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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, Košetice, 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.

Persistent organic pollutants (POPs) and polycyclic aromatic hydrocarbons (PAHs) were determined in abiotic samples from Concepción Bay in Central Chile. Samples were soxhlet extracted and injected in gas chromatography-mass spectrometry (GCMS). Polybrominated diphenyl ethers (PBDEs) showed the highest levels in air (3-1100 pg m -3 ), in water (2-64 pg L -1 ), in sediment, and soil (1-78 ng g -1 (dw)). PAHs were also high in the air (1-6 ng m -3 ), in water (1-7 ng L -1 ), in sediment (90-300 ng g -1 (dw)), and in soil (15-2300 ng g -1 (dw)). The polychlorinated biphenyls (PCBs) and chlorinated pesticides were generally low and did not show clear trends along the water column, with exception of PAHs. New data are presented in this work to assess the health status of a relevant coastal area in central Chile., (Copyright © 2021. Published by Elsevier Ltd.)

Chlorinated and brominated polycyclic aromatic hydrocarbons (ClPAHs and BrPAHs) are persistent organic pollutants that are ubiquitous in the atmospheric environment. The sources, fate, and sinks in the atmosphere of these substances are largely unknown. One of the reasons is the lack of widely accessible analytical instrumentation. In this study, a new analytical method for ClPAHs and BrPAHs using gas-chromatography coupled with triple quadrupole mass spectrometry is presented. The method was applied to determine ClPAHs and BrPAHs in total deposition samples collected at two sites in central Europe. Deposition fluxes of ClPAHs and BrPAHs ranged 580 (272-962) and 494 (161-936) pg m -2 day -1 , respectively, at a regional background site, Košetice, and 547 (351-724) and 449 (202-758) pg m -2 day -1 , respectively, at a semi-urban site, Praha-Libuš. These fluxes are similar to those of PCBs and more than 2 orders of magnitude lower than those of the parent PAHs in the region. Seasonal variations of the deposition fluxes of these halogenated PAHs were found with maxima in summer and autumn, and minima in winter at Košetice, but vice versa at Praha-Libuš. The distribution of ClPAHs and BrPAHs between the particulate and dissolved phases in deposition samples suggests higher degradability of particulate BrFlt/Pyr and BrBaA than of the corresponding ClPAHs. A number of congeners were detected for the first time in the atmospheric environment., (© 2021. The Author(s).)

Despite the success of passive sampler-based monitoring networks in capturing global atmospheric distributions of semivolatile organic compounds (SVOCs), their limited spatial resolution remains a challenge. Adequate spatial coverage is necessary to better characterize concentration gradients, identify point sources, estimate human exposure, and evaluate the effectiveness of chemical regulations such as the Stockholm Convention on Persistent Organic Pollutants. Land use regression (LUR) modelling can be used to integrate land use characteristics and other predictor variables (industrial emissions, traffic intensity, demographics, etc.) to describe or predict the distribution of air concentrations at unmeasured locations across a region or country. While LUR models are frequently applied to data-rich conventional air pollutants such as particulate matter, ozone, and nitrogen oxides, they are rarely applied to SVOCs. The MONET passive air sampling network (RECETOX, Masaryk University) continuously measures atmospheric SVOC levels across Czechia in monthly intervals. Using monitoring data from 29 MONET sites over a two-year period (2015-2017) and a variety of predictor variables, we developed LUR models to describe atmospheric levels and identify sources of polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs) and DDT across the country. Strong and statistically significant (R 2 > 0.6; p < 0.05) models were derived for PAH and PCB levels on a national scale. The PAH model retained three predictor variables - heating emissions represented by domestic fuel consumption, industrial PAH point sources, and the hill:valley index, a measure of site topography. The PCB model retained two predictor variables - site elevation, and secondary sources of PCBs represented by soil concentrations. These models were then applied to Czechia as a whole, highlighting the spatial variability of atmospheric SVOC levels, and providing a tool that can be used for further optimization of sampling network design, as well as evaluating potential human and environmental chemical exposures., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2021 Elsevier B.V. All rights reserved.)

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 (PM 2.5 ) 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 Σ 9 NPAHs and from 1.64 to 4330 pg m -3 for Σ 11 OPAHs, 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., Competing Interests: Declaration of competing interest The authors declare that they have no conflict of interest., (Copyright © 2021 The Authors. Published by Elsevier B.V. All rights reserved.)

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 Σ 17 NPAHs, from 32 to 2600 pg m -3 for Σ 10 OPAHs and from 5.1 to 4300 pg m -3 for Σ 2 O-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., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier Ltd. All rights reserved.)

