Polycyclic aromatic hydrocarbons and their metabolites in bronchoalveolar lavage and urine samples from patients with inhalation injury throughout their hospitalization: A prospective pilot study.

BACKGROUND: Specific toxic compounds, such as polycyclic aromatic hydrocarbons (PAHs) and their metabolites, may affect the inhalation injury (INHI) grade, patients' status, and prognosis for recovery. This pilot prospective study aimed to: i) evaluate the suitability of bronchoalveolar lavage (BAL) for determination of PAHs in the LRT and of urine for determination of hydroxylated metabolites (OH-PAHs) in patients with INHI, ii) describe the dynamic changes in the levels of these toxic compounds, and iii) correlate these findings with clinical variables of the patients with INHI. METHODS: The BAL and urine samples from 10 patients with INHI were obtained on Days 1, 3, 5, 7, and 14 of hospitalization, if possible, and PAHs (BAL) and OH-PAHs (urine) were analyzed using chromatographic methods (GC-MS and HPLC). RESULTS: Concentrations of analyzed PAHs were in most cases and time points below the limit of quantification in BAL samples. Nine OH-PAHs were detected in the urine samples; however, their concentrations sharply decreased within the first three days of the hospitalization. On Day 14, the total amount of OH-PAHs in urine was higher in surviving patients with High-grade INHI (≥3) than in those with Low-grade INHI (<3, p = 0.032). Finally, a significant correlation between certain OH-PAHs and clinical variables (AST/ALT, TBSA, ABSI) from Day 1 of the hospitalization was observed (p<0.05). CONCLUSIONS: BAL samples are not suitable for the analysis of PAHs. However, the OH-PAHs levels in urine can be measured reliably and were correlated with several clinical variables. Moreover, High-grade INHI was associated with higher total concentrations of OH-PAHs in urine.

Development of a supramolecular solvent-based extraction method for application to quantitative analyses of a wide range of organic contaminants in indoor dust.

This study investigates the efficacy of supramolecular solvent (SUPRAS) in extracting a diverse spectrum of organic contaminants from indoor dust. Initially, seven distinct SUPRAS were assessed across nine categories of contaminants to identify the most effective one. A SUPRAS comprising Milli-Q water, tetrahydrofuran, and hexanol in a 70:20:10 ratio, respectively, demonstrated the best extraction performance and was employed for testing a wider array of organic contaminants. Furthermore, we applied the selected SUPRAS for the extraction of organic compounds from the NIST Standard Reference Material (SRM) 2585. In parallel, we performed the extraction of NIST SRM 2585 with conventional extraction methods using hexane:acetone (1:1) for non-polar contaminants and methanol (100%) extraction for polar contaminants. Analysis from two independent laboratories (in Norway and the Czech Republic) demonstrated the viability of SUPRAS for the simultaneous extraction of twelve groups of organic contaminants with a broad range of physico-chemical properties including plastic additives, pesticides, and combustion by-products. However, caution is advised when employing SUPRAS for highly polar contaminants like current-use pesticides or volatile substances like naphthalene.

Widespread Pesticide Distribution in the European Atmosphere Questions their Degradability in Air.

Risk assessment of pesticide impacts on remote ecosystems makes use of model-estimated degradation in air. Recent studies suggest these degradation rates to be overestimated, questioning current pesticide regulation. Here, we investigated the concentrations of 76 pesticides in Europe at 29 rural, coastal, mountain, and polar sites during the agricultural application season. Overall, 58 pesticides were observed in the European atmosphere. Low spatial variation of 7 pesticides suggests continental-scale atmospheric dispersal. Based on concentrations in free tropospheric air and at Arctic sites, 22 pesticides were identified to be prone to long-range atmospheric transport, which included 15 substances approved for agricultural use in Europe and 7 banned ones. Comparison between concentrations at remote sites and those found at pesticide source areas suggests long atmospheric lifetimes of atrazine, cyprodinil, spiroxamine, tebuconazole, terbuthylazine, and thiacloprid. In general, our findings suggest that atmospheric transport and persistence of pesticides have been underestimated and that their risk assessment needs to be improved.

Air-soil cycling of oxygenated, nitrated and parent polycyclic aromatic hydrocarbons in source and receptor areas.

