Particle size distribution of halogenated flame retardants and implications for atmospheric deposition and transport.

This study investigates the distribution of polybrominated diphenyl ethers (PBDEs), hexabromocyclododecane (HBCD) and a group of novel flame retardants (NFRs) on atmospheric aerosols. Two high volume cascade impactors were used to collect particulate fractions of ambient air over a one year period at urban and rural sites. The majority of FRs were found on the finest aerosols (<0.95 µm). Concentrations of HBCD were higher than those of ΣPBDEs. Moreover, we noted seasonality and spatial differences in particle size distributions, yet a large portion of the observed differences were due to differences in particulate matter (PM) itself. When normalized by PM, the size distributions of the FRs exhibited much greater heterogeneity. Differences existed between the FR distributions by molecular weight, with the higher molecular weight FRs (e.g., BDE-209, Dechlorane Plus) distributed more uniformly across all particulate size fractions. The seasonal, spatial, and compound-specific differences are of crucial importance when estimating dry and wet deposition of FRs as smaller aerosols have longer atmospheric residence times. Estimated wet and dry deposition of four representative FRs (BDE-47, BDE-209, HBCD, and Dechlorane Plus) using size-segregated aerosol data resulted in lower deposition estimates than when bulk aerosol data were used. This has implications for estimates of long-range atmospheric transport and atmospheric residence times, as it suggests that without size-specific distributions, these parameters could be underestimated for FRs.

Composition and effects of inhalable size fractions of atmospheric aerosols in the polluted atmosphere: part I. PAHs, PCBs and OCPs and the matrix chemical composition.

Atmospheric particulate matter (PM) abundance, mass size distribution (MSD) and chemical composition are parameters relevant for human health effects. The MSD and phase state of semivolatile organic pollutants were determined at various polluted sites in addition to the PM composition and MSD. The distribution pattern of pollutants varied from side to side in correspondence to main particle sources and PM composition. Levels of particle-associated polycyclic aromatic hydrocarbons (PAHs) were 1-30 ng m(-3) (corresponding to 15-35 % of the total, i.e., gas and particulate phase concentrations), of polychlorinated biphenyls (PCBs) were 2-11 pg m(-3) (4-26 % of the total) and of DDT compounds were 2-12 pg m(-3) (4-23 % of the total). The PM associated amounts of other organochlorine pesticides were too low for quantification. The organics were preferentially found associated with particles <0.45 µm of aerodynamic equivalent diameter. The mass fractions associated with sub-micrometer particles (PM0.95) were 73-90 %, 34-71 % and 36-81 % for PAHs, PCBs and DDT compounds, respectively. The finest particles fraction had the highest aerosol surface concentration (6.3-29.7)×10(-6) cm(-1) (44-70 % of the surface concentration of all size fractions). The data set was used to test gas-particle partitioning models for semivolatile organics for the first time in terms of the organics' MSD and size-dependent PM composition. The results of this study prove that at the various sites particles with diverse size, matrix composition, amount of contaminants and toxicological effects occur. Legislative regulation based on gravimetric determination of PM mass can clearly be insufficient for assessment.

Composition and effects of inhalable size fractions of atmospheric aerosols in the polluted atmosphere. Part II. In vitro biological potencies.

Exposure to particulate matter (PM) in ambient air has been shown to lead to adverse health consequences. Six size fractions of PM with aerodynamic diameter smaller than 10µm (PM10) and gas phase were collected at six localities with different major pollution sources. Extracts of samples were assessed for AhR-mediated toxicity, (anti-)estrogenicity, (anti-)androgenicity and genotoxicity. The biological responses were interpreted relative to chemical characterization. Historically, for regulatory purposes, evaluation of air pollution was based mainly on assessment of the sum of PM10. In the case of AhR-mediated activity, PM1 was responsible for more than 75% of the activity of the particulate fraction from all localities. The assessed effects were correlated with concentrations of polycyclic aromatic hydrocarbons (PAH), organic carbon content and specific surface area of the PM. A significant proportion of biologically active chemicals seems to be present in the gas phase of air. The results suggest that an average daily exposure based just on the concentrations of contaminants contained in PM10, as regulated in EU legislation so far, is not a sufficient indicator of contaminants in air particulates and adoption of standards more similar to other countries and inclusion of other parameters besides mass should be considered.

Mineralogical, chemical and toxicological characterization of urban air particles.

Systematic characterization of morphological, mineralogical, chemical and toxicological properties of various size fractions of the atmospheric particulate matter was a main focus of this study together with an assessment of the human health risks they pose. Even though near-ground atmospheric aerosols have been a subject of intensive research in recent years, data integrating chemical composition of particles and health risks are still scarce and the particle size aspect has not been properly addressed yet. Filling this gap, however, is necessary for reliable risk assessment. A high volume ambient air sampler equipped with a multi-stage cascade impactor was used for size specific particle collection, and all 6 fractions were a subject of detailed characterization of chemical (PAHs) and mineralogical composition of the particles, their mass size distribution and genotoxic potential of organic extracts. Finally, the risk level for inhalation exposure associated to the carcinogenic character of the studied PAHs has been assessed. The finest fraction (<0.45 µm) exhibited the highest mass, highest active surface, highest amount of associated PAHs and also highest direct and indirect genotoxic potentials in our model air sample. Risk assessment of inhalation scenario indicates the significant cancer risk values in PM 1.5 size fraction. This presented new approach proved to be a useful tool for human health risk assessment in the areas with significant levels of air dust concentration.