Organic compounds like flame retardants (FRs), polychlorinated biphenyls (PCBs), organochlorine pesticides (OCPs) and polycyclic aromatic hydrocarbons (PAHs) are consistently found in both indoor and outdoor environments. There are many possible matrices for measurement of these compounds (e.g. indoor dust, air - passive and active air samples), but all methods have limitations, like the heterogeneous distribution of indoor dust, or noisy active air samplers. We used filters from building-wide heating, ventilation and air conditioning (HVAC) units to evaluate levels of PAHs, PCBs, OCPs and NFRs in indoor and outdoor environments, and to evaluate whether this method is feasible for screening semivolatile organic compounds (SVOCs) in indoor and near-building outdoor environments. Detectable levels of FRs, PCBs, OCPs and PAHs were found, demonstrating that HVAC filters do collect SVOCs, with generally higher levels of PAHs in the incoming air filters and higher levels of PCBs, OCPs and FRs in the outgoing air filters. Levels of FRs, PCBs and OCPs in outgoing air were comparable to those measured using conventional active air sampling in the same building. The advantages of using HVAC filters are (1) integrated and homogeneous samples, as the whole building is sampled over typically a long timescale (months), and (2) samples are easy and cheap to collect and do not require prior deployment of samplers. The key disadvantage is that HVAC filters are not designed for analytical chemistry and thus the filter materials can have variable or unknown gas sorption and particle capture, and can have strong matrix effects during analysis.

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 WHO 2005 -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., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

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 Σ 15 PAHs 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 Σ 15 PAHs was generally found in spring, while no seasonality was found for PCB deposition. For deposition fluxes for Σ 12 OCPs, 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.

Passive air sampling of semivolatile organic compounds (SVOCs) is a relatively inexpensive method that facilitates extensive campaigns with numerous sampling sites. An important question in the design of passive-sampling networks concerns the number and location of samplers. We investigate this question with the example of 17 SVOCs sampled at 14 background sites across the Czech Republic. More than 200 time series (length 5-11 years) were used to characterize SVOC levels and trends in air between 2003 and 2015. Six polychlorinated biphenyls (PCBs), 6 polyaromatic hydrocarbons (PAHs), and 5 organochlorine pesticides (OCPs) at 14 sites were assessed using data from the MONET passive sampling network. Significant decreases were found for most PCBs and OCPs whereas hexachlorobenzene (HCB) and most PAHs showed (mostly insignificant) increases. Spatial variability was rather low for PCBs and OCPs except for dichlorodiphenyltrichloroethane (DDT) and rather high for PAHs. The variability of the SVOC levels and trends depends on characteristics of the sites including their remoteness, landscape, population, and pollution sources. The sites can be grouped in distinct clusters, which helps to identify similar and, thereby, potentially redundant sites. This information is useful when monitoring networks need to be optimized regarding the location and number of sites.

Many attempts have been made to quantify the relationship between the amount of persistent organic pollutants sequestered by passive air sampling devices and their actual concentrations in ambient air. However, this information may not be necessary for some applications. In this study, two sets of 30 ten-year-long time series of simultaneous passive and high-volume active air sampling carried out at the Košetice observatory in the Czech Republic were used for a comparison of temporal trends. Fifteen polyaromatic hydrocarbons, seven polychlorinated biphenyls and eight organochlorine pesticides were investigated. In most cases, a good agreement was observed between the trends derived from passive and active monitoring with the exception of several compounds obviously affected by sampling artifacts. Two sampling artifacts were observed: breakthrough of high-volume sampler filters for penta- and hexachlorobenzene and semiquantitative values for PAHs with a high molecular weight. It has been suggested before that annually aggregated results of passive air monitoring may be used directly for the assessment of the long-term behavior of these compounds. The extensive set of long-term data used in this study allowed us to confirm this finding and to demonstrate that it is also possible to derive temporal trends and the compounds' half-lives in air from the passive-sampling time series.

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., (Copyright © 2015 Elsevier Ltd. All rights reserved.)

Seven types of indoor samples, covering five indoor matrices, were collected in a residential room, and analyzed for five classes of semivolatile organic compounds (SVOCs). The goal was to improve the understanding of the relationship between indoor air, surface films and dust, based on differences in sources, physicochemical properties, and indoor environmental characteristics. Comparisons of the five matrices (gas- and particle-phase air, floor dust, surface dust/films and window films) demonstrated that within our test room a semi-quantitative measurement of the SVOC distributions and concentrations could be obtained by air, and composite dust or furniture surface wipes. Dust concentrations varied within the room, and spot samples were not necessarily representative of the average room conditions. Polyurethane foam passive air samplers (PUF-PAS) successfully quantified the total air concentrations of the studied SVOC compound groups, as indoor air concentrations were dominated by gas-phase compounds, however air concentrations of individual particle-bound compounds had higher uncertainty. Measured concentrations of dust/surfaces could be used to estimate air concentrations of legacy SVOCs, demonstrating equilibrium in the room. However, air concentrations of current-use compounds (flame retardants, polycyclic aromatic hydrocarbons (PAHs)) could not be estimated from dust/surface concentrations, demonstrating the influence of ongoing primary emissions and non-equilibrium status in the room., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

