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Polycyclic aromatic hydrocarbons (PAHs) are organic pollutants in fine particulate matter (PM) long known to have mutagenic and carcinogenic effects, but much is unknown about the importance of local and remote sources to PAH levels observed in population-dense urban environments. A year-long sampling campaign in Athens, Greece, where more than 150 samples were analyzed for 31 PAHs and a wide range of chemical markers were used in combination with Positive Matrix Factorization (PMF) to constrain the temporal variability, sources and carcinogenic risk associated with PAHs. We find that biomass burning (BB), a source mostly effective during wintertime intense pollution events (observed for 18 % of measurement days in 2017), lead to wintertime PAH levels 7 times higher than in other seasons and was responsible for annual mean PAH concentrations (31 %) comparable to those from diesel/oil (33 %) and gasoline (29 %) sources. The contribution of non-local sources, although limited on an annual basis (7 %), was increased during summer, becoming comparable to that of local sources combined. The fraction of PAHs associated with BB is linked to increased health risk compared to the other sources, accounting for almost half the annual carcinogenic potential of PAHs (43 %). This can result in a larger number of excess cancer cases due to BB-related high PM levels and urges immediate action to reduce residential BB emissions in urban areas facing similar issues. [ABSTRACT FROM AUTHOR]

Droplet formation provides a direct microphysical link between aerosols and clouds (liquid or mixed phase), and its adequate description poses a major challenge for any atmospheric model. Observations are critical for evaluating and constraining the process. Towards this, aerosol size distributions, cloud condensation nuclei, hygroscopicity and lidar-derived vertical velocities were observed in Alpine mixed-phase clouds during the Role of Aerosols and Clouds Enhanced by Topography on Snow (RACLETS) field campaign in the Davos, Switzerland region during February and March 2019. Data from the mountain-top site of Weissfluhjoch (WFJ) and the valley site of Davos Wolfgang are studied. These observations are coupled with a state-of-the art droplet activation parameterization to investigate the aerosol-cloud droplet link in mixed-phase clouds. The mean CCN-derived hygroscopicity parameter, κ, at WFJ ranges between 0.2-0.3, consistent with expectations for continental aerosol. κ tends to decrease with size, possibly from an enrichment in organic material associated with the vertical transport of fresh ultrafine particle emissions (likely from biomass burning) from the valley floor in Davos. The parameterization provides droplet number that agrees with observations to within ~25 %. We also find that the susceptibility of droplet formation to aerosol concentration and vertical velocity variations can be appropriately described as a function of the standard deviation of the distribution of updraft velocities, σw, as the droplet number never exceeds a characteristic limit, termed limiting droplet number, of ~150-550 cm-3, which depends solely on σw. We also show that high aerosol levels in the valley, most likely from anthropogenic activities, increase cloud droplet number, reduce cloud supersaturation (<0.1 %) and shift the clouds to a state that is less susceptible to aerosol and become very sensitive to vertical velocity variations. The transition from aerosol to velocity-limited regime depends on the ratio of cloud droplet number to the limiting droplet number, as droplet formation becomes velocity-limited when this ratio exceeds 0.5. Under such conditions, droplet size tends to be minimal, reducing the likelihood that large drops are present that promote glaciation through rime splintering and droplet shattering. Identifying regimes where droplet number variability is dominated by dynamical - rather than aerosol - changes is key for interpreting and constraining when and which types of aerosol effects on clouds are active. [ABSTRACT FROM AUTHOR]

The Southeast United States has experienced a different climate warming trend compared to other places worldwide. Several hypotheses have been proposed to explain this trend, one being the interaction of anthropogenic and biogenic aerosol precursors that synergistically promote aerosol formation, elevate cloud droplet concentration and induce regional cooling. We examine these aerosol-cloud droplet links by analyzing regional scale data collected onboard the NOAA WP-3D aircraft during the 2013 Southeast Nexus (SENEX) campaign to quantify the sensitivity of droplet number to aerosol number, chemical composition and vertical velocity on a regional scale. The observed aerosol size distributions, chemical composition and vertical velocity distribution (Gaussian with standard deviation σw) are introduced into a state-of-the-art cloud droplet parameterization to show that cloud maximum supersaturations in the region are low, ranging from 0.02 to 0.52 % with an average of 0.14 ± 0.05 %. Based on these low values of supersaturation, the majority of activated droplets correspond to particles of diameter 90 nm and above. Droplet number shows little sensitivity to total aerosol owing to their strong competition for water vapor. Given, however, that σw exhibits considerable diurnal variability (ranging from 0.16 m/s during nighttime to over 1.2 m/s during day), its covariance with total aerosol number (Na) during the same period amplifies predicted response in cloud droplet number (Nd) by 3 to 5 times. Therefore, correct consideration of vertical velocity and its covariance with time and aerosol amount is important for fully understanding aerosol-cloud interactions and the magnitude of the aerosol indirect effect. Datasets and analysis such as the one presented here can provide the required constraints for addressing this important problem. [ABSTRACT FROM AUTHOR]

