Functional characterization of the water-soluble organic carbon of size-fractionated aerosol in the southern Mississippi Valley.

The chemical content of water-soluble organic carbon (WSOC) as a function of particle size was characterized in Little Rock, Arkansas in winter and spring 2013. The objectives of this study were to (i) compare the functional characteristics of coarse, fine and ultrafine WSOC and (ii) reconcile the sources of WSOC for periods when carbonaceous aerosol was the most abundant particulate component. The WSOC accounted for 5 % of particle mass for particles with δp > 0.96 µm and 10 % of particle mass for particles with δp < 0.96 µm. Non-exchangeable aliphatic (H-C), unsaturated aliphatic (H-C-C=), oxygenated saturated aliphatic (H-C-O), acetalic (O-CH-O) and aromatic (Ar-H) protons were determined by proton nuclear magnetic resonance (1H-NMR). The total non-exchangeable organic hydrogen concentrations varied from 4.1 ± 0.1 nmol m-3 for particles with 1.5 < δp < 3.0 µm to 73.9 ± 12.3 nmol m-3 for particles with δp < 0.49 µm. The molar H/C ratios varied from 0.48 ± 0.05 to 0.92 ± 0.09, which were comparable to those observed for combustion-related organic aerosol. The R-H was the most abundant group, representing about 45 % of measured total non-exchangeable organic hydrogen concentrations, followed by H-C-O (27 %) and H-C-C= (26 %). Levoglucosan, amines, ammonium and methanesulfonate were identified in NMR fingerprints of fine particles. Sucrose, fructose, glucose, formate and acetate were associated with coarse particles. These qualitative differences of 1H-NMR profiles for different particle sizes indicated the possible contribution of biological aerosols and a mixture of aliphatic and oxygenated compounds from biomass burning and traffic exhausts. The concurrent presence of ammonium and amines also suggested the presence of ammonium/aminium nitrate and sulfate secondary aerosol. The size-dependent origin of WSOC was further corroborated by the increasing δ13C abundance from -26.81 ± 0.18 ‰ for the smallest particles to -25.93 ± 0.31 ‰ for the largest particles and the relative distribution of the functional groups as compared to those previously observed for marine, biomass burning and secondary organic aerosol. The latter also allowed for the differentiation of urban combustion-related aerosol and biological particles. The five types of organic hydrogen accounted for the majority of WSOC for particles with δp > 3.0 µm and δp < 0.96 µm.

Soil humic-like organic compounds in prescribed fire emissions using nuclear magnetic resonance spectroscopy.

Here we present the chemical characterization of the water-soluble organic carbon fraction of atmospheric aerosol collected during a prescribed fire burn in relation to soil organic matter and biomass combustion. Using nuclear magnetic resonance spectroscopy, we observed that humic-like substances in fire emissions have been associated with soil organic matter rather than biomass. Using a chemical mass balance model, we estimated that soil organic matter may contribute up to 41% of organic hydrogen and up to 27% of water-soluble organic carbon in fire emissions. Dust particles, when mixed with fresh combustion emissions, substantially enhances the atmospheric oxidative capacity, particle formation and microphysical properties of clouds influencing the climatic responses of atmospheric aeroso. Owing to the large emissions of combustion aerosol during fires, the release of dust particles from soil surfaces that are subjected to intense heating and shear stress has, so far, been lacking.

Quantitative determination of regional contributions to fine and coarse particle mass in urban receptor sites.

In this study, we demonstrate that regression analysis of trajectories residence time estimates the contributions of geographical sectors to fine and coarse particle mass in urban receptor sites. We applied the methodology to coarse and fine particles in Amsterdam, Athens, Birmingham and Helsinki. The sectors with the highest contributions on PM2.5 and PM10-2.5 for Amsterdam and Birmingham were Central/Eastern Europe and the Atlantic Ocean/North Sea, respectively. For Athens, the four sectors within 500 km accounted for the largest fraction of PM2.5. The Mediterranean Sea and North Africa added more than half of PM10-2.5 in Athens. For Helsinki, more than 50% of PM2.5 and PM10-2.5 were from sources outside Finland. This approach may be applied to assess the impact of transport on particle mass levels, identify the spatial patterns of particle sources and generate valuable data to design national and transnational efficient emission control strategies.

Quantification of environmental tobacco smoke contribution on outdoor particulate aliphatic and polycyclic aromatic hydrocarbons.

