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.
A new method for stable carbon isotope ratio analysis of anhydrosugars from biomass burning aerosol particle source filter samples was developed by employing Thermal Desorption--2 Dimensional Gas Chromatography--Isotope Ratio Mass Spectrometry (TD-2DGC-IRMS). Compound specific isotopic measurements of levoglucosan, mannosan, and galactosan performed by TD-2DGC-IRMS in a standard mixture show good agreement with isotopic measurements of the bulk anhydrosugars, carried out by Elemental Analyzer--Isotope Ratio Mass Spectrometry (EA-IRMS). The established method was applied to determine the isotope ratios of levoglucosan, mannosan, and galactosan from source samples collected during combustion of hard wood, softwood, and crop residues. δ(13)C values of levoglucosan were found to vary between -25.6 and -22.2‰, being higher in the case of softwood. Mannosan and galactosan were detected only in the softwood samples showing isotope ratios of -23.5‰ (mannosan) and -25.7‰ (galactosan). The isotopic composition of holocellulose in the plant material used for combustion experiments was determined with δ(13)C values between -28.5 and -23.7‰. The difference in δ(13)C of levoglucosan in biomass burning aerosol particles compared to the parent fuel holocellulose was found to be -1.89 (±0.37)‰ for the investigated biomass fuels. Compound specific δ(13)C measurements of anhydrosugars should contribute to an improved source apportionment.
The chemical stability of levoglucosan was studied by exploring its isotopic fractionation during the oxidation by hydroxyl radicals. Aqueous solutions as well as mixed (NH4)2SO4‐levoglucosan particles were exposed to OH. In both cases, samples experiencing different extents of processing were isotopically analyzed by Thermal Desorption‐Gas Chromatography‐Isotope Ratio Mass Spectrometry (TD‐GC‐IRMS). From the dependence of levoglucosan δ13C and concentration on the reaction extent, the kinetic isotope effect (KIE) of the OH oxidation reactions was determined to be 1.00187±0.00027 and 1.00229±0.00018, respectively. Both show good agreement within the uncertainty range. For the heterogeneous oxidation of particulate levoglucosan by gas‐phase OH, a reaction rate constant of (2.67±0.03)·10−12 cm3 molecule−1S−1 was derived. The laboratory kinetic data, together with isotopic source and ambient observations, give information on the extent of aerosol chemical processing in the atmosphere.
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
Abstract. In many environments organic matter significantly contributes to the composition of atmospheric aerosol particles influencing its properties. Detailed chemical characterization of ambient aerosols is critical in order to understand the formation process, composition, and properties of aerosols and facilitates source identification and relative contributions from different types of sources to ambient aerosols in the atmosphere. However, current analytical methods are far from full speciation of organic aerosols and often require sampling times of up to one week. Offline methods are also subjected to artifacts during aerosol collection and storage.In the present work a new technique for quasi on-line compound specific measurements of organic aerosol particles was developed. The Aerosol Collection Module (ACM) focuses particles into a beam which is directed to a cooled sampling surface. The sampling takes place in a high vacuum environment where the gas phase from the sample volume is removed. After collection is completed volatile and semi-volatile compounds are evaporated from the collection surface through heating and transferred to a detector.For laboratory characterization the ACM was interfaced with a Gas Chromatograph Mass Spectrometer, Flame Ionization Detector system (GC/MS-FID), abbreviated as ACM GC-MS. The particle collection efficiency, gas phase transfer efficiency, and linearity of the ACM GC-MS were determined using laboratory generated octadecane aerosols. The ACM GC-MS is linear over the investigated mass range of Correspondence to: A. Kiendler-Scharr (a.kiendler-scharr@fz-juelich.de) 10 to 100 ng and a recovery rate of 100% was found for octadecane particles.The ACM GC-MS was applied to investigate secondary organic aerosol (SOA) formed from β-pinene oxidation.Nopinone, myrtanal, myrtenol, 1-hydroxynopinone, 3-oxonopinone, 3,7-dihydroxynopinone, and bicyclo[3,1,1]hept-3-ene-2-one were found as products in the SOA. The ACM GC-MS results are compared to quartz filter samples taken in parallel to the ACM GC-MS measurements. First measurements of ambient atmospheric aerosols are presented.
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