Polycyclic aromatic hydrocarbons (PAHs) and their oxygenated and nitrated derivatives, OPAHs and NPAHs, are semivolatile air pollutants which are distributed and cycling regionally. Subsequent to atmospheric deposition to and accumulation in soils they may re-volatilise, a secondary source which is understudied. We studied the direction of air-soil mass exchange fluxes of 12 OPAHs, 17 NPAHs, 25 PAHs and one alkylated PAH in two rural environments being influenced by the pollutant concentrations in soil and air, by season, and by land cover. The OPAHs and NPAHs in samples of topsoil, of ambient air particulate and gas phases and in the gas-phase equilibrated with soil were analysed by GC-APCI-MS/MS. The pollutants soil burdens show a pronounced seasonality, a winter maximum for NPAHs and PAHs and a summer maximum for OPAHs. One order of magnitude more OPAH and parent PAH are found stored in forest soil than in nearby grassland soil. Among a number of 3-4 ring PAHs, the OPAHs benzanthrone and 6H-benzo(c,d)pyren-6-one, and the NPAHs 1- and 2-nitronaphthalene, 9-nitrophenanthrene and 7-nitrobenz(a)anthracene are found to re-volatilise from soils at a rural background site in central Europe in summer. At a receptor site in northern Europe, net deposition of polycyclic aromatic compounds (PACs) prevails and re-volatilisation occurs only sporadic. Re-volatilisation of a number of PACs, including strong mutagens, from soils in summer and even in winter indicates that long-range atmospheric transport of primary PAC emissions from central Europe to receptor areas might be enhanced by secondary emissions from soils.

Spatial and Temporal Trends of Persistent Organic Pollutants across Europe after 15 Years of MONET Passive Air Sampling.

The Global Monitoring Plan of the Stockholm Convention on Persistent Organic Pollutants (POPs) was established to generate long-term data necessary for evaluating the effectiveness of regulatory measures at a global scale. After 15 years of passive air monitoring (2003-2019), MONET is the first network to produce sufficient data for the analysis of continuous long-term temporal trends of POPs in air across the entire European continent. This study reports long-term concentrations of 20 POPs monitored at 32 sites in 27 European countries. As of January 1, 2019, the concentration ranges (pg/m3) were 1.1-52.8 (∑6PCB), 0.3-8.5 (∑12dl-PCB), 0.007-0.175 (∑17PCDD/F), 0.02-2.2 (∑9PBDE), 0.4-24.7 (BDE 209), 0.5-247 (∑6DDT), 1.7-818 (∑4HCH), 15.8-74.7 (HCB), and 5.9-21.5 (PeCB). Temporal trends indicate that concentrations of most POPs have declined significantly over the past 15 years, with median annual decreases ranging from -8.0 to -11.5% (halving times of 6-8 years) for ∑6PCB, ∑17PCDD/F, HCB, PeCB, and ∑9PBDE. Furthermore, no statistically significant differences were observed in either the trends or the concentrations of specific POPs at sites in Western Europe (WEOG) compared to sites in Central and Eastern Europe (CEE), which suggests relatively uniform compound-specific distribution and removal at the continental scale.

Exposure to flame retardants in European children - Results from the HBM4EU aligned studies.

Many legacy and emerging flame retardants (FRs) have adverse human and environmental health effects. This study reports legacy and emerging FRs in children from nine European countries from the HBM4EU aligned studies. Studies from Belgium, Czech Republic, Germany, Denmark, France, Greece, Slovenia, Slovakia, and Norway conducted between 2014 and 2021 provided data on FRs in blood and urine from 2136 children. All samples were collected and analyzed in alignment with the HBM4EU protocols. Ten halogenated FRs were quantified in blood, and four organophosphate flame retardants (OPFR) metabolites quantified in urine. Hexabromocyclododecane (HBCDD) and decabromodiphenyl ethane (DBDPE) were infrequently detected (<16% of samples). BDE-47 was quantified in blood from Greece, France, and Norway, with France (0.36 ng/g lipid) having the highest concentrations. BDE-153 and -209 were detected in <40% of samples. Dechlorane Plus (DP) was quantified in blood from four countries, with notably high median concentrations of 16 ng/g lipid in Slovenian children. OPFR metabolites had a higher detection frequency than other halogenated FRs. Diphenyl phosphate (DPHP) was quantified in 99% of samples across 8 countries at levels ∼5 times higher than other OPFR metabolites (highest median in Slovenia of 2.43 ng/g lipid). FR concentrations were associated with lifestyle factors such as cleaning frequency, employment status of the father of the household, and renovation status of the house, among others. The concentrations of BDE-47 in children from this study were similar to or lower than FRs found in adult matrices in previous studies, suggesting lower recent exposure and effectiveness of PBDE restrictions.