A novel approach was developed for rapid assessment of bioavailability and potential mobility of contaminants in soil. The response of the same test organism to the organic extract, water extract and solid phase of soil was recorded and compared. This approach was designed to give an initial estimate of the total organic toxicity (response to organic extractable fraction), as well as the mobile (response to water extract) and bioavailable fraction (response to solid phase) of soil samples. Eighteen soil samples with different levels of pollution and content of organic carbon were selected to validate the novel three-step ecotoxicological evaluation approach. All samples were chemically analysed for priority contaminants, including aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs), hexachlorocyclohexane (HCH) and dichlordiphenyltrichloroethane (DDT). The ecotoxicological evaluation involved determination of toxicity of the organic, mobile and bioavailable fractions of soil to the test organism, bacterium Bacillus cereus. We found a good correlation between the chemical analysis and the toxicity of organic extract. The low toxicity of water extracts indicated low water solubility, and thus, low potential mobility of toxic contaminants present in the soil samples. The toxicity of the bioavailable fraction was significantly greater than the toxicity of water-soluble (mobile) fraction of the contaminants as deduced from comparing untreated samples and water extracts. The bioavailability of the contaminants decreased with increasing concentrations of organic carbon in evaluated soil samples. In conclusion, the three-step ecotoxicological evaluation utilised in this study can give a quick insight into soil contamination in context with bioavailability and mobility of the contaminants present. This information can be useful for hazard identification and risk assessment of soil-associated contaminants. Graphical Abstract New three-step ecotoxicological evaluation by using the same organism.

This paper reports the first study applying a triple-isotope approach for source apportionment of polycyclic aromatic hydrocarbons (PAHs). The (13)C/(12)C, (14)C/(12)C, and (2)H/(1)H isotope ratios of PAHs were determined in forest soils from mountainous areas of the Czech Republic, European Union. Statistical modeling applying a Bayesian Markov chain Monte Carlo (MCMC) framework to the environmental triple isotope PAH data and an end-member PAH isotope database allowed comprehensive accounting of uncertainties and quantitative constraints on the PAH sources among biomass combustion, liquid fossil fuel combustion, and coal combustion at low and high temperatures. The results suggest that PAHs in this central European region had a clear predominance of coal combustion sources (75 ± 6%; uncertainties represent 1 SD), mainly coal pyrolysis at low temperature (∼650 °C; 61 ± 8%). Combustion of liquid fossil fuels and biomass represented 16 ± 3 and 9 ± 3% of the total PAH burden (∑PAH14), respectively. Although some soils were located close to potential PAH point sources, the source distribution was within a narrow range throughout the region. These observation-based top-down constraints on sources of environmental PAHs provide a reference for both improved bottom-up emission inventories and guidance for efforts to mitigate PAH emissions.

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.

Atmospheric concentrations of high molecular weight polycyclic aromatic hydrocarbons (PAHs) were measured at five sites for almost two decades near the North American Great Lakes, as part of the Integrated Atmospheric Deposition Network (IADN), and at three remote sites around Europe, as part of the European Monitoring and Evaluation Programme (EMEP). The primary objectives were to reveal the spatial distributions, long-term temporal trends, and seasonal variations of atmospheric PAH concentrations and to investigate potential differences between these two regions. Atmospheric PAH concentrations at the urban sites in Chicago and Cleveland near Great Lakes were about 20 times (depending on PAH congener and sampling site) greater than those at the rural sites except for Košetice in the Czech Republic. Atmospheric PAH concentrations at Košetice, also a rural site, were about one-third of those at Chicago and Cleveland, but 10 times higher than those at other rural sites (Sturgeon Point, Sleeping Bear Dunes, Eagle Harbor, Aspvreten, and Spitsbergen). Significant long-term decreasing trends of all these PAH atmospheric concentrations were observed at Chicago and Cleveland. For the other sites, either less significant or no long-term decreasing trends were observed. Clear seasonality was observed at Sturgeon Point, Sleeping Bear Dunes, Košetice, and Spitsbergen, with the highest PAH concentrations observed in mid-January., (Copyright © 2013 Elsevier Ltd. All rights reserved.)

Dissolved waterborne polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs) and organochlorine pesticides (OCPs) were assessed over a period of one year at five sampling sites in a model industrial region in the Czech Republic using silicone rubber passive samplers. The spatial variability of POPs in the studied region in water was small and diffusive pollution sources predominate. Concentrations of the most volatile PAHs decreased with increasing water temperature in the whole region, which reflects the seasonality in atmospheric deposition. The dissolved concentrations of more hydrophobic PAHs, PCBs and OCPs in and downstream the industrial zone are related to desorption from suspended particles. Upstream the industrial area, a positive correlation of dissolved and particle-bound contamination was observed only for DDT metabolites and hexachlorobenzene. Calculated fugacities in water and bottom sediment indicated a fair degree of equilibrium between these compartments for OCPs and PCBs, whereas sediment represented a potential source of PAHs., (Copyright © 2012 Elsevier Ltd. All rights reserved.)

