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In this study, the processes behind observed new particle formation (NPF) events and subsequent organicdominated particle growth at the Pallas AtmosphereEcosystem Supersite in Northern Finland are explored with the one-dimensional column trajectory model ADCHEM. The modeled sub-micron particle mass is up to similar to 75% composed of SOA formed from highly oxidized multifunctional organic molecules (HOMs) with low or extremely low volatility. In the model the newly formed particles with an initial diameter of 1.5 nm reach a diameter of 7 nm about 2 h earlier than what is typically observed at the station. This is an indication that the model tends to overestimate the initial particle growth. In contrast, the modeled particle growth to CCN size ranges (> 50 nm in diameter) seems to be underestimated because the increase in the concentration of particles above 50 nm in diameter typically occurs several hours later compared to the observations. Due to the high fraction of HOMs in the modeled particles, the oxygen-to-carbon (O V C) atomic ratio of the SOA is nearly 1. This unusually high O V C and the discrepancy between the modeled and observed particle growth might be explained by the fact that the model does not consider any particle-phase reactions involving semi-volatile organic compounds with relatively low O V C. In the model simulations where condensation of low-volatility and extremely low-volatility HOMs explain most of the SOA formation, the phase state of the SOA (assumed either liquid or amorphous solid) has an insignificant impact on the evolution of the particle number size distributions. However, the modeled particle growth rates are sensitive to the method used to estimate the vapor pressures of the HOMs. Future studies should evaluate how heterogeneous reactions involving semi-volatility HOMs and other less-oxidized organic compounds can influence the SOA composition-and size-dependent particle growth.

A 1-D atmospheric boundary layer (ABL) model coupled with a detailed atmospheric chemistry and aerosol dynamical model, the model SOSAA, was used to predict the ABL and detailed aerosol population (characterized by the number size distribution) time evolution. The model was applied over a period of 10 days in May 2013 to a pine forest site in southern Finland. The period was characterized by frequent new particle formation events and simultaneous intensive aerosol transformation. The aim of the study was to analyze and quantify the role of aerosol and ABL dynamics in the vertical transport of aerosols. It was of particular interest to what extent the fluxes above the canopy deviate from the particle dry deposition on the canopy foliage due to the above-mentioned processes. The model simulations revealed that the particle concentration change due to aerosol dynamics frequently exceeded the effect of particle deposition by even an order of magnitude or more. The impact was, however, strongly dependent on particle size and time. In spite of the fact that the timescale of turbulent transfer inside the canopy is much smaller than the timescales of aerosol dynamics and dry deposition, leading us to assume well-mixed properties of air, the fluxes at the canopy top frequently deviated from deposition inside the forest. This was due to transformation of aerosol concentration throughout the ABL and resulting complicated pattern of vertical transport. Therefore we argue that the comparison of timescales of aerosol dynamics and deposition defined for the processes below the flux measurement level do not unambiguously describe the importance of aerosol dynamics for vertical transport above the canopy. We conclude that under dynamical conditions reported in the current study the micrometeorological particle flux measurements can significantly deviate from the dry deposition into the canopy. The deviation can be systematic for certain size ranges so that the time-averaged particle

New particle formation (NPF) is an important atmospheric phenomenon. During an NPF event, particles first form by nucleation and then grow further in size. The growth step is crucial because it controls the number of particles that can become cloud condensation nuclei. Among various physical and chemical processes contributing to particle growth, condensation by organic vapors has been suggested as important. In order to better understand the influence of biogenic emissions on particle growth, we carried out modeling studies of NPF events during the BEACHON-ROCS (Biohydro-atmosphere interactions of Energy, Aerosol, Carbon, H2O, Organics & Nitrogen - Rocky Mountain Organic Carbon Study) campaign at Manitou Experimental Forest Observatory in Colorado, USA. The site is representative of the semi-arid western USA. With the latest Criegee intermediate reaction rates implemented in the chemistry scheme, the model underestimates sulfuric acid concentration by 50 %, suggesting either missing sources of atmospheric sulfuric acid or an overestimated sink term. The results emphasize the contribution from biogenic volatile organic compound emissions to particle growth by demonstrating the effects of the oxidation products of monoterpenes and 2-Methyl-3-buten-2-ol (MBO). Monoterpene oxidation products are shown to influence the nighttime particle loadings significantly, while their concentrations are insufficient to grow the particles during the day. The growth of ultrafine particles in the daytime appears to be closely related to the OH oxidation products of MBO.

