Application of ¹⁴C analyses to source apportionment of carbonaceous PM_2.5 in the UK

Determination of the radiocarbon (<sup>14</sup>C) content of airborne particulate matter yields insight into the proportion of the carbonaceous material derived from fossil and contemporary carbon sources. Daily samples of PM<sub>2.5</sub> were collected by high-volume sampler at an urban background site in Birmingham, UK, and the fraction of <sup>14</sup>C in both the total carbon, and in the organic and elemental carbon fractions, determined by two-stage combustion to CO<sub>2</sub>, graphitisation and quantification by accelerator mass spectrometry. OC and EC content was also determined by Sunset Analyzer. The mean fraction contemporary TC in the PM<sub>2.5</sub> samples was 0.50 (range 0.27–0.66, n = 26). There was no seasonality to the data, but there was a positive trend between fraction contemporary TC and magnitude of SOC/TC ratio and for the high values of these two parameters to be associated with air-mass back trajectories arriving in Birmingham from over land. Using a five-compartment mass balance model on fraction contemporary carbon in OC and EC, the following average source apportionment for the TC in these PM<sub>2.5</sub> samples was derived: 27% fossil EC; 20% fossil OC; 2% biomass EC; 10% biomass OC; and 41% biogenic OC. The latter category will comprise, in addition to BVOC-derived SOC, other non-combustion contemporary carbon sources such as biological particles, vegetative detritus, humic material and tyre wear. The proportion of total PM<sub>2.5</sub> at this location estimated to derive from BVOC-derived secondary organic aerosol was 9–29%. The findings from this work are consistent with those from elsewhere in Europe and support the conclusion of a significant and ubiquitous contribution from non-fossil biogenic sources to the carbon in terrestrial aerosol

Characterization of Polar Organic Components in Fine Aerosols in the Southeastern United States: Identity, Origin, and Evolution

Filter samples of fine aerosols collected in the Southeastern United States in June 2004 were analyzed for the characterization of polar organic components. Four analytical techniques, liquid chromatography –mass spectrometry, ion trap mass spectrometry, laser desorption ionization mass spectrometry, and high-resolution mass spectrometry, were used for identification and quantification. Forty distinct species were detected, comprising on average 7.2% and 1.1% of the total particulate organic mass at three inland sites and a coastal site, respectively. The relative abundance of these species displays a rather consistent distribution pattern in the inland region, whereas a different pattern is found at the coastal site. Chemical and correlation analyses suggest that the detected species are secondary in nature and originate from terpene oxidation, with possible participation of NOx and SO2. It is estimated that polar, acidic components in fine aerosols in the Southeastern United States cover a molecular weight range of 150–400 Da and do not appear to be oligomeric. Other components with MW up to 800 Da may also be present. The detected polar organic species are similar to humic-like substances (HULIS) commonly found in fine aerosols in other rural areas. We present the first, direct evidence that atmospheric processing of biogenic emissions can lead to the formation of certain HULIS species in fine aerosols, and that this may be a typical pathway in the background atmosphere in continental regions; nevertheless, a natural source for HULIS, such as from aquatic and/or terrestrial humic/fulvic acids and their degradation products, cannot be precluded

Regional variation of organic functional groups in aerosol particles on four U.S. east coast platforms during the International Consortium for Atmospheric Research on Transport and Transformation 2004 campaign

Submicron atmospheric aerosol samples were collected during the International Consortium for Atmospheric Research on Transport and Transformation (ICARTT) 2004 campaign on four platforms: Chebogue Point (Nova Scotia, Canada), Appledore Island (Maine), the CIRPAS Twin Otter over Ohio, and the NOAA R/V Ronald H. Brown in the Gulf of Maine. Saturated aliphatic C-C-H, unsaturated aliphatic C=C−H, aromatic C=C−H, organosulfur C-O-S, carbonyl C=O, and organic hydroxyl C-OH functional groups were measured by calibrated Fourier Transform Infrared (FTIR) spectroscopy at all four sampling platforms. The ratio of molar concentrations of carbonyl C=O to saturated aliphatic C-C-H groups was nearly constant at each sampling platform, with the Twin Otter samples having the lowest ratio at 0.1 and the three more coastal platforms having ratios of 0.4 and 0.5. Organic mass (OM) to organic carbon (OC) ratios follow similar trends for the four platforms, with the Twin Otter having the lowest ratio of 1.4 and the coastal platforms having slightly higher values typically between 1.5 and 1.6. Organosulfur compounds were occasionally observed. Collocated organic aerosol sampling with two Aerodyne aerosol mass spectrometers for OM, a Sunset Laboratory thermo-optical analysis instrument for OC, and an ion chromatography-particle into liquid sampler (IC-PILS) for speciated carboxylic acids provided comparable results for most of the project, tracking the time series of FTIR OM, OC, and carbonyl groups, respectively, and showing simultaneous peaks of similar magnitude during most of the project. The FTIR/IC-PILS comparison suggests that about 9% of the carbonyl groups found in submicron organic particles on the Twin Otter are typically associated with low molecular weight carboxylic acids

Characterization of atmospheric aerosols at Monte Cimone, Italy, during summer 2004: Source apportionment and transport mechanisms

Atmospheric aerosols in the PM10 and PM1 fractions have been sampled at the Global Atmospheric Watch station Mount Cimone, Italy (2165 m above mean sea level) for 3 months during summer 2004, and simultaneous size distributions have been derived by means of an optical particle counter. Samples have been analyzed by X-ray fluorescence, ion chromatography, and thermal-optical methodology in order to quantify their elemental, ionic, and carbonaceous constituents. The concentration of PM10 was 16.1 \ub1 9.8 mg m3 (average and standard deviation). Source apportionment allowed us to identify, quantify and characterize the following aerosol classes: anthropogenic pollution (10 mg m3), mineral dust (4 mg m3), and sea salt (0.2 mg m3). Pollution has been further split into ammonium sulfate (44%), organic matter (42%), and other compounds (14%). The nitrate/sulfate ratio in the polluted aerosol was 0.1. Fine particles have been completely related to the polluted aerosol component, and they represented 70% in weight of pollution. Coarse particles characterized the dust and salt components, and crustal oxides have been found to be the largest responsible for the aerosol concentration variations that occurred during the campaign. Nitrate has also been found in the coarse particles, representing 10% of mineral dust. The analysis of the transport mechanisms responsible for aerosol fluctuations permitted us to identify the origin of the major aerosol components: Pollution has been ascribed to regional transport driven by boundary layer meteorology, whereas mineral dust has been related to long-range transport events originating in the Sahara and Sahel. A particularly significant Saharan episode has been identified on 10 August 2004 (PM10 daily concentration, 69.9 mg m3). Average elemental ratios for the African dust events were as follows: Si/Al = 2.31, Fe/Ca = 0.94, Ca/Al = 0.90, K/Ca = 0.44, Ti/Ca = 0.11, and Ti/Fe = 0.12