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

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

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.

• 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

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

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.

• MeSH
• aerosoly analýza   MeSH
• atmosféra chemie   MeSH
• chlorované uhlovodíky analýza   MeSH
• inhalační expozice analýza   MeSH
• látky znečišťující vzduch analýza   MeSH
• lidé MeSH
• monitorování životního prostředí MeSH
• pesticidy analýza   MeSH
• pevné částice analýza   MeSH
• polychlorované bifenyly analýza   MeSH
• polycyklické aromatické uhlovodíky analýza   MeSH
• Check Tag
• lidé MeSH
• Publikační typ
• časopisecké články MeSH
• práce podpořená grantem 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

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.

• 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

The effects of sampling artifacts are often not fully considered in the design of air monitoring with active air samplers. Semivolatile organic contaminants (SVOCs) are particularly vulnerable to a range of sampling artifacts because of their wide range of gas-particle partitioning and degradation rates, and these can lead to erroneous measurements of air concentrations and a lack of comparability between sites with different environmental and sampling conditions. This study used specially adapted filter-sorbent sampling trains in three types of active air samplers to investigate breakthrough of SVOCs, and the possibility of other sampling artifacts. Breakthrough volumes were experimentally determined for a range of polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs), organochlorine pesticides (OCPs) and polybrominated diphenyl ethers (PBDEs) in sampling volumes from 300 to 10,000 m(3), and sampling durations of 1-7 days. In parallel, breakthrough was estimated based on theoretical sorbent-vapor pressure relationships. The comparison of measured and theoretical determinations of breakthrough demonstrated good agreement between experimental and estimated breakthrough volumes, and showed that theoretical breakthrough estimates should be used when developing air monitoring protocols. Significant breakthrough in active air samplers occurred for compounds with vapor pressure >0.5 Pa at volumes <700 m(3). Sample volumes between 700 and 10,000 m(3) may lead to breakthrough for compounds with vapor pressures between 0.005 and 0.5 Pa. Breakthrough is largely driven by sample volume and compound volatility (therefore indirectly by temperature) and is independent of sampler type. The presence of significant breakthrough at "typical" sampling conditions is relevant for air monitoring networks, and may lead to under-reporting of more volatile SVOCs.

• MeSH
• artefakty * MeSH
• chlorované uhlovodíky analýza   MeSH
• halogenované difenylethery analýza   MeSH
• látky znečišťující vzduch analýza   MeSH
• monitorování životního prostředí metody   MeSH
• polychlorované bifenyly analýza   MeSH
• polycyklické aromatické uhlovodíky analýza   MeSH
• Publikační typ
• časopisecké články MeSH

Polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs) and organochlorine pesticides (OCPs) are ubiquitous and toxic contaminants. Their atmospheric deposition fluxes on the regional scale were quantified based on simultaneous sampling during 1 to 5 years at 1 to 6 background/rural sites in the Czech Republic and Austria. The samples were extracted and analysed by means of gas chromatography coupled to mass spectrometry. For all seasons and sites, total deposition fluxes for Σ15PAHs ranged 23-1100 ng m-2 d-1, while those for Σ6PCBs and Σ12OCPs ranged 64-4400 and 410-7800 pg m-2 d-1, respectively. Fluoranthene and pyrene were the main contributors to the PAH deposition fluxes, accounting on average for 19% each, while deposition fluxes of PCBs and OCPs were dominated by PCB153 (26%) and γ-hexachlorobenzene (30%), respectively. The highest deposition flux of Σ15PAHs was generally found in spring, while no seasonality was found for PCB deposition. For deposition fluxes for Σ12OCPs, no clear spatial trend was found, confirming the perception of long-lived regional pollutants. Although most OCPs and PCBs hardly partition to the particulate phase in ambient air, on average, 42% of their deposition fluxes were found on filters, confirming the perception that particle deposition is more efficient than dry gaseous deposition. Due to methodological constraints, fluxes derived from bulk deposition samplers should be understood as lower estimates, in particular with regard to those substances which in ambient aerosols mostly partition to the particulate phase.

• MeSH
• chlorované uhlovodíky analýza   MeSH
• hexachlorbenzen analýza   MeSH
• látky znečišťující vzduch analýza   MeSH
• monitorování životního prostředí * MeSH
• pesticidy analýza   MeSH
• plynová chromatografie s hmotnostně spektrometrickou detekcí MeSH
• polychlorované bifenyly analýza   MeSH
• polycyklické aromatické uhlovodíky analýza   MeSH
• Publikační typ
• časopisecké články MeSH
• Geografické názvy
• Česká republika MeSH
• Evropa MeSH
• Rakousko MeSH