Twenty-five biogenic and anthropogenic secondary organic aerosol (SOA) markers have been measured over a one-year period in both gaseous and PM10 phases in the Paris region (France). Seasonal and chemical patterns were similar to those previously observed in Europe, but significantly different from the ones observed in America and Asia due to dissimilarities in source precursor emissions. Nitroaromatic compounds showed higher concentrations in winter due to larger emissions of their precursors originating from biomass combustion used for residential heating purposes. Among the biogenic markers, only isoprene SOA marker concentrations increased in summer while pinene SOA markers did not display any clear seasonal trend. The measured SOA markers, usually considered as semi-volatiles, were mainly associated to the particulate phase, except for the nitrophenols and nitroguaiacols, and their gas/particle partitioning (GPP) showed a low temperature and OM concentrations dependency. An evaluation of their GPP with thermodynamic model predictions suggested that apart from equilibrium partitioning between organic phase and air, the GPP of the markers is affected by processes suppressing volatility from a mixed organic and inorganic phase, such as enhanced dissolution in aerosol aqueous phase and non-equilibrium conditions. SOA marker concentrations were used to apportion secondary organic carbon (SOC) sources applying both, an improved version of the SOA-tracer method and positive matrix factorization (PMF) Total SOC estimations agreed very well between both models, except in summer and during a highly processed Springtime PM pollution event in which systematic underestimation by the SOA tracer method was evidenced. As a first approach, the SOA-tracer method could provide a reliable estimation of the average SOC concentrations, but it is limited due to the lack of markers for aged SOA together with missing SOA/SOC conversion fractions for several sources.

• Klíčová slova
• Aerosol, Gas/particle partitioning, PMF, SOA, Source apportionment, Tracers,
• Publikační typ
• časopisecké články MeSH

21 PAHs, 27 oxy-PAHs and 32 nitro-PAHs were measured every third day over a year in both gaseous (G) and particulate PM10 (P) phases in ambient air of Grenoble (France). Mean total concentrations (G+P) of PAHs and oxy-PAHs were in the same range and about 10ngm(-3). Nitro-PAHs were 50 to 100 times less concentrated averaging 100pgm(-3). Polycyclic aromatic compound (PAC) concentrations were 5 to 7 times higher in "cold" period (October to March) than in "warm" period (April to September). Seasonal variations may be explained by higher primary emissions from residential heating, especially biomass burning in "cold" season. Meteorological conditions and influence of the geomorphology around Grenoble, with the formation of thermal inversion layers leading to the stagnation of pollutants, were additional key parameters. Maximum individual PAC concentrations were observed during two PM10 pollution events in December and February-March. Chemical processes and secondary formation of oxy- and nitro-PAH were probably enhanced by the accumulation of the pollutants during these events. PAC gas/particle partitioning depended on compound molecular weight and vapour pressure. Gas/particle partitioning of oxy- and nitro-PAHs were evaluated using a multi-phase poly-parameter linear free energy relationship model. The PAC cancer risk was assessed using toxic equivalency factors available in the literature (19 PAHs, 10 nitro-PAHs and 1 oxy-PAH). Overall, particle-bound PACs contributed about 76% of the cancer risk. While PAHs accounted for most of the total PAC cancer risk, oxy- and nitro-PAHs could account for up to 24%. The risk quantification across substance classes is limited by toxicological data availability.

• Klíčová slova
• Aerosol, Air quality, Gas/particle partitioning model, NPAH, OPAH, PAH,
• MeSH
• látky znečišťující vzduch analýza   MeSH
• monitorování životního prostředí MeSH
• nádory epidemiologie   MeSH
• pevné částice analýza   MeSH
• plyny analýza   MeSH
• polycyklické aromatické uhlovodíky analýza   MeSH
• riziko MeSH
• roční období MeSH
• velkoměsta MeSH
• Publikační typ
• časopisecké články MeSH
• Geografické názvy
• Francie epidemiologie   MeSH
• velkoměsta MeSH
• Názvy látek
• látky znečišťující vzduch MeSH
• pevné částice MeSH
• plyny MeSH
• polycyklické aromatické uhlovodíky MeSH

