygroscopic growth factors, which increased subsequent to particle aging.
Measurements of size-resolved cloud condensation nuclei (CCN) concentrations, subsaturated hygroscopic growth, size distribution, and chemical composition were collected from March through May, 2007, ...in the remote Boreal forests of Hyytiälä, Finland, as part of the European Integrated project on Aerosol Cloud Climate and Air Quality Interactions (EUCAARI) campaign. Hygroscopicity parameter, κ, distributions were derived independently from Continuous Flow-Streamwise Thermal Gradient CCN Chamber (CFSTGC) and Hygroscopicity Tandem Differential Mobility Analyzer (HTDMA) measurements. CFSTGC-derived κ values for 40, 60, and 80 nm particles range mostly between 0.10 and 0.40 with an average characteristic of highly oxidized organics of 0.20 ± 0.10, indicating that organics play a dominant role for this environment. HTDMA-derived κ were generally 30% lower. Diurnal trends of κ show a minimum at sunrise and a maximum in the late afternoon; this trend covaries with inorganic mass fraction and the m/z 44 organic mass fraction given by a quadrupole aerosol mass spectrometer, further illustrating the importance of organics in aerosol hygroscopicity. The chemical dispersion inferred from the observed κ distributions indicates that while 60 and 80 nm dispersion increases around midday, 40 nm dispersion remains constant. Additionally, 80 nm particles show a markedly higher level of chemical dispersion than both 40 and 60 nm particles. An analysis of droplet activation kinetics for the sizes considered indicates that most of the CCN activate as rapidly as (NH4)2SO4 calibration aerosol.
Climatic effects of newly-formed atmospheric secondary aerosol particles are to a large extent determined by their condensational growth rates. However, all the vapours condensing on atmospheric ...nanoparticles and growing them to climatically relevant sizes are not identified yet and the effects of particle phase processes on particle growth rates are poorly known. Besides sulfuric acid, organic compounds are known to contribute significantly to atmospheric nanoparticle growth. In this study a particle growth model MABNAG (Model for Acid-Base chemistry in NAnoparticle Growth) was developed to study the effect of salt formation on nanoparticle growth, which has been proposed as a potential mechanism lowering the equilibrium vapour pressures of organic compounds through dissociation in the particle phase and thus preventing their evaporation. MABNAG is a model for monodisperse aqueous particles and it couples dynamics of condensation to particle phase chemistry. Non-zero equilibrium vapour pressures, with both size and composition dependence, are considered for condensation. The model was applied for atmospherically relevant systems with sulfuric acid, one organic acid, ammonia, one amine and water in the gas phase allowed to condense on 3–20 nm particles. The effect of dissociation of the organic acid was found to be small under ambient conditions typical for a boreal forest site, but considerable for base-rich environments (gas phase concentrations of about 1010 cm−3 for the sum of the bases). The contribution of the bases to particle mass decreased as particle size increased, except at very high gas phase concentrations of the bases. The relative importance of amine versus ammonia did not change significantly as a function of particle size. While our results give a reasonable first estimate on the maximum contribution of salt formation to nanoparticle growth, further studies on, e.g. the thermodynamic properties of the atmospheric organics, concentrations of low-volatility organics and amines, along with studies investigating the applicability of thermodynamics for the smallest nanoparticles are needed to truly understand the acid-base chemistry of atmospheric nanoparticles.
The formation of new aerosol particles in the atmosphere is a key process influencing the aerosol number concentration as well as the climate, in particular at high altitude, where the newly formed ...particles directly influence cloud formation. However, free tropospheric new particle formation (NPF) is poorly documented due to logistic limitations and complex atmospheric dynamics around high-altitude stations that make the observation of this day-time process challenging. Recent improvements in measurement techniques make now possible the detection of neutral clusters down to ~ 1 nm sizes, which opens new horizons in our understanding of the nucleation process. Indeed, only the charged fraction of clusters has been reported in the upper troposphere up to now. Here we report day-time concentrations of charged and neutral clusters (1 to 2.5 nm mobility diameter) recorded at the interface between the boundary layer (BL) and the FT as well as in the FT at the altitude site of Puy de Dôme (1465 m a.s.l.), central France, between 10 and 29 February 2012. Our findings demonstrate that in the FT, and especially at the interface between the BL and the FT, the formation of 1.5 nm neutral clusters significantly exceeds the one of ionic clusters during NPF events, clearly indicating that they dominate in the nucleation process. We also observe that the total cluster concentration significantly increases during NPF events compared to the other days, which was not clearly observed for the charged cluster population in the past. During the studied period, the nucleation process does not seem to be sulfuric acid-limited and could be promoted by the transport of pollutants to the upper troposphere, coupled with low temperatures.
Gaseous sulphuric acid is a key precursor for new particle formation in the atmosphere. Previous experimental studies have confirmed a strong correlation between the number concentrations of freshly ...formed particles and the ambient concentrations of sulphuric acid. This study evaluates a body of experimental gas phase sulphuric acid concentrations, as measured by Chemical Ionization Mass Spectrometry (CIMS) during six intensive measurement campaigns and one long-term observational period. The campaign datasets were measured in Hyytiälä, Finland, in 2003 and 2007, in San Pietro Capofiume, Italy, in 2009, in Melpitz, Germany, in 2008, in Atlanta, Georgia, USA, in 2002, and in Niwot Ridge, Colorado, USA, in 2007. The long term data were obtained in Hohenpeissenberg, Germany, during 1998 to 2000. The measured time series were used to construct proximity measures ("proxies") for sulphuric acid concentration by using statistical analysis methods. The objective of this study is to find a proxy for sulfuric acid that is valid in as many different atmospheric environments as possible. Our most accurate and universal formulation of the sulphuric acid concentration proxy uses global solar radiation, SO2 concentration, condensation sink and relative humidity as predictor variables, yielding a correlation measure (R) of 0.87 between observed concentration and the proxy predictions. Interestingly, the role of the condensation sink in the proxy was only minor, since similarly accurate proxies could be constructed with global solar radiation and SO2 concentration alone. This could be attributed to SO2 being an indicator for anthropogenic pollution, including particulate and gaseous emissions which represent sinks for the OH radical that, in turn, is needed for the formation of sulphuric acid.
Boreal forests emit large amounts of volatile organic compounds (VOCs) which react with the hydroxyl radical (OH) to influence regional ozone levels and form secondary organic aerosol. Using OH ...reactivity measurements within a boreal forest in Finland, we investigated the budget of reactive VOCs. OH reactivity was measured using the comparative reactivity method, whereas 30 individual VOCs were measured using proton transfer reaction mass spectrometry, thermal-desorption gas chromatography mass spectrometry, and liquid chromatography mass spectrometry, in August 2008. The measured OH reactivity ranged from below detection limit (3.5 s−1), to ∼60 s−1 in a single pollution event. The average OH reactivity was ∼9 s−1 and no diel variation was observed in the profiles. The measured OH sinks (∼30 species) accounted for only 50% of the total measured OH reactivity, implying unknown reactive VOCs within the forest. The five highest measured OH sinks were: monoterpenes (1 s−1), CO (0.7 s−1), isoprene (0.5 s−1), propanal and acetone (0.3 s−1), and methane (0.3 s−1). We suggest that models be constrained by direct OH reactivity measurements to accurately assess the impact of boreal forest emissions on regional atmospheric chemistry and climate.
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