Submicron aerosol chemical composition has been studied during a year-long period (26/07/2016–31/07/2017) and two winter-time intensive campaigns (18/12/2013–21/02/2014 and 23/12/2015–17/02/2016), at a central site in Athens, Greece, using an Aerosol Chemical Speciation Monitor (ACSM). Concurrent measurements include a Particle-Into-Liquid Sampler (PILS-IC), a Scanning Mobility Particle Sizer (SMPS), an AE-33 Aethalometer and Ion Chromatography analysis on 24 or 12 hour filter samples. Quality of the ACSM data was assured by comparison versus the above mentioned measurements. The aim of the study was to characterize the seasonal variability of the main fine aerosol constituents and decipher the sources of organic aerosol (OA). Organics were found to contribute almost half of the submicron mass, with concentrations during wintertime reaching up to 200 μg m−3, on occasions. During this season, the primary sources contribute about 34 % of the organic fraction, comprising of biomass burning (10 %), fossil fuel combustion (16 %) and cooking (8 %), while the remaining 66 % is attributed to secondary aerosol. The semi-volatile component of the oxidized organic aerosol (SV-OOA; 31 %) was found to be clearly linked to combustion sources and in particular biomass burning, and even a part of the very oxidized, low-volatility component (LV-OOA; 35 %) could also be attributed to the oxidation of emissions from these primary combustion sources. These results highlight the rising importance of biomass burning in urban environments during wintertime, as revealed through this characteristic example of Athens, Greece, where the economic recessions led to an abrupt shift to biomass burning for heating purposes in winter. During summer, when concentrations of fine aerosols are considerably lower, more than 80 % of the organic fraction is attributed to secondary aerosol (SV-OOA 30 % and LV-OOA 53 %). In contrast to winter, SV-OOA appears to result from a well-mixed type of aerosol, linked to fast photochemical processes and the oxidation of primary traffic and biogenic emissions. Finally, LV-OOA presents a more regional character in summer, owing to the oxidation, within a few days, of organic aerosol. [ABSTRACT FROM AUTHOR]

Atmospheric New Particle Formation (NPF) is a common phenomenon all over the world. In this study we present the longest time series of NPF records in the eastern Mediterranean region by analyzing seven years of aerosol number size distribution data obtained with a mobility particle sizer. The measurements were performed at the Finokalia environmental research station on Crete, Greece during the period June 2008–June 2015. We found that NPF took place 29 % of the available days, undefined days were 26 % and non-event days 45 %. NPF is more frequent in April and May probably due to the biogenic activity and is less frequent in August and November. The NPF frequency increased during the measurement period, while particle growth rates showed a decreasing trend, indicating possible changes in the ambient sulfur dioxide concentrations in the area. Throughout the period under study, we frequently observed production of particles in the nucleation mode during night-time, a feature rarely observed in the ambient atmosphere. Nucleation mode particles had the highest concentration in winter, mainly because of the minimum sinks, and their average contribution to the total particle number concentration was 9 %. Nucleation mode particle concentrations were low outside periods of active NPF and growth, so there are hardly any other local sources of sub-25 nm particles. Additional atmospheric ion size distribution data simultaneously collected for more than two years period were also analyzed. Classification of NPF events based on ion measurements differed from the corresponding classification based on mobility spectrometer measurements, possibly indicating a different representation of local and regional NPF events between these two measurement data sets. We used MALTE-box model for a simulation case study of NPF in the eastern Mediterranean region. Monoterpenes contributing to NPF can explain a large fraction of the observed NPF events according to our model simulations. However the parametrization that resulted after sensitivity tests was significantly different from the one applied for the boreal environment. [ABSTRACT FROM AUTHOR]

