No abstract

An aerosol time-of-flight mass spectrometer (ATOFMS) was used to detect trimethylamine (TMA) in 0.52-1.9 μm particles at urban and rural sites in Southern Ontario during the summer and winter of 2007. During the summer, TMA-containing particles were observed exclusively during high relative humidity or fog events at both the urban and rural sites. In the wintertime, greater concentrations of TMA-containing particles were linked to cloud processing of aerosol in air masses originating from over agricultural and livestock areas. A laboratory study revealed that, at high relative humidity (∼ 100%), gas phase TMA at concentrations ranging from 2 to 20,000 ppt partitions preferentially to acidic particles present in the ambient air. On the basis of the field and laboratory studies, it appears that gas phase TMA present in ambient air partitions onto pre-existing particles preferentially during periods of acidic cloud/fog processing, leading to the presence of TMA-containing particles in the 0.52-1.9 μm size range.

Three differing techniques were used to measure ambient black carbon (BC) aerosols in downtown Toronto through 20 December 2006 to 23 January 2007. These techniques were thermal analysis, as performed by a Sunset Labs OCEC Analyzer (OCEC); light attenuation, as performed by an Aethalometer (AE); and photoacoustic analysis, as performed by a Photoacoustic Instrument (PA). These measurements of ambient PM 2.5 were used to investigate the effects of coating thickness on BC Mass Absorption Cross-section (MAC). MAC values were determined by comparing 880 nm and 370 nm AE measurements and PA measurements of b abs (absorption coefficient, Mm -1 ) to the OCEC measurements. Based on mass size distributions and supporting criteria, the PM 2.5 was classified as fresh, semi-aged, or aged. The average MAC values in these categories, based on the PA measurements, were 9.3 ± 1.8, 9.9 ± 2.0, and 9.3 ± 2.2 m 2 /g (mean ± standard deviation), respectively, suggesting that any difference in coating thickness as a result of aging, on the time scale observed, did not produce a difference in MAC. In a second type of experiment, a thermodenuder was installed upstream of the AE, PA, and OCEC and samples were heated to 340 • C in order to evaporate volatile and semi-volatile components within the coating. Based on the PA measurements, the average MAC values of these heated samples, for the fresh, semi-aged, and aged categories were 7.7 ± 2.2, 6.9 ± 2.2, and 9.1 ± 2.0 m 2 /g, respectively. Similar differences in MAC were also observed by the AE. The decrease in MAC in the fresh and semi-aged samples was interpreted in terms of the degree of coating of the PM 2.5 . Results agreed well with predictions made by absorption amplification theory and had ramifications for calibration of filter-base attenuation and photoacoustic instruments.

Single-particle mixing state information can be a powerful tool for assessing the relative impact of local and regional sources of ambient particulate matter in urban environments. However, quantitative mixing state data are challenging to obtain using single-particle mass spectrometers. In this study, the quantitative chemical composition of carbonaceous single particles has been determined using an aerosol time-of-flight mass spectrometer (ATOFMS) as part of the MEGAPOLI 2010 winter campaign in Paris, France. Relative peak areas of marker ions for elemental carbon (EC), organic aerosol (OA), ammonium, nitrate, sulfate and potassium were compared with concurrent measurements from an Aerodyne high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS), a thermal-optical OCEC analyser and a particle into liquid sampler coupled with ion chromatography (PILS-IC). ATOFMS-derived estimated mass concentrations reproduced the variability of these species well (R-2 = 0.67-0.78), and 10 discrete mixing states for carbonaceous particles were identified and quantified. The chemical mixing state of HR-ToF-AMS organic aerosol factors, resolved using positive matrix factorisation, was also investigated through comparison with the ATOFMS dataset. The results indicate that hydrocarbon-like OA (HOA) detected in Paris is associated with two EC-rich mixing states which differ in their relative sulfate content, while fresh biomass burning OA (BBOA) is associated with two mixing states which differ significantly in their OA/EC ratios. Aged biomass burning OA (OOA(2)-BBOA) was found to be significantly internally mixed with nitrate, while secondary, oxidised OA (OOA) was associated with five particle mixing states, each exhibiting different relative secondary inorganic ion content. Externally mixed secondary organic aerosol was not observed. These findings demonstrate the range of primary and secondary organic aerosol mixing states in Paris. Examination of the temporal behaviour and chemical composition of the ATOFMS classes also enabled estimation of the relative contribution of transported emissions of each chemical species and total particle mass in the size range investigated. Only 22% of the total ATOFMS-derived particle mass was apportioned to fresh, local emissions, with 78% apportioned to regional/continental-scale emissions. Single-particle mixing state information can be a powerful tool for assessing the relative impact of local and regional sources of ambient particulate matter in urban environments. However, quantitative mixing state data are challenging to obtain using single-particle mass spectrometers. In this study, the quantitative chemical composition of carbonaceous single particles has been determined using an aerosol time-of-flight mass spectrometer (ATOFMS) as part of the MEGAPOLI 2010 winter campaign in Paris, France. Relative peak areas of marker ions for elemental carbon (EC), organic aerosol (OA), ammonium, nitrate, sulfate and potassium were compared with concurrent measurements from an Aerodyne hi...