Gas phase precursors to anthropogenic secondary organic aerosol: Using the Master Chemical Mechanism to probe detailed observations of 1,3,5-trimethylbenzene photo-oxidation

A detailed gas-phase photochemical chamber box model, incorporating the Master Chemical Mechanism (MCMv3.1) degradation scheme for the model anthropogenic aromatic compound 1,3,5-trimethylbenzene, has been used to simulate data measured during a series of aerosol chamber experiments in order to evaluate the mechanism under a variety of VOC/NO_x conditions.The chamber model was used in the interpretation of comprehensive high (mass and time) resolution measurements of 1,3,5-trimethylbenzene and its photo-oxidation products recorded by a Chemical Ionisation Reaction Time-of-Flight Mass Spectrometer (CIR-TOF-MS). Supporting gas and aerosol measurements have also enabled us to explore the ‘missing link’ between the gas and aerosol phases. Model-measurement comparisons have been used to gain insight into the complex array of oxygenated products formed, including the peroxide bicyclic ring opening products (α,β-unsaturated-γ-dicarbonyls and furanones) and the O₂-bridged peroxide bicyclic ring-retaining products. To our knowledge this is the first time such high molecular weight species, corresponding to various peroxide bicyclic products represented in the MCMv3.1, have been observed in the gas-phase. The model was also used to give insight into which gas-phase species were participating in SOA formation, with the primary and secondary peroxide products, formed primarily under low NO_x conditions, identified as likely candidates.     

Determination of primary and secondary sources of organic acids and carbonaceous aerosols using stable carbon isotopes

Stable carbon isotope ratio (δ¹³C) data can provide important information regarding the sources and the processing of atmospheric organic carbon species. Formic, acetic and oxalic acid were collected from Zurich city in August–September 2002 and March 2003 in the gas and aerosol phase, and the corresponding δ¹³C analysis was performed using a wet oxidation method followed by isotope ratio mass spectrometry. In August, the δ¹³C values of gas phase formic acid showed a significant correlation with ozone (coefficient of determination (r²) = 0.63) due to the kinetic isotope effect (KIE). This indicates the presence of secondary sources (i.e. production of organic acids in the atmosphere) in addition to direct emission. In March, both gaseous formic and acetic acid exhibited similar δ¹³C values and did not show any correlation with ozone, indicating a predominantly primary origin. Even though oxalic acid is mainly produced by secondary processes, the δ¹³C value of particulate oxalic acid was not depleted and did not show any correlation with ozone, which may be due to the enrichment of ¹³C during the gas - aerosol partitioning.The concentrations and δ¹³C values of the different aerosol fractions (water soluble organic carbon, water insoluble organic carbon, carbonate and black carbon) collected during the same period were also determined. Water soluble organic carbon (WSOC) contributed about 60% to the total carbon and was enriched in ¹³C compared to other fractions indicating a possible effect of gas - aerosol partitioning on δ¹³C of carbonaceous aerosols. The carbonate fraction in general was very low (3% of the total carbon).     

Modelling of Air Quality with CAMx: A Case Study in Switzerland

The three-dimensional Eulerian model CAMx (Comprehensive Air QualityModel with Extensions) was applied for the first time to simulate bothgaseous and particulate photochemical air pollution in Switzerland during July 28–30, 1993. The meteorological input data were prepared using the Systems Applications International Mesoscale Model (SAIMM). The CAMx model results were compared with the measurements carried out at ground level andfrom airborne measuring platforms within the frame of the Swiss POLLUMET research programme. In general, the CAMx performance for gaseous species wasfound to be better than that of the previously used Urban Airshed Model (UAM)and the Variable Grid Urban Airshed Model (UAM-V). The most significant improvement for the gaseous species is in the prediction of HNO₃ concentrations, due to the inclusion of aerosol chemistry. Aerosol species such as NO₃ ^-, NH₄ ⁺, SO₄ ^2-, and secondary organic aerosols were calculated in one particle size range (0.04–2.5 m) and compared with a few measurements available. Although July 29 was reasonably well simulated, overestimated wind speeds by SAIMM for July 30 caused a too fast transport of pollutants. Similarly to measurements, significant spatial correlation of the secondarily formed aerosols with ozone and formaldehyde is found in the afternoon.