Forests emit large quantities of volatile organic compounds (VOCs) to the atmosphere. Their condensable oxidation products can form secondary organic aerosol, a significant and ubiquitous component of atmospheric aerosol, which is known to affect the Earth's radiation balance by scattering solar radiation and by acting as cloud condensation nuclei. The quantitative assessment of such climate effects remains hampered by a number of factors, including an incomplete understanding of how biogenic VOCs contribute to the formation of atmospheric secondary organic aerosol. The growth of newly formed particles from sizes of less than three nanometres up to the sizes of cloud condensation nuclei (about one hundred nanometres) in many continental ecosystems requires abundant, essentially non-volatile organic vapours, but the sources and compositions of such vapours remain unknown. Here we investigate the oxidation of VOCs, in particular the terpene α-pinene, under atmospherically relevant conditions in chamber experiments. We find that a direct pathway leads from several biogenic VOCs, such as monoterpenes, to the formation of large amounts of extremely low-volatility vapours. These vapours form at significant mass yield in the gas phase and condense irreversibly onto aerosol surfaces to produce secondary organic aerosol, helping to explain the discrepancy between the observed atmospheric burden of secondary organic aerosol and that reported by many model studies. We further demonstrate how these low-volatility vapours can enhance, or even dominate, the formation and growth of aerosol particles over forested regions, providing a missing link between biogenic VOCs and their conversion to aerosol particles. Our findings could help to improve assessments of biosphere-aerosol-climate feedback mechanisms, and the air quality and climate effects of biogenic emissions generally.

Abstract. We describe a novel inlet that allows measurement of both gas and particle molecular composition when coupled to mass spectrometric, chromatographic, or optical sensors: the Filter Inlet for Gases and AEROsols (FIGAERO). The design goals for the FIGAERO are to allow unperturbed observation of ambient air while simultaneously analyzing gases and collecting particulate matter on a Teflon ® (hereafter Teflon) filter via an entirely separate sampling port. The filter is analyzed periodically by the same sensor on hourly or faster timescales using temperature-programmed thermal desorption. We assess the performance of the FI-GAERO by coupling it to a high-resolution time-of-flight chemical-ionization mass spectrometer (HRToF-CIMS) in laboratory chamber studies of α-pinene oxidation and field measurements at a boreal forest location. Low instrument backgrounds give detection limits of ppt or lower for compounds in the gas-phase and in the picogram m −3 range for particle phase compounds. The FIGAERO-HRToF-CIMS provides molecular information about both gases and particle composition on the 1 Hz and hourly timescales, respectively for hundreds of compounds. The FIGAERO thermal desorptions are highly reproducible (better than 10 %), allowing a calibrated assessment of the effective volatility of desorbing compounds and the role of thermal decomposition during the desorption process. We show that the often multi-modal desorption thermograms arising from secondary organic aerosol (SOA) provide additional insights into molecular composition and/or particle morphology, and exhibit changes with changes in SOA formation or aging pathways.

Abstract. We measured a large suite of gas-and particlephase multi-functional organic compounds with a Filter Inlet for Gases and AEROsols (FIGAERO) coupled to a highresolution time-of-flight chemical ionization mass spectrometer (HR-ToF-CIMS) developed at the University of Washington. The instrument was deployed on environmental simulation chambers to study monoterpene oxidation as a secondary organic aerosol (SOA) source. We focus here on results from experiments utilizing an ionization method most selective towards acids (acetate negative ion proton transfer), but our conclusions are based on more general physical and chemical properties of the SOA. Hundreds of compounds were observed in both gas and particle phases, the latter being detected by temperature-programmed thermal desorption of collected particles. Particulate organic compounds detected by the FIGAERO-HR-ToF-CIMS are highly correlated with, and explain at least 25-50 % of, the organic aerosol mass measured by an Aerodyne aerosol mass spectrometer (AMS). Reproducible multi-modal structures in the thermograms for individual compounds of a given elemental composition reveal a significant SOA mass contribution from high molecular weight organics and/or oligomers (i.e., multiphase accretion reaction products). Approximately 50 % of the HR-ToF-CIMS particle-phase mass is associated with compounds having effective vapor pressures 4 or more orders of magnitude lower than commonly measured monoterpene oxidation products. The relative importance of these accretion-type and other extremely low volatility products appears to vary with photochemical conditions. We present a desorption-temperature-based framework for apportionment of thermogram signals into volatility bins. The volatilitybased apportionment greatly improves agreement between measured and modeled gas-particle partitioning for select major and minor components of the SOA, consistent with thermal decomposition during desorption causing the conversion of lower volatility components into the detected higher volatility compounds.