On Zugspitze (2670 m a.s.l.), Alps, higher concentrations were observed during a winter than during a summer measurement campaign of PAHs, chlorobenzenes (43.6 vs. 2.0 pg m(-3)) and DDTs (3.7 vs. 1.2 pg m(-3)), while hexachlorocyclohexanes and PCBs were found at similar levels. The PCB, HCH and DDT levels are among the lowest ever reported from outside the Arctic. Mostly lower levels were found in samples collected in summer than in winter despite a significant boundary layer air influence, but no such influence on samples collected during the winter campaign. Boundary layer influence was quantified by Lagrangian particle dispersion model retroplume analyses. Photochemical lifetimes corresponding to k(OH) < 1.5 x 10(-12) cm(3) molec(-1) s(-1) are found for p,p'-DDT, k(OH) < 0.75 x 10(-12) cm(3) molec(-1) s(-1) for p,p'-DDE and k(OH) < 1.0 x 10(-12) cm(3) molec(-1) s(-1) for p,p'-DDD.

To explain observed decadal trends in concentrations of polycyclic aromatic hydrocarbons (PAHs) in soil at the Kosetice observatory, Czech Republic, an environmental distribution model for persistent organic pollutants (POPs) based on the fugacity approach was developed. Weekly air concentrations were used as input data for the unsteady state model and concentrations in soil were calculated. In general, agreement between measured and predicted soil concentrations of PAHs was observed. Temporal trends in PAH concentrations in Kosetice can be related to changes in residential heating. Predicted soil concentrations of volatile PAHs namely acenaphthylene, fluorene and phenanthrene are in better correspondence with observed data than concentrations of less volatile PAHs i.e. dibenzo(ah)anthracene, benzo(a)pyrene and benzo(ghi)perylene. These discrepancies between model results and field data are probably a result of a simplified description of degradation and aging processes in soil. The results from our dynamic multicompartmental model confirmed our hypothesis about unsteady state conditions between the air and soil, and suggested that a commonly used simple steady state model should be only applied as a predictive tool in a small region when local sources and sinks are well described.

Polyurethane foam (PUF) disk passive air samplers were evaluated under field conditionsto assessthe effect of temperature and wind speed on the sampling rate for polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs), and organochlorine pesticides (OCPs). Passive samples integrated over 28-day periods were compared to high-volume air samples collected for 24 h, every 7 days. This provided a large data set of 42 passive sampling events and 168 high-volume samples over a 3-year period, starting in October 2003. Average PUF disk sampling rates for gas-phase chemicals was approximately 7 m3 d(-1) and comparable to previous reports. The high molecular weight PAHs, which are mainly particle-bound, experienced much lower sampling rates of approximately 0.7 m3 d(-1). This small rate was attributed to the ability of the sampling chamber to filter out coarse particles with only the fine/ultrafine fraction capable of penetration and collection on the PUF disk. Passive sampler-derived data were converted to equivalent air volumes (V(EQ), m3) using the high-volume air measurement results. Correlations of V(EQ) against meteorological data collected on-site yielded different behavior for gas- and particle-associated compounds. For gas-phase chemicals, sampling rates varied by about a factor of 2 with temperature and wind speed. The higher sampling rates at colder temperatures were explained bythe wind effecton sampling rates. Temperature and wind were strongly correlated with the greatest winds at coldertemperatures. Mainly particle-phase compounds (namely, the high molecular weight PAHs) had more variable sampling rates. Sampling rates increased greatly atwarmertemperatures as the high molecular weight PAH burden was shifted toward the gas phase and subject to higher gas-phase sampling rates. At colder temperatures, sampling rates were reduced as the partitioning of the high molecular weight PAHs was shifted toward the particle phase. The observed wind effect on sampling for the particle-phase compounds is believed to be tied to this strong temperature dependence on phase partitioning and hence sampling rate. For purposes of comparing passive sampler derived data for persistent organic pollutants, the factor of 2 variability observed for mainly gas-phase compounds is deemed to be acceptable in many instances for semiquantitative analysis. Depuration compounds may be used to improve accuracy and provide site-specific sampling rates, although this adds a level of complexity to the analysis. More research is needed to develop and test passive air samplers for particle-associated chemicals.

Much effort has been made to standardise sampling procedures, laboratory analysis, data analysis, etc. for semi volatile organic contaminants (SVOCs). Yet there are some unresolved issues in regards to comparing measurements from one of the most commonly used passive samplers (PAS), the polyurethane foam (PUF) disk PAS (PUF-PAS), between monitoring networks or different studies. One such issue is that there is no universal means to derive a sampling rate ( R s ) or to calculate air concentrations ( C air ) from PUF-PAS measurements for SVOCs. C air was calculated from PUF-PAS measurements from a long-term monitoring program at a site in central Europe applying current understanding of passive sampling theory coupled with a consideration for the sampling of particle associated compounds. C air were assessed against concurrent active air sampler (AAS) measurements. Use of “site-based/sampler-specific” variables: R s , calculated using a site calibration, provided similar results for most gas-phase SVOCs to air concentrations derived using “default” values (commonly accepted R s ). Individual monthly PUF-PAS-derived air concentrations for the majority of the target compounds were significantly different (Wilcoxon signed-rank (WSR) test; p < 0.05) to AAS regardless of the input values (site/sampler based or default) used to calculate them. However, annual average PUF-PAS-derived air concentrations were within the same order of magnitude as AAS measurements except for the particle-phase polycyclic aromatic hydrocarbons (PAHs). Underestimation of PUF-derived air concentrations for particle-phase PAHs was attributed to a potential overestimation of the particle infiltration into the PUF-PAS chamber and underestimation of the particle bound fraction of PAHs. [ABSTRACT FROM AUTHOR]