Comparability of semivolatile organic compound concentrations from co-located active and passive air monitoring networks in Europe.

Passive air sampling (PAS) has been used to monitor semivolatile organic compounds (SVOCs) for the past 20 years, but limitations and uncertainties persist in the derivation of effective sampling volumes, sampling rates, and concentrations. As a result, the comparability of atmospheric levels measured by PAS and concentrations measured by active air sampling (AAS) remains unclear. Long-term PAS data, without conversion into concentrations, provide temporal trends that are similar to, and consistent with, trends from AAS data. However, for more comprehensive environmental and human health assessments of SVOCs, it is also essential to harmonize and pool air concentration data from the major AAS and PAS monitoring networks in Europe. To address this need, we calculated and compared concentration data for 28 SVOCs (including organochlorine pesticides (OCPs), polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers (PBDEs), and polycyclic aromatic hydrocarbons (PAHs)) at the six monitoring sites in Europe with 10 years of co-located AAS (EMEP) and PAS (MONET) data: Birkenes, Kosetice, Pallas, Råö, Stórhöfði, and Zeppelin. Atmospheric SVOC concentrations were derived from PAS data using the two most common computation models. Long-term agreement between the AAS and PAS data was strong for most SVOCs and sites, with 79% of the median PAS-derived concentrations falling within a factor of 3 of their corresponding AAS concentrations. However, in both models it is necessary to set a sampler-dependent correction factor to prevent underestimation of concentrations for primarily particle-associated SVOCs. In contrast, the models overestimate concentrations at sites with wind speeds that consistently exceed 4 m s-1. We present two recommendations that, if followed, allow MONET PAS to provide sufficiently accurate estimates of SVOC concentrations in air so that they can be deployed together with AAS in regional and global monitoring networks.

Application of 96-well plate SPE method for analysis of persistent organic pollutants in low volume blood serum samples.

Though many persistent organic pollutants (POPs) are closely regulated the human population is still exposed to these ubiquitous chemicals from the environment and diet. Safe management and human biomonitoring of POPs is necessary to understand the risk of exposure. Within human biomonitoring the mass of sample is often limited, therefore robust methods using smaller sample amounts are necessary. This study developed a 96-well plate solid phase extraction (SPE) method for determination of selected POPs: polychlorinated biphenyls (PCBs), organochlorine pesticides (OCPs), polybrominated diphenyl ethers (PBDEs), hexabromocyclododecane (HBCD) and non-persistent novel flame retardants (NFRs) in low volume blood serum. Non-destructive clean-up coupling Oasis HLB extraction plate with Phree phospholipid removal plate was employed. Extraction efficiency was determined at low and high concentrations in certified reference materials NIST SRM 1957 and 1958, respectively. Target compounds deviated from certified values on average by 15% and 21% for SRM 1957 and SRM 1958, respectively. Observed limit of detections (LODs) ranged from 0.36 pg/mL (PCB 180) to 66.07 pg/mL (δ-HCH). The applicability for real samples is demonstrated on 48 samples from pregnant women enrolled in the pilot phase of the CELSPAC: TNG study. In total, 30 target compounds were detected in at least one sample. The method developed here provides a fast and reliable analysis of human blood serum with possibility to introduce automation for the sample preparation procedure.

Seasonal variations in air concentrations of 27 organochlorine pesticides (OCPs) and 25 current-use pesticides (CUPs) across three agricultural areas of South Africa.

