Journal cover Journal topic
Geoscientific Model Development An interactive open-access journal of the European Geosciences Union
doi:10.5194/gmd-2016-163
© Author(s) 2016. This work is distributed
under the Creative Commons Attribution 3.0 License.
Development and technical paper
11 Aug 2016
Review status
A revision of this discussion paper was accepted for the journal Geoscientific Model Development (GMD) and is expected to appear here in due course.
Constraining a hybrid volatility basis set model for aging of wood burning emissions using smog chamber experiments
Giancarlo Ciarelli1, Imad El Haddad1, Emily Bruns1, Sebnem Aksoyoglu1, Ottmar Möhler2, Urs Baltensperger1, and André S. H. Prévôt1 1Paul Scherrer Institute, Laboratory of Atmospheric Chemistry, 5232 Villigen PSI, Switzerland
2Karlsruhe Institute of Technology, Institute of Meteorology and Climate Research, Germany
Abstract. Semi-volatile and intermediate volatility organic compounds (SVOCs, IVOCs) are not included in the current non-methane volatile organic compounds (NMVOCs) emission inventories but may be important for the formation of secondary organic aerosol (SOA). In this study, novel wood combustion aging experiments performed at different temperatures (263 K and 288 K) in a ~7 m3 smog chamber were modelled using a hybrid volatility basis set (VBS) box model, representing the emission partitioning and their oxidation against OH. We combine aerosol-chemistry box model simulations with unprecedented measurements of nontraditional volatile organic compounds (NTVOCs) from a high-resolution proton transfer reaction mass spectrometer (PTR-MS) and with organic aerosol measurements from an aerosol mass spectrometer (AMS). In so-doing, we are able to observationally-constrain the amounts of different NTVOCs aerosol precursors (in the model) relative to low-volatility and semi-volatile primary organic material (OMsv) which is partitioned based on current published volatility distribution data. By comparing the NTVOCs/OMsv ratios at different temperatures, we determine the enthalpies of vaporization of primary biomass burning organic aerosols. Further, the developed model allows for evaluating the evolution of oxidation products of the semi-volatile and volatile precursors with aging. More than 30,000 box model simulations were performed to retrieve the combination of parameters that fit best the observed organic aerosol mass and O:C ratios. The parameters investigated include the NTVOC reaction rates and yields as well as enthalpies of vaporization and the O:C of secondary organic aerosol surrogates. Our results suggest an average ratio of NTVOCs to the sum of non-volatile and semi-volatile organic compounds of ~4.75. The mass yields of these compounds determined for a wide range of atmospherically relevant temperatures and organic aerosol (OA) concentrations were predicted to vary between 8 and 30 % after 5 hours of continuous aging. Based on the reaction scheme used, reaction rates of the NTVOC mixture range from 3.0 × 10–11 cm3 molec−1 s−1 to 4.0 × 10–11 cm3 molec−1 s−1. The average enthalpy of vaporization of SOA surrogates was determined to be between 55,000 J mol−1 and 35,000 J mol−1 which implies a yield increase of 0.03–0.06 % K−1 with decreasing temperature. The improved VBS scheme is suitable for implementation into chemical transport models to predict the burden and oxidation state of primary and secondary biomass burning aerosols.

Citation: Ciarelli, G., El Haddad, I., Bruns, E., Aksoyoglu, S., Möhler, O., Baltensperger, U., and Prévôt, A. S. H.: Constraining a hybrid volatility basis set model for aging of wood burning emissions using smog chamber experiments, Geosci. Model Dev. Discuss., doi:10.5194/gmd-2016-163, in review, 2016.
Giancarlo Ciarelli et al.
Giancarlo Ciarelli et al.

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Short summary
In Europe, residential wood-burning emissions constitute one of the main anthropogenic sources of air pollution. Novel wood-burning experiments performed in a state-of-the-art smog chamber, provide valuable information about the chemical properties of wood burning emissions and the transformation in the atmosphere. In this study, these new data were used in a box model to constrain a parameterization suitable to predict the contribution of wood-burning to air pollution with large-scale models.
In Europe, residential wood-burning emissions constitute one of the main anthropogenic sources...
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