A model for gas-particle partitioning of polycyclic aromatic hydrocarbons (PAHs) was evaluated using polyparameter linear free energy relationships (ppLFERs) following a multiphase aerosol scenario. The model differentiates between various organic (i.e., liquid water-soluble (WS)/organic soluble (OS) organic matter (OM), and solid/semisolid organic polymers) and inorganic phases of the particulate matter (PM). Dimethyl sulfoxide and polyurethane were assigned as surrogates to simulate absorption into the above-mentioned organic phases, respectively, whereas soot, ammonium sulfate, and ammonium chloride simulated adsorption processes onto PM. The model was tested for gas and PM samples collected from urban and nonurban sites in Europe and the Mediterranean, and the output was compared with those calculated using single-parameter linear free energy relationship (spLFER) models, namely Junge-Pankow, Finizio, and Dachs-Eisenreich. The ppLFER model on average predicted 96 ± 3% of the observed partitioning constants for semivolatile PAHs, fluoranthene, and pyrene, within 1 order of magnitude accuracy with root-mean-square errors (RMSE) of 0.35-0.59 across the sites. This was a substantial improvement compared to Finizio and Dachs-Eisenreich models (37 ± 17 and 46 ± 18% and RMSE of 1.03-1.40 and 0.94-1.36, respectively). The Junge-Pankow model performed better among spLFERs but at the same time showed an overall tendency for overestimating the partitioning constants. The ppLFER model demonstrated the best overall performance without indicating a substantial intersite variability. The ppLFER analysis with the parametrization applied in this study suggests that the absorption into WSOSOM could dominate the overall partitioning process, while adsorption onto salts could be neglected.

• MeSH
• látky znečišťující vzduch * MeSH
• monitorování životního prostředí MeSH
• pevné částice MeSH
• plyny MeSH
• polycyklické aromatické uhlovodíky * MeSH
• Publikační typ
• časopisecké články MeSH
• práce podpořená grantem MeSH
• Názvy látek
• látky znečišťující vzduch * MeSH
• pevné částice MeSH
• plyny MeSH
• polycyklické aromatické uhlovodíky * MeSH

Derivatives of polycyclic aromatic hydrocarbons (PAHs) such as nitrated- and oxygenated-PAHs (NPAHs and OPAHs) could be even more toxic and harmful for the environment and humans than PAHs. We assessed the spatial and seasonal variations of NPAHs and OPAHs atmospheric levels, their cancer risks and their gas-to-particle partitioning. To this end, about 250 samples of fine particulate matter (PM2.5) and 50 gaseous samples were collected in 2017 in central Europe in the cities of Brno and Ljubljana (two traffic and two urban background sites) as well as one rural site. The average particulate concentrations were ranging from below limit of quantification to 593 pg m-3 for Σ9NPAHs and from 1.64 to 4330 pg m-3 for Σ11OPAHs, with significantly higher concentrations in winter compared to summer. In winter, the particulate levels of NPAHs and OPAHs were higher at the traffic site compared to the urban background site in Brno while the opposite was found in Ljubljana. NPAHs and OPAHs particulate levels were influenced by the meteorological parameters and co-varied with several air pollutants. The significance of secondary formation on the occurrence of some NPAHs and OPAHs is indicated. In winter, 27-47% of samples collected at all sites were above the acceptable lifetime carcinogenic risk. The gas-particle partitioning of NPAHs and OPAHs was influenced by their physico-chemical properties, the season and the site-specific aerosol composition. Three NPAHs and five OPAHs had higher particulate mass fractions at the traffic site, suggesting they could be primarily emitted as particles from vehicle traffic and subsequently partitioning to the gas phase along air transport. This study underlines the importance of inclusion of the gas phase in addition to the particulate phase when assessing the atmospheric fate of polycyclic aromatic compounds and also when assessing the related health risk.

• Klíčová slova
• Atmosphere, Cancer risk, Fine particles, Polycyclic aromatic hydrocarbons, Spatial variations,
• MeSH
• látky znečišťující vzduch * analýza   MeSH
• lidé MeSH
• monitorování životního prostředí MeSH
• nádory * epidemiologie   MeSH
• pevné částice analýza   MeSH
• polycyklické aromatické uhlovodíky * analýza   MeSH
• roční období MeSH
• velkoměsta MeSH
• Check Tag
• lidé MeSH
• Publikační typ
• časopisecké články MeSH
• Geografické názvy
• velkoměsta MeSH
• Názvy látek
• látky znečišťující vzduch * MeSH
• pevné částice MeSH
• polycyklické aromatické uhlovodíky * MeSH

