Long-term exposure to polycyclic aromatic hydrocarbons (PAHs) and their nitrated (NPAHs) and oxygenated (OPAHs) derivatives can cause adverse health effects due to their carcinogenicity, mutagenicity and oxidative potential. The distribution of PAH derivatives in the terrestrial environment has hardly been studied, although several PAH derivatives are ubiquitous in air and long-lived in soil and water. We report the multi-annual variations in the concentrations of NPAHs, OPAHs and PAHs in soils sampled at a semi-urban (Mokrá, Czech Republic) and a regional background site (Košetice, Czech Republic) in central Europe. The concentrations of the Σ18NPAHs and the Σ11+2OPAHs and O-heterocycles were 0.31 ± 0.23 ng g-1 and 4.03 ± 3.03 ng g-1, respectively, in Košetice, while slightly higher concentrations of 0.54 ± 0.45 ng g-1 and 5.91 ± 0.45 ng g-1, respectively, were found in soil from Mokrá. Among the 5 NPAHs found in the soils, 1-nitropyrene and less so 6-nitrobenzo(a)pyrene were most abundant. The OPAHs were more evenly distributed. The ratios of the PAH derivatives to their parent PAHs in Košetice indicate that they were long-range transported to the background site. Our results show that several NPAHs and OPAHs are abundant in soil and that gas-particle partitioning is a major factor influencing the concentration of several semi-volatile NPAHs and OPAHs in the soils. Complete understanding of the long-term variations of NPAH and OPAH concentrations in soil is limited by the lack of kinetic data describing their formation and degradation.

• Klíčová slova
• Background, Nitrated PAHs, Polycyclic aromatic compounds, soil pollution, Soil exposure, Temporal variation,
• MeSH
• dusičnany MeSH
• látky znečišťující vzduch * analýza   MeSH
• monitorování životního prostředí metody   MeSH
• pastviny MeSH
• polycyklické aromatické uhlovodíky * analýza   MeSH
• půda MeSH
• Publikační typ
• časopisecké články MeSH
• Názvy látek
• dusičnany MeSH
• látky znečišťující vzduch * MeSH
• polycyklické aromatické uhlovodíky * MeSH
• půda 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

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

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

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

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

BACKGROUND: Air pollution, which represents a major environmental risk to human health, comprises a complex mixture of compounds where only little is known about its specific toxicities. OBJECTIVES: This study examined the specific toxicities associated with ambient air pollutant mixtures with respect to gas/particle partitioning, particulate matter (PM) size, pollutant polarity and bioaccessibility from PM, and evaluated the contribution of PAHs and their oxygenated and nitrated derivatives (OPAHs, NPAHs). METHODS: Air samples (gas phase, PM10 and size-segregated PM), were collected at urban (in winter and summer) and background (winter) sites in the Czech Republic. The total and bioaccessible concentrations were addressed using organic solvent extraction and simulated lung fluid extraction, respectively. Organic extracts were also further fractionated according to polarity. Aryl hydrocarbon receptor (AhR)-mediated activity, anti-/estrogenicity, anti-/androgenicity, thyroid receptor (TR)-mediated activity and cytotoxicity for bronchial cells were determined by human cell-based in vitro bioassays. The contribution of studied compounds to observed effects was assessed by both modelling and reconstructing the mixtures. RESULTS: Significant effects were detected in the sub-micrometre size fraction of PM (estrogenicity, androgenicity, TR- and AhR-mediated activities) and in the gas phase (TR-mediated activity, antiandrogenicity). Compounds interacting with TR showed high bioaccessibility to simulated lung fluid. Relatively lower bioaccessibility was observed for estrogenicity and AhR-mediated activity. However, the toxicity testing of reconstructed mixtures revealed that the targeted pollutants are not the main contributors, except for urban PM air pollution in winter, where they accounted for 5-88% of several effects detected in the original complex environmental samples. DISCUSSION: Studied toxicities were mostly driven by polar compounds largely attributed to the easily inhalable PM1, which is of high relevance for human health risk assessment. Except of parent PAHs in some cases, the targeted compounds contributed to the detected effects mostly to a relatively low extent implying huge data gaps in terms of endocrine disruptive potencies of targeted substances and the significance of other polar compounds present in ambient air.