Abstract. The aim of this study was to investigate oxidation of SOA formed from ozonolysis of α-pinene and limonene by hydroxyl radicals. This paper focuses on changes of particle volatility, using a Volatility Tandem DMA (VTDMA) set-up, in order to explain and elucidate the mechanism behind atmospheric ageing of the organic aerosol. The experiments were conducted at the AIDA chamber facility of Karlsruhe Institute of Technology (KIT) in Karlsruhe and at the SAPHIR chamber of Forchungzentrum Jülich (FZJ) in Jülich. A fresh SOA was produced from ozonolysis of α-pinene or limonene and then aged by enhanced OH exposure. As an OH radical source in the AIDA-chamber the ozonolysis of tetramethylethylene (TME) was used while in the SAPHIR-chamber the OH was produced by natural light photochemistry. A general feature is that SOA produced from ozonolysis of α-pinene and limonene initially was rather volatile and becomes less volatile with time in the ozonolysis part of the experiment. Inducing OH chemistry or adding a new portion of precursors made the SOA more volatile due to addition of new semi-volatile material to the aged aerosol. The effect of OH chemistry was less pronounced in high concentration and low temperature experiments when lower relative amounts of semi-volatile material were available in the gas phase. Conclusions drawn from the changes in volatility were confirmed by comparison with the measured and modelled chemical composition of the aerosol phase. Three quantified products from the α-pinene oxidation; pinonic acid, pinic acid and methylbutanetricarboxylic acid (MBTCA) were used to probe the processes influencing aerosol volatility. A major conclusion from the work is thatCorrespondence to: K. Salo (kent.salo@chem.gu.se) the OH induced ageing can be attributed to gas phase oxidation of products produced in the primary SOA formation process and that there was no indication on significant bulk or surface reactions. The presented results, thus, strongly emphasise the importance of gas phase oxidation of semi-or intermediate-volatile organic compounds (SVOC and IVOC) for atmospheric aerosol ageing.

Abstract. Secondary organic aerosol (SOA) formation from mixed anthropogenic and biogenic precursors has been studied exposing reaction mixtures to natural sunlight in the SAPHIR chamber in Jülich, Germany. In this study aromatic compounds served as examples of anthropogenic volatile organic compound (VOC) and a mixture of α-pinene and limonene as an example for biogenic VOC. Several experiments with exclusively aromatic precursors were performed to establish a relationship between yield and organic aerosol mass loading for the atmospheric relevant range of aerosol loads of 0.01 to 10 μg m−3. The yields (0.5 to 9%) were comparable to previous data and further used for the detailed evaluation of the mixed biogenic and anthropogenic experiments. For the mixed experiments a number of different oxidation schemes were addressed. The reactivity, the sequence of addition, and the amount of the precursors influenced the SOA properties. Monoterpene oxidation products, including carboxylic acids and dimer esters were identified in the aged aerosol at levels comparable to ambient air. OH radicals were measured by Laser Induced Fluorescence, which allowed for establishing relations of aerosol properties and composition to the experimental OH dose. Furthermore, the OH measurements in combination with the derived yields for aromatic SOA enabled application of a simplified model to calculate the chemical turnover of the aromatic precursor and corresponding anthropogenic contribution to the mixed aerosol. The estimated anthropogenic contributions were ranging from small (≈8%) up to significant fraction (>50%) providing a suitable range to study the effect of aerosol composition on the aerosol volatility (volume fraction remaining (VFR) at 343 K: 0.86–0.94). The aromatic aerosol had higher oxygen to carbon ratio O/C and was less volatile than the biogenic fraction. However, in order to produce significant amount of aromatic SOA the reaction mixtures needed a higher OH dose that also increased O/C and provided a less volatile aerosol. The SOA yields, O/C, and f44 (the mass fraction of CO2+ ions in the mass spectra which can be considered as a measure of carboxylic groups) in the mixed photo-chemical experiments could be described as linear combinations of the corresponding properties of the pure systems. For VFR there was in addition an enhancement effect, making the mixed aerosol significantly less volatile than what could be predicted from the pure systems. A strong positive correlation was found between changes in volatility and O/C with the exception during dark hours where the SOA volatility decreased while O/C did not change significantly. Thus, this change in volatility under dark conditions as well as the anthropogenic enhancement is due to chemical or morphological changes not affecting O/C.