The occurrence and atmospheric behavior of tri- to deca-polybrominated diphenyl ethers (PBDEs) were investigated during a 2-week campaign concurrently conducted in July 2012 at four background sites around the Aegean Sea. The study focused on the gas/particle (G/P) partitioning at three sites (Ag. Paraskevi/central Greece/suburban, Finokalia/southern Greece/remote coastal, and Urla/Turkey/rural coastal) and on the size distribution at two sites (Neochorouda/northern Greece/rural inland and Finokalia/southern Greece/remote coastal). The lowest mean total (G + P) concentrations of ∑7PBDE (BDE-28, BDE-47, BDE-66, BDE-99, BDE-100, BDE-153, BDE-154) and BDE-209 (0.81 and 0.95 pg m-3, respectively) were found at the remote site Finokalia. Partitioning coefficients, K P, were calculated, and their linear relationships with ambient temperature and the physicochemical properties of the analyzed PBDE congeners, i.e., the subcooled liquid pressure (P L°) and the octanol-air partition coefficient (K OA), were investigated. The equilibrium adsorption (P L°-based) and absorption (K OA-based) models, as well as a steady-state absorption model including an equilibrium and a non-equilibrium term, both being functions of log K OA, were used to predict the fraction Φ of PBDEs associated with the particle phase. The steady-state model proved to be superior to predict G/P partitioning of BDE-209. The distribution of particle-bound PBDEs across size fractions < 0.95, 0.95-1.5, 1.5-3.0, 3.0-7.2, and > 7.2 μm indicated a positive correlation between the mass median aerodynamic diameter and log P L° for the less brominated congeners, whereas a negative correlation was observed for the high brominated congeners. The potential source regions of PBDEs were acknowledged as a combination of long-range transport with short-distance sources.

• Klíčová slova
• Absorption/adsorption models, Aerosol mass size distribution, Gas/particle partitioning, Long-range transport,
• MeSH
• adsorpce MeSH
• halogenované difenylethery analýza   MeSH
• látky znečišťující vzduch analýza   MeSH
• monitorování životního prostředí * MeSH
• Publikační typ
• časopisecké články MeSH
• Geografické názvy
• Řecko MeSH
• Názvy látek
• halogenované difenylethery MeSH
• látky znečišťující vzduch MeSH

Gas-particle partitioning is one of the key factors that affect the environmental fate of semivolatile organic chemicals. Many organophosphate esters (OPEs) have been reported to primarily partition to particles in the atmosphere. However, because of the wide range of their physicochemical properties, it is unlikely that OPEs are mainly in the particle phase "as a class". We compared gas-particle partitioning predictions for 32 OPEs made by the commonly used OECD POV and LRTP Screening Tool ("the Tool") with the partitioning models of Junge-Pankow (J-P) and Harner-Bidleman (H-B), as well as recently measured data on OPE gas-particle partitioning. The results indicate that half of the tested OPEs partition into the gas phase. Partitioning into the gas phase seems to be determined by an octanol-air partition coefficient (log KOA) < 10 and a subcooled liquid vapor pressure (log PL) > -5 (PL in Pa), as well as the total suspended particle concentration (TSP) in the sampling area. The uncertainty of the physicochemical property data of the OPEs did not change this estimate. Furthermore, the predictions by the Tool, J-P- and H-B-models agreed with recently measured OPE gas-particle partitioning.

• MeSH
• atmosféra chemie   MeSH
• estery * MeSH
• látky znečišťující vzduch * MeSH
• organofosfáty MeSH
• teoretické modely MeSH
• Publikační typ
• časopisecké články MeSH
• práce podpořená grantem MeSH
• Názvy látek
• estery * MeSH
• látky znečišťující vzduch * MeSH
• organofosfáty MeSH

Polycyclic aromatic hydrocarbons (PAHs) were monitored at 20 sites in semi-rural, urban, and industrial areas of Ulsan, the largest industrial city in South Korea, for one year. The target compounds were the 16 priority PAHs designated by the US Environmental Protection Agency except for naphthalene, acenaphthene, and acenaphthylene. Gaseous PAHs collected using polyurethane foam-based passive air samplers (PUF-PASs) and particulate PAHs predicted using gas/particle partitioning models were used to estimate the human health risks. The mean total cancer risk through inhalation intake and dermal absorption for all target age groups (children, adolescents, adults, and lifetime) ranged from 0.10 × 10-7 to 2.62 × 10-7, lower than the acceptable risk level (10-6), thus representing a safe level for residents. The cancer risk through dermal absorption and inhalation intake was predicted to be highest in winter, mostly due to the higher concentrations of PAHs, especially high-molecular-weight species with greater toxicity. Additionally, gaseous and particulate PAHs contributed more to dermal absorption and inhalation intake, respectively. As a consequence of local emissions and advection, the risks were higher in the industrial and semi-rural areas. This study suggests that human health risks can be cost-effectively mapped on a local scale using passive air sampling.