Ozone concentrations in the Po Valley of northern Italy often exceed international regulations. As both a source of radicals and an intermediate in the oxidation of most volatile organic compounds (VOCs), formaldehyde (HCHO) is a useful tracer for the oxidative processing of hydrocarbons that leads to ozone production. We investigate the sources of HCHO in the Po Valley using vertical profile measurements acquired from the airship Zeppelin NT over an agricultural region during the PEGASOS 2012 campaign. Using a 1-D model, the total VOC oxidation rate is examined and discussed in the context of formaldehyde and ozone production in the early morning. While model and measurement discrepancies in OH reactivity are small (on average 3.4 ± 13%), HCHO concentrations are underestimated by as much as 1.5 ppb (45%) in the convective mixed layer. A similar underestimate in HCHO was seen in the 2002–2003 FORMAT Po Valley measurements, though the additional source of HCHO was not identified. Oxidation of unmeasured VOC precursors cannot explain the missing HCHO source, as measured OH reactivity is explained by measured VOCs and their calculated oxidation products. We conclude that local direct emissions from agricultural land are the most likely source of missing HCHO. Model calculations demonstrate that radicals from degradation of this non-photochemical HCHO source increase model ozone production rates by as much as 0.6 ppb h-1 (12%) before noon.

Measurements of hydroxyl ( OH) and hydroperoxy (HO2) radicals were made during the Mexico City Metropolitan Area (MCMA) field campaign as part of the MILAGRO (Megacity Initiative: Local and Global Research Observations) project during March 2006. These measurements provide a unique opportunity to test current models of atmospheric ROx (OH + HO2 + RO2) photochemistry under polluted conditions. A zero-dimensional box model based on the Regional Atmospheric Chemical Mechanism (RACM) was constrained by 10-min averages of 24 J-values and the concentrations of 97 chemical species. Several issues related to the ROx chemistry under polluted conditions are highlighted in this study: (i) Measured concentrations of both OH and HO2 were underpredicted during morning hours on a median campaign basis, suggesting a significant source of radicals is missing from current atmospheric models under polluted conditions, consistent with previous urban field campaigns. (ii) The model-predicted HO2/OH ratios underestimate the measurements for NO mixing ratios higher than 5 ppb, also consistent with previous urban field campaigns. This suggests that under high NOx conditions, the HO2 to OH propagation rate may be overestimated by the model or a process converting OH into HO2 may be missing from the chemical mechanism. On a daily basis ( 08: 40 a. m.-06: 40 p. m.), an analysis of the radical budget indicates that HONO photolysis, HCHO photolysis, O-3-alkene reactions and dicarbonyls photolysis are the main radical sources. O-3 photolysis contributes to less than 6% of the total radical production.

Measurements of hydroxyl ( OH) and hydroperoxy (HO2) radicals were made during the Mexico City Metropolitan Area (MCMA) field campaign as part of the MILAGRO (Megacity Initiative: Local and Global Research Observations) project during March 2006. These measurements provide a unique opportunity to test current models of atmospheric ROx (OH + HO2 + RO2) photochemistry under polluted conditions. A zero-dimensional box model based on the Regional Atmospheric Chemical Mechanism (RACM) was constrained by 10-min averages of 24 J-values and the concentrations of 97 chemical species. Several issues related to the ROx chemistry under polluted conditions are highlighted in this study: (i) Measured concentrations of both OH and HO2 were underpredicted during morning hours on a median campaign basis, suggesting a significant source of radicals is missing from current atmospheric models under polluted conditions, consistent with previous urban field campaigns. (ii) The model-predicted HO2/OH ratios underestimate the measurements for NO mixing ratios higher than 5 ppb, also consistent with previous urban field campaigns. This suggests that under high NOx conditions, the HO2 to OH propagation rate may be overestimated by the model or a process converting OH into HO2 may be missing from the chemical mechanism. On a daily basis ( 08: 40 a. m.-06: 40 p. m.), an analysis of the radical budget indicates that HONO photolysis, HCHO photolysis, O-3-alkene reactions and dicarbonyls photolysis are the main radical sources. O-3 photolysis contributes to less than 6% of the total radical production.