Abstract. The composition of fine particulate matter (PM) in two major Greek cities (Athens and Patras) was measured during two wintertime campaigns, one conducted in 2013 and the other in 2012. A major goal of this study is to quantify the sources of organic aerosol (OA) and especially residential wood burning, which has dramatically increased due to the Greek financial crisis. A high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS) was deployed at both sites. PM with diameter less than 1 µm (PM 1 ) consisted mainly of organics (60-75 %), black carbon (5-20 %), and inorganic salts (around 20 %) in both Patras and Athens. In Patras, during evening hours, PM 1 concentrations were as high as 100 µg m −3 , of which 85 % was OA. In Athens, the maximum hourly value observed during nighttime was 140 µg m −3 , of which 120 µg m −3 was OA. Forty to 60 % of the average OA was due to biomass burning for both cities, while the remaining mass originated from traffic (12-17 %), cooking (12-16 %), and long-range transport (18-24 %). The contribution of residential wood burning was even higher (80-90 %) during the nighttime peak concentration periods, and less than 10 % during daytime. Cooking OA contributed up to 75 % during mealtime hours in Patras, while trafficrelated OA was responsible for 60-70 % of the OA during the morning rush hour.

The formation, atmospheric evolution, properties, and removal of organic particulate matter remain some of the least understood aspects of atmospheric chemistry despite the importance of organic aerosol (OA) for both human health and climate change. Here, we summarize our recent efforts to deal with the chemical complexity of the tens of thousands of organic compounds in the atmosphere using the volatility-oxygen content framework (often called the 2D-Volatility Basis Set, 2D-VBS). Our current ability to measure the ambient OA concentration as a function of its volatility and oxygen to carbon (O:C) ratio is evaluated. The combination of a thermodenuder, isothermal dilution and Aerosol Mass Spectrometry (AMS) together with a mathematical aerosol dynamics model is a promising approach. The development of computational modules based on the 2D-VBS that can be used in chemical transport models (CTMs) is described. Approaches of different complexity are tested against ambient observations, showing the challenge of simulating the complex chemical evolution of atmospheric OA. The results of the simplest approach describing the net change due to functionalization and fragmentation are quite encouraging, reproducing both the observed OA levels and O : C in a variety of conditions. The same CTM coupled with source-apportionment algorithms can be used to gain insights into the travel distances and age of atmospheric OA. We estimate that the average age of OA near the ground in continental locations is 1-2 days and most of it was emitted (either as precursor vapors or particles) hundreds of kilometers away. Condensation of organic vapors on fresh particles is critical for the growth of these new particles to larger sizes and eventually to cloud condensation nuclei (CCN) sizes. The semivolatile organics currently simulated by CTMs are too volatile to condense on these tiny particles with high curvature. We show that chemical aging reactions converting these semivolatile compounds to extremely low volatility compounds can explain the observed growth rates of new particles in rural environments.

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.