• Klíčová slova
• PAHs, PAS, Risk assessment, Ulsan, gas/particle partitioning model,
• Publikační typ
• časopisecké články MeSH
• práce podpořená grantem MeSH

A total of 74 high volume air samples were collected at a background site in Czech Republic from 2012 to 2014 in which the concentrations of 20 per- and polyfluoroalkyl substances (PFASs) were investigated. The total concentrations (gas + particle phase) ranged from 0.03 to 2.08 pg m-3 (average 0.52 pg m-3) for the sum of perfluoroalkyl carboxylic acids (∑PFCAs), from 0.02 to 0.85 pg m-3 (average 0.28 pg m-3) for the sum of perfluoroalkyl sulfonates (ΣPFSAs) and from below detection to 0.18 pg m-3 (average 0.05 pg m-3) for the sum of perfluorooctane sulfonamides and sulfonamidoethanols (ΣFOSA/Es). The gas phase concentrations of most PFASs were not controlled by temperature dependent sources but rather by long-range atmospheric transport. Air mass backward trajectory analysis showed that the highest concentrations of PFASs were mainly originating from continental areas. The average particle fractions (θ) of ΣPFCAs (θ = 0.74 ± 0.26) and ΣPFSAs (θ = 0.78 ± 0.22) were higher compared to ΣFOSA/Es (θ = 0.31 ± 0.35). However, they may be subject to sampling artefacts. This is the first study ever reporting PFASs concentrations in air samples collected over consecutive years. Significant decreases in 2012-2014 for PFOA, MeFOSE, EtFOSE and ∑PFCAs were observed with apparent half-lives of 1.01, 0.86, 0.92 and 1.94 years, respectively.

• Klíčová slova
• Gas-particle partitioning, Long-range atmospheric transport, Multi-year variations, Per- and polyfluoroalkyl substances, Seasonal variations,
• MeSH
• fluorokarbony analýza   MeSH
• kyseliny karboxylové MeSH
• monitorování životního prostředí MeSH
• Publikační typ
• časopisecké články MeSH
• Geografické názvy
• Česká republika MeSH
• Evropa MeSH
• Názvy látek
• fluorokarbony MeSH
• kyseliny karboxylové MeSH

Nitrated and oxygenated polycyclic aromatic hydrocarbons (NPAHs, OPAHs) are abundant in the atmosphere and contribute significantly to the health risk associated with inhalation of polluted air. Despite the health hazard they pose, NPAHs and OPAHs were rarely included in monitoring. The aim of this study is to provide the first multi-year temporal trends of the concentrations, composition pattern and fate of NPAHs and OPAHs in air from a site representative of background air quality conditions in central Europe. Samples were collected every second week at a rural background site in the Czech Republic during 2015-2017. Concentrations ranged from 1.3 to 160 pg m-3 for Σ17NPAHs, from 32 to 2600 pg m-3 for Σ10OPAHs and from 5.1 to 4300 pg m-3 for Σ2O-heterocycles. The average particulate mass fraction (θ) ranged from 0.01 ± 0.02 (2-nitronaphthalene) to 0.83 ± 0.22 (1-nitropyrene) for individual NPAHs and from <0.01 ± 0.01 (dibenzofuran) to 0.96 ± 0.08 (6H-benzo (c,d)pyren-6-one) for individual OPAHs and O-heterocycles. The multiyear variations showed downward trends for a number of targeted compounds. This suggests that on-going emission reductions of PAHs are effective also for co-emitted NPAHs and OPAHs.

• Klíčová slova
• Continental background, Gas-particle partitioning, NPAHs, Nitrobenzanthron, OPAHs, Polycyclic aromatic compounds,
• MeSH
• dusičnany MeSH
• kyslík analýza   MeSH
• látky znečišťující vzduch * analýza   MeSH
• lidé MeSH
• monitorování životního prostředí MeSH
• pevné částice analýza   MeSH
• polycyklické aromatické uhlovodíky * analýza   MeSH
• Check Tag
• lidé MeSH
• Publikační typ
• časopisecké články MeSH
• Geografické názvy
• Česká republika MeSH
• Evropa MeSH
• Názvy látek
• dusičnany MeSH
• kyslík MeSH
• látky znečišťující vzduch * MeSH
• pevné částice MeSH
• polycyklické aromatické uhlovodíky * MeSH

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.

• MeSH
• dusičnany MeSH
• látky znečišťující vzduch * MeSH
• lidé MeSH
• monitorování životního prostředí MeSH
• pevné částice MeSH
• polycyklické aromatické uhlovodíky * MeSH
• Check Tag
• lidé MeSH
• Publikační typ
• časopisecké články MeSH
• práce podpořená grantem MeSH
• Geografické názvy
• Evropa MeSH
• Názvy látek
• dusičnany MeSH
• látky znečišťující vzduch * MeSH
• pevné částice MeSH
• polycyklické aromatické uhlovodíky * MeSH