• Klíčová slova
• Air pollutant mixture, Bioassay, Endocrine disruption, Human health, PAHs, OPAHs, NPAHs, Toxic potential,
• MeSH
• látky znečišťující vzduch * analýza   toxicita   MeSH
• látky znečišťující životní prostředí * MeSH
• lidé MeSH
• monitorování životního prostředí MeSH
• pevné částice analýza   toxicita   MeSH
• polycyklické aromatické uhlovodíky * analýza   toxicita   MeSH
• Check Tag
• lidé MeSH
• Publikační typ
• časopisecké články MeSH
• práce podpořená grantem MeSH
• Geografické názvy
• Česká republika MeSH
• Názvy látek
• látky znečišťující vzduch * MeSH
• látky znečišťující životní prostředí * 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

This study presents four years ambient monitoring data of seventeen 2,3,7,8-chlorine substituted polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/Fs), twelve dioxin-like polychlorinated biphenyls (dl-PCBs) and sixteen polycyclic aromatic hydrocarbons (PAHs) designed by the US EPA at a background site in central Europe during 2011-2014. The concentrations expressed as toxic equivalents (TEQs) using the WHO2005-scheme for PCDD/Fs (0.2 fg m-3-61.1 fg m-3) were higher than for dl-PCBs (0.01 fg m-3-2.9 fg m-3), while the opposite was found in terms of mass concentrations. ΣPAHs ranged from 0.20 ng m-3 to 134 ng m-3. The mass concentration profile of PCDD/Fs, dl-PCBs and PAHs was similar throughout the four years. PCDD/Fs and PAHs concentrations were dominated by primary sources peaking in winter, while those of dl-PCBs were controlled by secondary sources characterized by a spring-summer peak. During 2011-2014, no significant decrease in the atmospheric levels of ΣPCDD/Fs was observed. On the other hand, the concentrations of Σdl-PCBs and ΣPAHs were decreasing, with halving times of 5.7 and 2.7 years, respectively. We estimated that 422 pg m-2 year-1-567 pg m-2 year-1 TEQ PCDD/Fs and 3.48 pg m-2 year-1-15.8 pg m-2 year-1 TEQ dl-PCBs were transferred from the air to the ground surfaces via dry particulate deposition during 2011-2014.

• Klíčová slova
• Atmospheric deposition, Gas-particle partitioning, Multi-year variations, Persistent organic pollutants, Seasonal variations,
• MeSH
• látky znečišťující vzduch analýza   MeSH
• monitorování životního prostředí MeSH
• polychlorované bifenyly analýza   MeSH
• polychlorované dibenzodioxiny analýza   MeSH
• polychlorované dibenzofurany analýza   MeSH
• polycyklické aromatické uhlovodíky analýza   MeSH
• roční období MeSH
• Publikační typ
• časopisecké články MeSH
• Geografické názvy
• Česká republika MeSH
• Názvy látek
• látky znečišťující vzduch MeSH
• polychlorované bifenyly MeSH
• polychlorované dibenzodioxiny MeSH
• polychlorované dibenzofurany MeSH
• polycyklické aromatické uhlovodíky MeSH

Scientists and decision makers need accurate, accessible and fast tools to assess and prioritize the persistence (POV) and environmental long-range transport potential (LRTP) of chemicals. Here we evaluated the Organisation for Economic Co-operation and Development (OECD) POV and LRTP Screening Tool ("the Tool") with respect to the POV and LRTP estimates that the Tool provides for organophosphate esters (OPEs). We found that the use of default parameter values could significantly underestimate POV and LRTP values of OPEs and, potentially, other Persistent Mobile Organic Compounds (PMOCs), by not accounting for episodic atmospheric transport and poleward river-based transport in the northern hemisphere. Specifically, sensitivity and Monte Carlo uncertainty analyses indicate that non-chlorinated OPEs could be subject to LRTP when uncertainties in gas-particle partitioning and its implications for atmospheric degradation are considered, and chlorinated OPEs when river-based transport is considered. Further, the analyses showed strong dependence of results on the accuracy of the environmental half-lives used as input parameters. We suggest that the Tool could be modified to include an optional "Arctic (PMOC) LRTP setting" that incorporates episodic atmospheric and river-based transport as well as decreased environmental half-lives due to cold temperatures.

• MeSH
• estery MeSH
• látky znečišťující životní prostředí * analýza   MeSH
• monitorování životního prostředí MeSH
• Organizace pro hospodářskou spolupráci a rozvoj * MeSH
• organofosfáty * analýza   MeSH
• Publikační typ
• časopisecké články MeSH
• Geografické názvy
• Arktida MeSH
• Názvy látek
• estery MeSH
• látky znečišťující životní prostředí * MeSH
• organofosfáty * MeSH