For decades pesticides have been used in agriculture, however, the occurrence of legacy organochlorine pesticides (OCPs) and current-use pesticides (CUPs) is poorly understood in Africa. This study investigates air concentrations of OCPs and CUPs in three South African agricultural areas, their spatial/seasonal variations and mixture profiles. Between 2017 and 2018, 54 polyurethane foam-disks passive air-samplers (PUF-PAS) were positioned in three agricultural areas of the Western Cape, producing mainly apples, table grapes and wheat. Within areas, 25 CUPs were measured at two sites (farm and village), and 27 OCPs at one site (farm). Kruskal-Wallis tests investigated area differences in OCPs concentrations, and linear mixed-effect models studied differences in CUPs concentrations between areas, sites and sampling rounds. In total, 20 OCPs and 16 CUPs were detected. A median of 16 OCPs and 10 CUPs were detected per sample, making a total of 11 OCPs and 24 CUPs combinations. Eight OCPs (trans-chlordane, o,p'-/p,p'-dichlorodiphenyldichloroethylene (DDE)/dichlorodiphenyltrichloroethane (DDT), endosulfan sulfate, γ-hexachlorocyclohexane and mirex) and two CUPs (carbaryl and chlorpyrifos) were quantified in all samples. p,p'-DDE (median 0.14 ng/m3) and chlorpyrifos (median 0.70 ng/m3) showed the highest concentrations throughout the study. Several OCPs and CUPs showed different concentrations between areas and seasons, although CUPs concentrations did not differ between sites. OCPs ratios suggest ongoing chlordane use in the region, while DDT and endosulfan contamination result from past-use. Our study revealed spatial and seasonal variations of different OCPs and CUPs combinations detected in air. Further studies are needed to investigate the potential cumulative or synergistic risks of the detected pesticides.

Toxicity to bronchial cells and endocrine disruptive potentials of indoor air and dust extracts and their association with multiple chemical classes.

Pollution of indoor environment, where people spend much of their time, comprises complex mixtures of compounds with vastly understudied hazard potential. This study examined several important specific toxic effects and pollutant levels (177 compounds) of indoor samples (air gas phase, PM10 and dust) from different microenvironments after two extractions with focus on their gas/particle/dust distribution and polarity. The endocrine disruptive (ED) potential was assessed by human cell-based in vitro bioassays addressing anti-/estrogenicity, anti-/androgenicity, aryl hydrocarbon, thyroid and peroxisome proliferator-activated receptor-mediated activities. Potential toxicity to respiratory tract tissue was assessed using human bronchial cell line. The toxicological analyses pointed out the relevance of both inhalation and ingestion exposure, with significant effects detected after exposure to extracts from all three studied matrices with distinct gas/particle distribution patterns. Chemical analyses document the high complexity of indoor pollutant mixtures with greatest levels of phthalates, their emerging alternatives, and PAHs in dust. Despite the detection of up to 108 chemicals, effects were explained only to low extent. This emphasizes data gaps regarding ED potencies of many detected abundant indoor contaminants, but also potential presence of other unidentified ED compounds. The omnipresent ED potentials in indoor environment rise concern regarding associated human health risk.

NPAHs and OPAHs in the atmosphere of two central European cities: Seasonality, urban-to-background gradients, cancer risks and gas-to-particle partitioning.

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.

A comprehensive assessment of endocrine-disrupting chemicals in an Indian food basket: Levels, dietary intakes, and comparison with European data.

Endocrine-disrupting chemicals (EDCs) in diet are a health concern and their monitoring in food has been introduced in the European Union. In developing countries, EDC dietary exposure data are scarce, especially from areas perceived as pollution hotspots, including industrialized countries like India. Several persistent organic pollutants (POPs) act as EDCs and pose a pressure to human health mainly through dietary exposure. In the present study, a range of organochlorine pesticides (OCPs), polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers (PBDEs), dioxins and furans were measured in several food items collected from Indian urban (Delhi) and peri-urban (Dehradun) areas. Food basket contamination data were used to estimate EDC dietary exposure and compare it with that of the average European population estimated from available monitoring data. All the target contaminants were found in most food items, especially in dairies and meat products. OCPs were the main contributers to the measured EDC contamination. Food supplied to Delhi's markets had higher EDC contamination than that supplied to the peri-urban market in Dehradun. Despite lax compliance and control measures, Indian dietary exposure of OCPs and PBDEs were comparable with that of Europe and were lower for PCBs and dioxins. Higher meat consumption in Europe only partly explained this pattern which was driven also by the higher EDC residues in some European food items. A substantial part of endocrine disrupting potential in the diet derives from food and animal feeds internationally traded between developed and developing countries. With increasingly globalized food systems, internationally harmonized policies on EDC content in food can lead to better protection of health in both these contexts.

Open, High-Resolution EI+ Spectral Library of Anthropogenic Compounds.

