Oxygenated and Nitrated Polycyclic Aromatic Hydrocarbons in Ambient Air-Levels, Phase Partitioning, Mass Size Distributions, and Inhalation Bioaccessibility.

Among the nitrated and oxygenated polycyclic aromatic hydrocarbons (NPAHs and OPAHs) are some of the most hazardous substances to public health, mainly because of their carcinogenicity and oxidative potential. Despite these concerns, the concentrations and fate of NPAHs and OPAHs in the atmospheric environment are largely unknown. Ambient air concentrations of 18 NPAHs, 5 quinones, and 5 other OPAHs were determined at two urban and one regional background sites in central Europe. At one of the urban sites, the total (gas and particulate) concentrations of Σ10OPAHs were 10.0 ± 9.2 ng/m3 in winter and 3.5 ± 1.6 ng/m3 in summer. The gradient to the regional background site exceeded 1 order of magnitude. Σ18NPAH concentrations were typically 1 order of magnitude lower than OPAHs. Among OPAHs, 9-fluorenone and (9,10)-anthraquinone were the most abundant species, accompanied by benzanthrone in winter. (9,10)-Anthraquinone represented two-thirds of quinones. We found that a large fraction of the target substance particulate mass was carried by submicrometer particles. The derived inhalation bioaccessibility in the PM10 size fraction is found to be ≈5% of the total ambient concentration of OPAHs and up to ≈2% for NPAHs. For 9-fluorenone and (9,10)-anthraquinone, up to 86 and 18%, respectively, were found at the rural site. Our results indicate that water solubility could function as a limiting factor for bioaccessibility of inhaled particulate NPAHs and OPAHs, without considerable effect of surfactant lipids and proteins in the lung lining fluid.

Source Impact Determination using Airborne and Ground Measurements of Industrial Plumes.

Industrial particulate matter (PM) air pollution exposing nearby residential areas forms several European air pollution hot-spots. One of these hot-spot is the residential district of Ostrava Radvanice-Bartovice with frequent exceedances for PM and benzo[a]pyrene B[a]P, a carcinogenic polycyclic aromatic hydrocarbon (PAH) of MW > 228 amu. Such PAHs are highly bonded to the ultrafine particles (UFPs), the smallest PM size fraction, which deposits most efficiently in the alveolar region of human lungs. Airborne measurements identified UFP point sources in the adjacent metallurgical complex and mapped limited horizontal and vertical dispersion of industrial plumes enriched with UFPs (3.2 × 10(5)cm(-3)). The plumes, episodes of simultaneous peaks of UFPs (1.4 × 10(5)cm(-3)), SO2 (88.2 ppb), and CO (11.3 ppm), were recorded on the ground downwind in the residential district when wind speeds >1 ms(-1). In the plumes, UFPs were mostly 19-44 nm in diameter, enriched with PAHs/B[a]P up to 43.8/3.5 mg·g(-1). Electron microscopy showed that these plume UFPs were mostly agglomerates of spherules of 30-50 nm in diameter. These source impact measurements, that combine airborne and ground-level measurements, are applicable to clearly identify specific industrial air pollution sources and provide information to assess their possible impact to human health in similar hot-spots worldwide.

Nitrated monoaromatic hydrocarbons (nitrophenols, nitrocatechols, nitrosalicylic acids) in ambient air: levels, mass size distributions and inhalation bioaccessibility.

Nitrated monoaromatic hydrocarbons (NMAHs) are ubiquitous in the environment and an important part of atmospheric humic-like substances (HULIS) and brown carbon. They are ecotoxic and with underresearched toxic potential for humans. NMAHs were determined in size-segregated ambient particulate matter collected at two urban sites in central Europe, Ostrava and Kladno, Czech Republic. The average sums of 12 NMAHs (Σ12NMAH) measured in winter PM10 samples from Ostrava and Kladno were 102 and 93 ng m-3, respectively, and 8.8 ng m-3 in summer PM10 samples from Ostrava. The concentrations in winter corresponded to 6.3-7.3% and 2.6-3.1% of HULIS-C and water-soluble organic carbon (WSOC), respectively. Nitrocatechols represented 67-93%, 61-73% and 28-96% of NMAHs in PM10 samples collected in winter and summer at Ostrava and in winter at Kladno, respectively. The mass size distribution of the targeted substance classes peaked in the submicrometre size fractions (PM1), often in the PM0.5 size fraction especially in summer. The bioaccessible fraction of NMAHs was determined by leaching PM3 samples in two simulated lung fluids, Gamble's solution and artificial lysosomal fluid (ALF). More than half of NMAH mass is found bioaccessible, almost complete for nitrosalicylic acids. The bioaccessible fraction was generally higher when using ALF (mimics the chemical environment created by macrophage activity, pH 4.5) than Gamble's solution (pH 7.4). Bioaccessibility may be negligible for lipophilic substances (i.e. log KOW > 4.5).

