Date of Award

Winter 2-2017

Embargo Period

3-9-2019

Degree Type

Dissertation

Degree Name

Doctor of Philosophy (PhD)

Department

Chemical Engineering

Advisor(s)

Spyros Pandis

Abstract

Organic particulate matter represents a significant fraction of sub-micrometer atmospheric aerosol mass. However, organic aerosol (OA) consists of thousands of different organic compounds making the simulation of its concentration, chemical evolution, physical and chemical properties extremely challenging. The identity of the great majority of these compounds remains unknown. The volatility of atmospheric OA is one of its most important physical properties since it determines the partitioning of these organic compounds between the gas and particulate phases. The use of lumped compounds with averaged properties is a promising solution for the representation of OA in atmospheric chemical transport models. The two-dimensional volatility basis set (2D-VBS) is a proposed method used to describe OA distribution as a function of the volatility and oxygen content of the corresponding compounds. In the first part of the work we evaluate our ability to measure the OA volatility distribution using a thermodenuder (TD). We use a new method combining forward modeling, introduction of ‘experimental’ error and inverse modeling with error minimization for the interpretation of TD measurements. The OA volatility distribution, its effective vaporization enthalpy, the mass accommodation coefficient and the corresponding uncertainty ranges are calculated. Our results indicate that existing TD-based approaches quite often cannot estimate reliably the OA volatility distribution, leading to large uncertainties, since there are many different combinations of the three properties that can lead to similar thermograms. We propose an improved experimental approach combining TD and isothermal dilution measurements. We evaluate this experimental approach using the same model and show that it is suitable for studies of OA volatility in the lab and the field. Measurements combining a thermodenuder (TD) and a High Resolution Time-of-Flight Aerosol Mass Spectrometer (HR-ToF-AMS) took place during summer and winter in Paris, France as part of the collaborative project MEGAPOLI and during the winter of 2013 in the city of Athens. The above volatility estimation method with the uncertainty estimation algorithm is applied to these datasets in order to estimate the volatility distribution for the organic aerosol (OA) and its components during the two campaigns. The concentrations of the OA components as a function of temperature were measured combining data from the thermodenuder and the aerosol mass spectrometer (AMS) with Positive Matrix Factorization (PMF) analysis. Combining the bulk average O:C ratios and volatility distributions of the various factors, our results are placed into the two-dimensional volatility basis set (2D-VBS) framework. The OA factors cover a broad spectrum of volatilities with no direct link between the average volatility and average O:C of the OA components. An intercomparison among the OA components of both campaigns and their physical properties is also presented. The approach combining thermodenuder and isothermal dilution measurements is tested in smog chamber experiments using OA produced during meat charbroiling. The OA mass fraction remaining is measured as a function of temperature in the TD and as a function of time in the isothermal dilution chamber. These two sets of measurements are used together to estimate the volatility distribution of the OA and its effective vaporization enthalpy and accommodation coefficient. In the isothermal dilution experiments approximately 20% of the OA evaporate within 15 min. In the TD almost all the OA evaporated at approximately 200oC. The resulting volatility distributions suggest that around 60-75% of the cooking OA (COA) at concentrations around 500 μg m-3 consists of low volatility organic compounds (LVOCs), 20-30% of semi-volatile organic compounds (SVOCs) and around 10% of intermediate volatility organic compounds (IVOCs). The estimated effective vaporization enthalpy of COA is 100 ± 20 kJ mol-1 and the effective accommodation coefficient is around 0.05. The characteristics of the COA factor from the Athens campaign are compared to those of the OA produced from meat charbroiling in these experiments. In the next step, different parameterizations of the organic aerosol (OA) formation and evolution in the two-dimensional Volatility Basis Set (2D-VBS) framework are evaluated using ground and airborne measurements collected in the 2012 Pan-European Gas AeroSOls-climate-interaction Study (PEGASOS) field campaign in the Po Valley, Italy. A number of chemical schemes are examined, taking into account various functionalization and fragmentation pathways for biogenic and anthropogenic OA components. Model predictions and measurements, both at the ground and aloft, indicate a relatively oxidized OA with little average diurnal variation. Total OA concentration and O:C ratios were reproduced within experimental error by a number of chemical aging schemes. Anthropogenic SOA is predicted to contribute 15-25% of the total OA, while SOA from intermediate volatility compounds oxidation another 20-35%. Biogenic SOA contributions varied from 15 to 45% depending on the modeling scheme. The average OA and O:C diurnal variation and their vertical profiles showed a surprisingly modest sensitivity to the assumed vaporization enthalpy for all aging schemes. This can be explained by the intricate interplay between the changes in partitioning of the semivolatile compounds and their gas-phase chemical aging reactions. The same set of different parameterizations of the organic aerosol (OA) formation and evolution in the two-dimensional Volatility Basis Set (2D-VBS) framework are evaluated using ground measurements collected in the 2013 PEGASOS field campaign in the boreal forest station of Hyytiälä in Southern Finland. The most successful is the simple functionalization scheme of Murphy et al. (2012) while all seven aging schemes have satisfactory results, consistent with the ground measurements. Despite their differences, these schemes predict similar contributions of the various OA sources and formation pathways. Anthropogenic SOA is predicted to contribute 11- 18% of the total OA, while SOA from intermediate volatility compounds oxidation another 18- 27%. The highest contribution comes from biogenic SOA, as expected contributing 40 to 63% depending on the modeling scheme. The primary OA contributes 4% while the SOA resulting from the oxidation of the evaporated POA varies between 4 to 6%. Finally, 5-6% is according to the model the results of long range transport from outside the modeling domain.

Available for download on Saturday, March 09, 2019

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