Abstract. Secondary organic aerosol (SOA) yields from the photo-oxidation of α-pinene were investigated in smog chamber (SC) experiments at low (23-29 %) and high (60-69 %) relative humidity (RH), various NO x / VOC ratios (0.04-3.8) and with different aerosol seed chemical compositions (acidic to neutralized sulfate-containing or hydrophobic organic). A combination of a scanning mobility particle sizer and an Aerodyne high-resolution time-of-flight aerosol mass spectrometer was used to determine SOA mass concentration and chemical composition. We used a Monte Carlo approach to parameterize smog chamber SOA yields as a function of the condensed phase absorptive mass, which includes the sum of OA and the corresponding bound liquid water content. High RH increased SOA yields by up to 6 times (1.5-6.4) compared to low RH. The yields at low NO x / VOC ratios were in general higher compared to yields at high NO x / VOC ratios. This NO x dependence follows the same trend as seen in previous studies for α-pinene SOA.A novel approach of data evaluation using volatility distributions derived from experimental data served as the basis for thermodynamic phase partitioning calculations of model mixtures in this study. These calculations predict liquidliquid phase separation into organic-rich and electrolyte phases. At low NO x conditions, equilibrium partitioning between the gas and liquid phases can explain most of the increase in SOA yields observed at high RH, when in addition to the α-pinene photo-oxidation products described in the literature, fragmentation products are added to the model mixtures. This increase is driven by both the increase in the absorptive mass and the solution non-ideality described by the compounds' activity coefficients. In contrast, at high NO x , equilibrium partitioning alone could not explain the strong increase in the yields with RH. This suggests that other processes, e.g. reactive uptake of semi-volatile species into the liquid phase, may occur and be enhanced at higher RH, especially for compounds formed under high NO x conditions, e.g. carbonyls.

Small volatile organic compounds (VOC) such as methane (CH4) have long been considered non-relevant to aerosol formation due to the high volatility of their oxidation products. However, even low aerosol yields from CH4 , the most abundant VOC in the atmosphere, would contribute significantly to the total particulate carbon budget. In this study, organic aerosol (OA) mass yields from CH 4 oxidation were evaluated at the Paul Scherrer Institute (PSI) smog chamber in the presence of inorganic and organic seed aerosols. Using labeled 13C methane, we could detect its oxidation products in the aerosol phase, with yields up to 0.09(+0.26 / -0.09) %. Overall, we estimate a maximum contribution of CH4 oxidation of 0.13% to the total global organic aerosol budget. We present evidence that oxidation of formaldehyde, a product of methane oxidation, contributes only a minor fraction to the observed aerosol yields. Therefore, other mechanisms appear to be more important for OA production from CH4 oxidation. A thorough elucidation of such mechanisms is still required. However, our results imply that many other small, volatile, and abundant hydrocarbons thus far considered irrelevant for OA production may contribute to the atmospheric OA budget

<p><strong>Abstract.</strong> Secondary organic aerosol (SOA) yields from the photooxidation of α-pinene were investigated in smog chamber (SC) experiments at low (23–29 %) and high (60–69 %) relative humidity (RH), various NO<sub><i>x</i></sub>/VOC ratios (0.04–3.8) and with different aerosol seed chemical compositions (acidic to neutralized sulfate-containing or hydrophobic organic). A combination of a scanning mobility particle sizer and an Aerodyne high resolution time-of-flight aerosol mass spectrometer was used to determine SOA mass concentration and chemical composition. We present wall-loss-corrected yields as a function of absorptive masses combining organics and the bound liquid water content. High RH increased SOA yields by up to six times (1.5–6.4) compared to low RH. The yields at low NO<sub><i>x</i></sub>/VOC ratios were in general higher compared to yields at high NO<sub><i>x</i></sub>/VOC ratios. This NO<sub><i>x</i></sub> dependence follows the same trend as seen in previous studies for α-pinene SOA. A novel approach of data evaluation using volatility distributions derived from experimental data served as basis for thermodynamic phase partitioning calculations of model mixtures in this study. These calculations predict liquid-liquid phase separation into organic-rich and electrolyte phases. At low NO<sub><i>x</i></sub> conditions, equilibrium partitioning between the gas and liquid phases can explain most of the increase in SOA yields at high RH. This is indicated by the model results, when in addition to the α-pinene photooxidation products described in the literature, more fragmented and oxidized organic compounds are added to the model mixtures. This increase is driven by both the increase in the absorptive mass due to the additional particulate water and the solution non-ideality described by the activity coefficients. In contrast, at high NO<sub><i>x</i></sub>, equilibrium partitioning alone could not explain the strong increase in the yields with increased RH. This suggests that other processes including the reactive uptake of semi-volatile species into the liquid phase may occur and be enhanced at higher RH, especially for compounds formed under high NO<sub><i>x</i></sub> conditions such as carbonyls.</p>

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