Purpose: A multi-compartment monitoring study was performed to characterize the effect of environmental variables, such as temperature and water flow as well as sediment characteristics, on the distribution and transport of persistent organic pollutants (POPs) in a dynamic river system during 1 year in an industrial region in central Europe. Materials and methods: Waterborne polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs) and organochlorine pesticides (OCPs) were assessed over a period of 1 year at five sampling sites in the Morava River in the Czech Republic. Contaminants were measured monthly in riverbed sediments, freshly deposited sediments, water samples and passive samplers. Results and discussion: Sediments are the main carrier of POPs in the river. Distinguishable patterns of PAHs, OCPs and PCBs in sediment indicate that their origin is from distinct sources and different transport pathways. The PAHs were identified as the dominant contaminant group of compounds with a mean concentration in sediment of 5,900 μg kg. Such concentrations are up to 10 times higher than in the Danube River, into which Morava drains. In contrast, mean concentrations of PCBs, hexachlorocyclohexanes (HCHs), dichlorodiphenyltrichloroethane and its breakdown products (DDTs) and hexachlorobenzene (HCB) of 6.0, 0.4, 4.2 and 6.0 μg kg, respectively, are similar to those in the Danube. With some exceptions, no significant difference in composition of surficial riverbed sediments and those collected using sediment traps was observed. Despite the presence of potential local pollutant sources, the differences in contaminant concentrations between sites in the region were in most cases not significant. Variations in POP concentrations in sediments are mainly induced by high flow events, whereas seasonal variability was not observed. Conclusions: The changes in contaminant concentrations in Morava River sediments are induced by episodic high flow events that cause erosion of contaminant-containing particles and their deposition at suitable downstream sites. [ABSTRACT FROM AUTHOR]

Although passive sampling has been previously used for the monitoring of volatile and semi-volatile contaminants in air, there are limited data on the use of this technique coupled with bioassays based on specific biological responses. Biological responses including those mediated by the aryl hydrocarbon (AhR) receptor as well as (anti-)estrogenicity and (anti-)androgenicity of samples from four Eastern European countries (Lithuania, Slovakia, Romania, and Serbia) were determined. To address the potential differences of specific toxic potencies of pollutant mixtures in ambient air in Eastern Europe, each country was characterized by a single more remote location that served to determine regional background conditions and one location in more urbanized and industrialized locations, which were defined as 'impacted' areas. Besides samples from Lithuania, a significant gradient in concentrations of AhR-mediated potency from background and impacted localities was observed. Greatest potencies were measured in samples from impacted locations in Romania and Slovakia. Concentrations of polycyclic aromatic hydrocarbons (PAHs) that were quantified accounted for 3-33 % of the 2,3,7,8-tetrachlorodibenzo- p-dioxin equivalents determined by use of the bioassay. No significant estrogenic potency was detected but anti-estrogenic effects were produced by air from two background locations (Lithuania, Slovakia) and three impacted locations (Lithuania, Romania, and Serbia). Anti-androgenic potency was observed in all samples. The greatest anti-estrogenic potency was observed at the background location in Slovakia. Anti-estrogenic and anti-androgenic potencies of studied air samples were probably associated with compounds that are not routinely monitored. The study documents suitability of passive air sampling for the assessment of specific toxic potencies of ambient air pollutants. [ABSTRACT FROM AUTHOR]

Abstract: Polycyclic aromatic hydrocarbons (PAHs) were measured together with inorganic air pollutants at two urban sites and one rural background site in the Banja Luka area, Bosnia and Hercegovina, during 72 h in July 2008 using a high time resolution (5 samples per day) with the aim to study gas-particle partitioning, aerosol mass size distributions and to explore the potential of a higher time resolution (4 h-sampling). In the particulate phase the mass median diameters of the PAHs were found almost exclusively in the accumulation mode (0.1–1.0 μm of size). These were larger for semivolatile PAHs than for non-volatile PAHs. Gas-particle partitioning of semivolatile PAHs was strongly influenced by temperature. The results suggest that the Junge–Pankow model is inadequate to explain the inter-species variation and another process must be significant for phase partitioning which is less temperature sensitive than adsorption. Care should be taken when interpreting slopes m of plots of the type log Kp = m log pL 0 + b based on 24 h means, as these are found sensitive to the time averaging, i.e. tend to be higher than when based on 12 h-mean samples. [ABSTRACT FROM AUTHOR]