The objective of this study was to identify and quantify the sources of fine particulate aliphatic and polycyclic aromatic hydrocarbons (PAHs) in an urban area in southeastern Europe. A total of 91 urban PM2.5 samples were analyzed by gas chromatography coupled with mass spectrometry for alkanes and PAHs. Exploratory statistical tools were applied to resolve a decreased number of components based on the variation of measurements. Molecular markers and diagnostic ratios were examined to assign retained components to specific sources. The contributions of the sources were estimated by multivariate linear regression. Sources of aliphatic and PAHs hydrocarbons included primary particles from traffic (3.9 ng/m(3) for alkanes and 240 pg/m(3) for PAHs), evaporative fugitive (4.0 ng/m(3) for alkanes and 93 pg/m(3) for PAHs), and unburnt fuels and oil residues (1.1 ng/m(3) for alkanes and 230 pg/m(3) for PAHs). For the first time, we quantified the contribution of environmental tobacco smoke (ETS), which accounted for 5.2 ng/m(3) of alkanes and 128 pg/m(3) of PAHs. The findings of this study underlined the persistence of ETS and possible exposures to significant quantities of tobacco residues outdoors. Tobacco smoke is known to induce adverse respiratory and cardiovascular illnesses and increased risk for cancer.

Ambient air pollution and respiratory health effects in mail carriers.

Mail carriers represent an occupational group suffering from respiratory symptoms and lung function impairment. Although environmental conditions may play role, information on the effects of air pollution exposure in this population is lacking. The present study was conducted in Athens, Greece, in order to investigate the adverse effects of long-term air pollution exposure on respiratory outcomes in mail carriers. A total of 226 mail carriers and 73 office employees were enrolled. Information on respiratory symptoms, medical, occupational, residential and smoking history was obtained through a questionnaire. Flow-volume curves were performed in the workplace using a portable spirometer. Individualised personal exposure assessment has been applied based on long-term residential and occupational subject history linked with geographical air pollution distribution. Furthermore, personal measurements were obtained for forty-one mail carriers using NO(2) and O(3) passive samplers, assuming that current air pollution exposure is sufficiently representative of long-term, previous exposure to make a plausible link with current health status. The analysis based on exposures estimated on the basis of residential and work addresses showed that the most exposed to PM(10) postal workers have rhinitis at a higher rate (OR=1.67, 95% CI: 1.01-2.75). In mail carriers there is indication that those exposed to higher concentrations of Omicron(3) or PM(10) have a greater possibility to present rhinitis (OR=1.63, 95% CI: 0.93-2.88 and OR=1.70, 95% CI: 0.96-3.03, respectively). The effect of O(3) on rhinitis became even more apparent in the analysis based on exposures assessed by personal measurements (OR=6.74, 95% CI: 1.24-36.55). Exposure to NO(2) was significantly associated with decrements in lung function. For office employees the exposure to air pollutants was not associated to any adverse respiratory outcome. Our findings suggest that air pollution is a contributing factor for the occurrence of rhinitis and lung function impairment in mail carriers.

Performance of a high-volume cascade impactor in six European urban environments: mass measurement and chemical characterization of size-segregated particulate samples.

The performance of a modified Harvard high-volume cascade impactor (HVCI) was evaluated in six field campaigns with size-segregated particulate samplings for chemical and toxicological characterization. The 7-week sampling campaigns in 2002-2003 in Duisburg (autumn), Prague (winter), Amsterdam (winter), Helsinki (spring), Barcelona (spring), and Athens (summer) were selected to represent contrasting urban environments and seasons of public health interest due to high particulate concentrations or previous findings in epidemiological studies. Particulate samples were collected in parallel with the HVCI (PM(10-2.5), PM(2.5-1), PM(1-0.2), PM(0.2)), a virtual impactor (VI; PM(10-2.5), PM(2.5)), and a Berner low-pressure impactor (BLPI; 10 stages between 0.035 and 10 mum in particle diameter) using a 3- or 4-day sampling duration. The campaigns exhibited different profiles with regard to particulate mass concentration, size distribution, chemical composition and meteorological conditions, thus providing a demanding setup for an overall field comparison of the HVCI with the VI and BLPI reference samplers. Size-segregated particulate mass concentration could be reasonably well measured with the present HVCI configuration. The coarse (PM(10-2.5)) and fine (PM(2.5)) particulate mass agreed within 10% with the low-volume reference samplers, and the four-stage size distribution of the HVCI followed the modal pattern of urban aerosol. The concentrations of chemical constituents measured and integrated especially for the HVCI-PM(2.5) differed to some extent from those measured from the corresponding VI-PM(2.5) samples. This implies that when investigating the association of toxicological responses with the chemical constituents of particulate matter, it is necessary to use the chemical composition data of the same samples as used in toxicological experiments.