To address the lack of high-resolution electron ionisation mass spectral libraries (HR-[EI+]-MS) for environmental chemicals, a retention-indexed HR-[EI+]-MS library has been constructed following analysis of authentic compounds via GC-Orbitrap MS. The library is freely provided alongside a compound database of predicted physicochemical properties. Currently, the library contains over 350 compounds from 56 compound classes and includes a range of legacy and emerging contaminants. The RECETOX Exposome HR-[EI+]-MS library expands the number of freely available resources for use in full-scan chemical exposure studies and is available at: https://doi.org/10.5281/zenodo.4471217.

Three years of atmospheric concentrations of nitrated and oxygenated polycyclic aromatic hydrocarbons and oxygen heterocycles at a central European background site.

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.

Temporal Trends of Persistent Organic Pollutants across Africa after a Decade of MONET Passive Air Sampling.

The Global Monitoring Plan of the Stockholm Convention on Persistent Organic Pollutants (POPs) was established to generate long-term data necessary for evaluating the effectiveness of regulatory measures at a global scale. After a decade of passive air monitoring (2008-2019), MONET is the first network to produce sufficient data for the analysis of long-term temporal trends of POPs in the African atmosphere. This study reports concentrations of 20 POPs (aldrin, chlordane, chlordecone, DDT, dieldrin, endrin, endosulfan, HBCDD, HCB, HCHs, heptachlor, hexabromobiphenyl, mirex, PBDEs, PCBs, PCDDs, PCDFs, PeCB, PFOA, and PFOS) monitored in 9 countries (Congo, Ghana, Ethiopia, Kenya, Mali, Mauritius, Morocco, Nigeria, and Sudan). As of January 1, 2019, concentrations were in the following ranges (pg/m3): 0.5-37.7 (∑6PCB), 0.006-0.724 (∑17PCDD/F), 0.05-5.5 (∑9PBDE), 0.6-11.3 (BDE 209), 0.1-1.8 (∑3HBCDD), 1.8-138 (∑6DDT), 0.1-24.3 (∑3endosulfan), 0.6-14.6 (∑4HCH), 9.1-26.4 (HCB), 13.8-18.2 (PeCB). Temporal trends indicate that concentrations of many POPs (PCBs, DDT, HCHs, endosulfan) have declined significantly over the past 10 years, though the rate was slow at some sites. Concentrations of other POPs such as PCDD/Fs and PBDEs have not changed significantly over the past decade and are in fact increasing at some sites, attributed to the prevalence of open burning of waste (particularly e-waste) across Africa. Modeled airflow back-trajectories suggest that the elevated concentrations at some sites are primarily due to sustained local emissions, while the low concentrations measured at Mt. Kenya represent the continental background level and are primarily influenced by long-range transport.

Trends of Diverse POPs in Air and Water Across the Western Atlantic Ocean: Strong Gradients in the Ocean but Not in the Air.

Oceans have remained the least well-researched reservoirs of persistent organic pollutants (POPs) globally, due to their vast scale, difficulty of access, and challenging (trace) analysis. Little data on POPs exists along South America and the effect of different currents and river plumes on aqueous concentrations. Research cruise KN210-04 (R/V Knorr) offered a unique opportunity to determine POP gradients in air, water, and their air-water exchange along South America, covering both hemispheres. Compounds of interest included polychlorinated biphenyls (PCBs), organochlorine pesticides (OCPs), polybrominated diphenylethers (PBDEs), and polycyclic aromatic hydrocarbons (PAHs). Remote tropical Atlantic Ocean atmospheric concentrations varied little between both hemispheres; for HCB, BDEs 47 and 99, they were ∼5 pg/m3, PCBs were ∼1 pg/m3, α-HCH was ∼0.2 pg/m3, and phenanthrene and other PAHs were in the low 100s pg/m3. Aqueous concentrations were dominated by PCB 52 (mean 4.1 pg/L), HCB (1.6 pg/L), and ß-HCH (1.9 pg/L), with other compounds <1 pg/L. Target PCBs tended to undergo net volatilization from the surface ocean, while gradients indicated net deposition for a-HCH. In contrast to atmospheric concentrations, which were basically unchanged between hemispheres, we detected strong gradients in aqueous POPs, with mostly nondetects in the tropical western South Atlantic. These results highlight the importance of currents and loss processes on ocean scales for the distribution of POPs.

Toxic potentials of particulate and gaseous air pollutant mixtures and the role of PAHs and their derivatives.

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.

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.

Multiyear levels of PCDD/Fs, dl-PCBs and PAHs in background air in central Europe and implications for deposition.

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.