Abstract: Polycyclic aromatic hydrocarbons (PAHs) were measured together with inorganic air pollutants at two urban sites and one rural background site in the Banja Luka area, Bosnia and Hercegovina, during 72h in July 2008 using a high time resolution (5 samples per day) with the aim to study the spatial and temporal variabilities and to explore the significance of averaging effects inherent to 24h-sampling. Measurement uncertainty was quantified on basis of three independent side-by-side samplers, deployed at one of the sites. PAH abundances in the urban and rural environments differed largely. Levels at the urban sites exceeded the levels at the rural site by >100%. The discrepancy was largely dominated by emission of 3–4 ring PAHs in the city, while 5–6 ring PAHs were more evenly distributed between city sites and the hill site. During the night a higher fraction of the semivolatile PAHs might have been stored in the soil or sorbed to surfaces. PAH patterns were undistinguishable across the three sites. However, concentrations of more particle-associated substances differed significantly between the urban sites than between one of the urban sites and the rural site (3σ uncertainty). Time-averaging (on a 24h-basis) would have masked the significant inter-site differences of half of the substances which were found at different levels (on a 4h-basis). [ABSTRACT FROM AUTHOR]

River sediments are a dynamic system, especially in areas where floods occur frequently. In the present study, an integrative approach is used to investigate the seasonal and spatial dynamics of contamination of sediments from a regularly flooded industrial area in the Czech Republic, which presents a suitable model ecosystem for pollutant distribution research at a regional level. Surface sediments were sampled repeatedly to represent two different hydrological situations: spring (after the peak of high flow) and autumn (after longer period of low flow). Samples were characterized for abiotic parameters and concentrations of priority organic pollutants. Toxicity was assessed by Microtox test; genotoxicity by SOS-chromotest and green fluorescent protein (GFP)-yeast test; and the presence of compounds with specific mode of action by in vitro bioassays for dioxin-like activity, anti-/androgenicity, and anti-/estrogenicity. Distribution of organic contaminants varied among regions and seasonally. Although the results of Microtox and genotoxicity tests were relatively inconclusive, all other specific bioassays led to statistically significant regional and seasonal differences in profiles and allowed clear separation of upstream and downstream regions. The outcomes of these bioassays indicated an association with concentrations of polycyclic aromatic hydrocarbons (PAHs) and polychlorinated biphenyls (PCBs) as master variables. There were significant interrelations among dioxin-like activity, antiandrogenicity and content of organic carbon, clay, and concentration of PAHs and PCBs, which documents the significance of abiotic factors in accumulation of pollutants. The study demonstrates the strength of the specific bioassays in indicating the changes in contamination and emphasizes the crucial role of a well-designed sampling plan, in which both spatial and temporal dynamics should be taken into account, for the correct interpretations of information in risk assessments. Environ. Toxicol. Chem. 2010;29:522–534. © 2009 SETAC [ABSTRACT FROM AUTHOR]

Soil and sediment samples from James Ross Island were analyzed for their PCB, OCP and PAH contents. Soil concentrations ranged between 0.51 and 1.82ngg−1 for seven indicator PCB congeners, between 0.49 and 1.34ngg−1 for HCH congeners, between 0.51 and 3.68ngg−1 for the sum of p,p′-DDT, DDE, and DDD, and between 34.9 and 171ngg−1 for the sum of 16 EPA PAHs. Sediment levels from 0.32 to 0.83ngg−1 were found for PCBs, from 0.14 to 0.76ngg−1 for HCHs, from 0.19 to 1.15ngg−1 for DDTs, and from 1.4 to 205ngg−1 for PAHs. A prevalence of low-mass PAHs, less chlorinated PCBs, and more volatile chemicals indicates that the long-range atmospheric transport from populated areas of Africa, South America, and Australia is the most probable contamination source for the solid matrices in James Ross Island. [Copyright &y& Elsevier]