The volatility distribution of the organic aerosol (OA) and its sources during the Southern Oxidant and Aerosol Study (SOAS; Centerville, Alabama) was constrained using measurements from an Aerodyne High-Resolution Time-of-Flight Aerosol Mass Spectrometer (HR-ToF-AMS) and a thermodenuder. Positive Matrix Factorization (PMF) analysis was applied on both the ambient and thermodenuded high resolution mass spectra, leading to four factors: more oxidized oxygenated OA (MO-OOA), less oxidized oxygenated OA (LO-OOA), an isoprene epoxydiols (IEPOX) related factor (Isoprene-OA) and biomass burning OA (BBOA). BBOA had the highest mass fraction remaining (MFR) at 100 °C, followed by the isoprene-OA, and the LO-OOA. Surprisingly the MO-OOA evaporated the most in the TD. The estimated effective vaporization enthalpies assuming an evaporation coefficient equal to unity were 58 ± 13 kJ mol-1 for the LO-OOA, 89 ± 10 kJ mol-1 for the MO-OOA, 55 ± 11 kJ mol-1 for the BBOA, and 63 ± 15 kJ mol-1 for the Isoprene-OA. The estimated volatility distribution of all factors covered a wide range including both semi-volatile and low-volatility components. BBOA had the lowest average volatility of all factors, even though it had the lowest O : C ratio among all factors. LO-OOA was the more volatile factor and its high MFR was due according to the model to its low enthalpy of vaporization. The Isoprene-OA factor had intermediate volatility, quite higher than suggested by a few other studies. The analysis suggests that deducing the volatility of a factor only from its MFR could lead to erroneous conclusions. The oxygen content of the factors can be combined with their estimated volatility and hygroscopicity to provide a better view of their physical properties. [ABSTRACT FROM AUTHOR]

Secondary organic aerosol (SOA) constitutes a substantial fraction of fine particulate matter and has important impacts on climate and human health. The extent to which human activities alter SOA formation from biogenic emissions in the atmosphere is largely undetermined. Here, we present direct observational evidence on the magnitude of anthropogenic influence on biogenic SOA formation based on comprehensive ambient measurements in the southeastern United States (US). Multiple high-time-resolution mass spectrometry organic aerosol measurements were made during different seasons at various locations, including urban and rural sites in the greater Atlanta area and Centreville in rural Alabama. Our results provide a quantitative understanding of the roles of anthropogenic SO2 and NOx in ambient SOA formation. We show that isoprene-derived SOA is directly mediated by the abundance of sulfate, instead of the particle water content and/or particle acidity as suggested by prior laboratory studies. Anthropogenic NOx is shown to enhance nighttime SOA formation via nitrate radical oxidation of monoterpenes, resulting in the formation of condensable organic nitrates. Together, anthropogenic sulfate and NOx can mediate 43-70% of total measured organic aerosol (29-49% of submicron particulate matter, PM1) in the southeastern US during summer. These measurements imply that future reduction in SO2 and NOx emissions can considerably reduce the SOA burden in the southeastern US. Updating current modeling frameworks with these observational constraints will also lead to more accurate treatment of aerosol formation for regions with substantial anthropogenic-biogenic interactions and consequently improve air quality and climate simulations. [ABSTRACT FROM AUTHOR]

Atmospheric new particle formation (NPF) events taking place over large distances between locations, featuring similar characteristics, have been the focus of studies during the last decade. The exact mechanism which triggers NPF still remains indefinable, so are the circumstances under which simultaneous occurrence of such events take place in different environments, let alone in environments which are parted by over 1200 km. In this study, concurrent number size distribution measurements were conducted in the urban environments of Athens (Greece) and Amman (Jordan) as well as the regional background site of Finokalia, Crete, all located within a distance of almost 1300 km for a 6-month period (February–July 2017). During the study period Athens and Finokalia had similar occurrence of NPF (around 20%), while the occurrence in Amman was double. When focusing on the dynamic characteristics at each site, it occurs that formation and growth rates at Amman are similar to those at Finokalia, while lower values in Athens can be ascribed to a higher pre-existing particle number at this urban site. By comparing common NPF events there are 5 concomitant days between all three sites, highly related to air masses origin. Additionally, for another 19 days NPF takes place simultaneously between Finokalia and Amman, which also share common meteorological characteristics, adding to a total of 60% out of 41 NPF events observed at Finokalia, also simultaneously occurring in Amman. [ABSTRACT FROM AUTHOR]