Spatial-temporal variability of aerosol sources based on chemical composition and particle number size distributions in an urban settlement influenced by metallurgical industry.

The Moravian-Silesian region of the Czech Republic with its capital city Ostrava is a European air pollution hot spot for airborne particulate matter (PM). Therefore, the spatiotemporal variability assessment of source contributions to aerosol particles is essential for the successful abatement strategies implementation. Positive Matrix Factorization (PMF) was applied to highly-time resolved PM0.15-1.15 chemical composition (1 h resolution) and particle number size distribution (PNSD, 14 nm - 10 µm) data measured at the suburban (Ostrava-Plesná) and urban (Ostrava-Radvanice) residential receptor sites in parallel during an intensive winter campaign. Diel patterns, meteorological variables, inorganic and organic markers, and associations between the chemical composition factors and PNSD factors were used to identify the pollution sources and their origins (local, urban agglomeration and regional). The source apportionment analysis resolved six and four PM0.15-1.15 sources in Plesná and Radvanice, respectively. In Plesná, local residential combustion sources (coal and biomass combustion) followed by regional combustion sources (residential heating, metallurgical industry) were the main contributors to PM0.15-1.15. In Radvanice, local residential combustion and the metallurgical industry were the most important PM0.15-1.15 sources. Aitken and accumulation mode particles emitted by local residential combustion sources along with common urban sources (residential heating, industry and traffic) were the main contributors to the particle number concentration (PNC) in Plesná. Additionally, accumulation mode particles from local residential combustion sources and regional pollution dominated the particle volume concentration (PVC). In Radvanice, local industrial sources were the major contributors to PNC and local coal combustion was the main contributor to PVC. The source apportionment results from the complementary datasets elucidated the relevance of highly time-resolved parallel measurements at both receptor sites given the specific meteorological conditions produced by the regional orography. These results are in agreement with our previous studies conducted at this site. Graphical abstract.

Source apportionment of aerosol particles at a European air pollution hot spot using particle number size distributions and chemical composition.

Ostrava in the Moravian-Silesian region (Czech Republic) is a European air pollution hot spot for airborne particulate matter (PM), polycyclic aromatic hydrocarbons (PAHs), and ultrafine particles (UFPs). Air pollution source apportionment is essential for implementation of successful abatement strategies. UFPs or nanoparticles of diameter <100 nm exhibit the highest deposition efficiency in human lungs. To permit apportionment of PM sources at the hot-spot including nanoparticles, Positive Matrix Factorization (PMF) was applied to highly time resolved particle number size distributions (NSD, 14 nm-10 µm) and PM0.09-1.15 chemical composition. Diurnal patterns, meteorological variables, gaseous pollutants, organic markers, and associations between the NSD factors and chemical composition factors were used to identify the pollution sources. The PMF on the NSD reveals two factors in the ultrafine size range: industrial UFPs (28%, number mode diameter - NMD 45 nm), industrial/fresh road traffic nanoparticles (26%, NMD 26 nm); three factors in the accumulation size range: urban background (24%, NMD 93 nm), coal burning (14%, volume mode diameter - VMD 0.5 µm), regional pollution (3%, VMD 0.8 µm) and one factor in the coarse size range: industrial coarse particles/road dust (2%, VMD 5 µm). The PMF analysis of PM0.09-1.15 revealed four factors: SIA/CC/BB (52%), road dust (18%), sinter/steel (16%), iron production (16%). The factors in the ultrafine size range resolved with NSD have a positive correlation with sinter/steel production and iron production factors resolved with chemical composition. Coal combustion factor resolved with NSD has moderate correlation with SIA/CC/BB factor. The organic markers homohopanes correlate with coal combustion and the levoglucosan correlates with urban background. The PMF applications to NSD and chemical composition datasets are complementary. PAHs in PM1 were found to be associated with coal combustion factor.