Ambient air pollution, namely exposure to air particulate matter (PM), has been shown to be connected with a number of adverse health effects. At least part of the effects can be caused by organic pollutant mixtures associated with PM, which can elicit a wide range of specific toxic potentials. These potentials could be affected by seasonal variation of pollutant mixtures and PM size fraction. To examine this, six size subfractions of PM 10 were collected at rural and urban site in the Czech Republic in a year-long sampling campaign. The samples were assessed for aryl hydrocarbon (AhR)-mediated activity, estrogenicity and anti-androgenicity using mammalian cell models. The concentrations of detected toxic potentials differed among seasons. The greatest levels were observed in samples collected during winter when AhR-mediated effects and estrogenicity were at least 10-times greater than in summer. While the observed potentials were mostly less pronounced in samples from rural area, during winter, their AhR-mediated activity was twice as great as at the urban site. This was probably caused by the low-quality of fuel used for heating at the rural site. Assessed toxic potentials were associated mainly with PM size fractions with lesser aerodynamic diameters (<1 μm). Toxic potentials were compared with data from chemical analyses covering 102 chemicals from different pollutant groups to model their contribution to the observed effects. For AhR-mediated activity, chemical analyses explained on average 44% of the effect and the main identified effect-drivers were polycyclic aromatic hydrocarbons. For estrogenicity and anti-androgenicity, detected chemicals were able to explain on average less than 1.6% and 11% of the potentials, with their highest explicability reaching 13% and 57%, respectively. This was affected by the lack of data on specific toxic potency of some detected air pollutants, but also indicates a possible role of further not analyzed chemicals in these effects. Image 1 • Endocrine disrupting potential of pollutant mixtures in ambient air particulate matter. • Strong seasonal and particle-size related pattern of the studied effects. • Greatest endocrine disrupting potential in rural and urban sites during winter. • Bioactivities largely associated with easily inhalable particles (PM 1). • Wide spectra of detected pollutants contribute only partly to these bioactivities. Endocrine disrupting potential of ambient air particulate matter-associated pollutants show strong seasonal and particle-size dependent pattern and only partial explicability by analyzed pollutants. [ABSTRACT FROM AUTHOR]

Despite the fact that the occurrence of polycyclic aromatic hydrocarbons (PAHs) in the atmospheric environment has been studied for decades the photochemistry, deposition and, consequently, the long-range transport potential (LRTP) are not well understood. The reason is gas-particle partitioning (GPP) in the aerosol, its sensitivity to temperature and particulate phase composition, and sampling artefacts', and reactivity's sensitivities towards particulate phase composition. Furthermore, most PAHs are subject to re-volatilisation upon deposition to surfaces (multihopping). Levels and sources of 2-6-ring unsubstituted PAHs were studied in remote environments of Europe, Africa and Antarctica. Global atmospheric transport and fate of 3-5-ring PAHs were simulated under various scenarios of photochemistry and GPP. GPP influences drastically the atmospheric lifetime, compartmental distributions and the LRTP of PAH. Mid latitude emissions seem to reach the Arctic but not the Antarctic. [ABSTRACT FROM AUTHOR]

Abstract: Ratios of levels of 9 polycyclic aromatic hydrocarbons (PAHs) in air at central European sites during 1996–2008 were used to assess the suitability of 5 commonly used diagnostic ratios (DRs) for PAH source apportionment. DRs derived from a detailed literature study on emission factors were reflected in ambient air samples only at sites located near major sources. A significant seasonality was observed in a long-term time series of ambient DRs at a background site indicating possible capability of this method to reflect changes in source characteristics. The results of a mass balance study suggest that current knowledge of PAH reactivities is insufficient for a source apportionment based on DRs at receptor sites, even when limited to major types of PAH sources. However, DRs could be used to narrow down ozone and hydroxyl radical reaction rate coefficients’ uncertainties: kO3 (2) of pyrene and benzo(ghi)perylene in the particulate phase seem to be≤10% of the highest rate coefficient measured using model aerosols in the laboratory and kO3 (2) of indeno(1,2,3-cd)pyrene in the gas phase could be higher than previously estimated by three orders of magnitude. The suitability of DRs for source apportionment at (especially background) receptor sites cannot be expected in the general case. However, measurements carried out close to sources are in accordance with literature data suggesting that the ratios of benzo(a)anthracene/(benzo(a)anthracene+chrysene) and indeno(123cd)pyrene/(indeno(123cd)pyrene+benzo(ghi)perylene) are capable of distinguishing between traffic and residential heating, while the ratio of anthracene/(anthracene+phenanthrene) was the least useful DR due to its low variability. [ABSTRACT FROM AUTHOR]

Abstract: A majority of ongoing monitoring of persistent organic pollutants (POPs) is currently focused on chemicals emphasized in the Stockholm Convention. Quantitative detection of other substances (especially those with numerous anthropogenic sources such as polyaromatic hydrocarbons (PAHs)) is, however, also needed since their concentrations are usually several orders of magnitude higher. A goal of this study was to determine how various groups of compounds contribute to total human health risks at the variety of sampling sites in the region of Western Balkan. Distribution of the risks between the gas and particulate phases was also addressed. Results showed that inhalation exposure to organochlorine pesticides (OCPs) does not represent a significant risk to humans, while polychlorinated biphenyls (PCBs) re-volatilized to the atmosphere from contaminated soils and buildings can pose a problem. PCB evaporation from primary sources (currently used PCB-filled transformers or non-adequate storage facilities) generally resulted in much higher atmospheric concentrations than evaporation from the secondary sources (soils at the sites of war destructions). A majority of the human health risks at the urban sites were associated with PAHs. Between 83 and 94% of the cumulative risk at such sites was assigned to chemicals sorbed to particles, and out of it, PAHs were responsible for 99%. [Copyright &y& Elsevier]

