Formation of anthropogenic secondary organic aerosol (SOA) and its influence on biogenic SOA properties

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. Several experiments with exclusively anthropogenic 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<sup>−3</sup>. The yields (0.5–9%) 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 anthropogenic SOA enabled application of a simplified model to calculate the chemical turnover of the anthropogenic 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 at 343 K: 0.86–0.94). The anthropogenic 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 anthropogenic SOA the reaction mixtures needed a higher OH dose that also increased O/C and provided a less volatile aerosol. 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. This change in volatility under dark conditions is likely due to chemical or morphological changes not affecting O/C

Benchmarking source specific isotopic ratios of levoglucosan to better constrain the contribution of domestic heating to the air pollution

We report source specific isotope ratios of levoglucosan, the specific biomass burning tracer, in aerosol particle from the combustion of selected woods used for domestic heating in Europe, of coals containing cellulose (lignites) as well as of corn, a C4 plant. Here, we combine compound specific δ13C measurements of levoglucosan with total carbon δ13C of parent materials, to assess isotopic fractionations due to biosynthetic pathways or combustion processes. Levoglucosan formed during the combustion of cellulose from coals shows with δ13C of −21.1‰ and −18.6‰ a moderate enrichment in the heavier isotope compared to the C3 plant samples. Contrarily, observed levoglucosan isotope ratios of −25.0 to −21.5‰ for C3 plant samples are significantly lower than for the C4 plant sample (−12.4‰), as expected from the stronger 13C discrimination during the carbon fixation process by C3 compared to C4 plants. Overall, the C4 plant sample shows a 13C enrichment in all bulk measurements, on average by 12.2‰, 14.2‰ and 14.2‰ for total carbon (TC) in aerosol particle, whole plant/coal material and cellulose samples, respectively. Further, δ13C measurements of levoglucosan and TC of biomass burning aerosol particles, bulk plant/coal and cellulose in C3 plant samples agree well with the published observations. The combined levoglucosan/TC isotopic analyses can be used to differentiate among C3/coal/C4 origin of the smoke emissions from the cellulose-containing-fuel combustion. Noticeably, there is a consistent δ13C offset between C3 plant material and levoglucosan, which allows deriving emission levoglucosan isotope ratios when the combusted plant types are known