Semivolatile organic compounds (SVOCs) emitted from consumer products, building materials, and indoor and outdoor activities can be highly persistent in indoor environments. Human exposure to and environmental contamination with polychlorinated biphenyls (PCBs) was previously reported in a region near a former PCB production facility in Slovakia. However, we found that the indoor residential PCB levels did not correlate with the distance from the facility. Rather, indoor levels in this region and those reported in the literature were related to the historic PCB use on a national scale and the inferred presence of primary sources of PCBs in the homes. Other SVOCs had levels linked with either the activities in the home, e.g., polycyclic aromatic hydrocarbons (PAHs) with wood heating; or outdoor activities, e.g., organochlorine pesticides (OCPs) with agricultural land use and building age. We propose a classification framework to prioritize SVOCs for monitoring in indoor environments and to evaluate risks from indoor SVOC exposures. Application of this framework to 88 measured SVOCs identified several PCB congeners (CB-11, -28, -52), hexachlorobenzene (HCB), benzo(a)pyrene, and γ-HCH as priority compounds based on high exposure and toxicity assessed by means of toxicity reference values (TRVs). Application of the framework to many emerging compounds such as novel flame retardants was not possible because of either no or outdated TRVs. Concurrent identification of seven SVOC groups in indoor environments provided information on their comparative levels and distributions, their sources, and informed our assessment of associated risks. • Indoor residential PCB levels do not correlate with the distance from PCB factory. • Indoor PAH levels are linked with use of wood heating in home. • Indoor OCP levels are linked with building age and agricultural land use. • PCBs, HCB, BAP and γ-HCH are priority compounds based on high exposure and toxicity. [ABSTRACT FROM AUTHOR]

Polycyclic aromatic hydrocarbons (PAHs) are ubiquitous semi-volatile organic pollutants. Their environmental occurrence is of global concern as some of them are carcinogens, mutagens, and teratogens. In this study, concentrations and distributions of 16 priority PAHs (∑PAHs) were measured in air, atmospheric deposition, and surface water at various locations in Himalayan, Middle, and Lower Reaches of the Ganges River, covering a spatial transect of 2500 km, during two seasons (pre-monsoon and monsoon). The concentration of ∑PAHs ranged between 2.2 and 182.2 ng m −3 in air, between 186 and 8810 ng m −2 day −1 in atmospheric deposition, and between 0.05 and 65.9 ng L −1 in surface water. Air concentrations were strongly correlated with human population density. In the Middle and Lower Reaches of the Ganges River, atmospheric PAHs were mainly attributed to fossil fuel combustion sources. In the Himalayan Reach the influence of forest fire or biomass combustion was evident during the dry pre-monsoon season. Seasonality in concentrations of PAHs in river water was evident in the Himalayan Reach of the river, as a probable consequence of climate-modulated secondary source intensity (i.e. releases from glacier melting). Seasonality faded in the Middle and Lower Reaches of the Ganges where water contamination is expected to mainly reflect anthropogenic primary sources. Ambient air concentrations were used to calculate the probabilistic incremental lifetime cancer risk (ILCR). It was expectedly found to be higher in the Middle and Lower Reaches compared to the Himalayan Reach. The strong correlation between population density and air concentrations suggests population density may be used as a surrogate variable to assess human health risk in data-sparse regions such as the Ganges River basin. [ABSTRACT FROM AUTHOR]

This study presents the seasonal size distribution of particulate polycyclic aromatic hydrocarbons (PAHs), polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) and dioxin-like polychlorinated biphenyls (dl-PCBs) in the atmosphere. Particles were sampled from October 2009 to October 2010 on a seasonal basis using a cascade impactor collecting six size fractions at a rural and urban site in the Brno area, Czech Republic. Higher concentrations of PAHs, PCDD/Fs and dl-PCBs were observed in cold seasons at both sites, attributed to the seasonality of the gas-particle partitioning, the increase of emissions and the lower boundary mixing layer in winter. All of the compounds showed a strong accumulation in the fine fraction, with, on average, 71% of ΣPAHs, 73% of ΣPCDD/Fs and 60% of Σdl-PCBs associated with particles <0.95 μm. The human risk assessment via inhalation was addressed and followed the same pattern as for concentrations, with 41 and 7 times higher risk in winter compared to summer at the rural and urban sites, respectively. More than 70% of cancer risks of PAHs, PCDD/Fs and dl-PCBs was associated with particles <0.95 μm. Moreover, an overestimation of the cancer risk via inhalation of up to 50% occurred when the size distribution of related compounds was not considered. [ABSTRACT FROM AUTHOR]

This study introduces a new combined air concentration measurement and modeling approach that we propose can be useful in medium and long term air quality assessment. A dispersion study was carried out for four high molecular weight polycyclic aromatic hydrocarbons (PAHs) in an urban area with industrial, traffic and domestic heating sources. A geographic information system (GIS) was used both for processing of input data as well as visualization of the modeling results. The outcomes of the dispersion model were compared to the results of passive air sampling (PAS). Despite discrepancies between measured and modeled concentrations, an approach combining the two techniques is promising for future air quality assessment. Differences between measured and modeled concentrations, in particular when measured values exceed the modeled concentrations, are indicative of undocumented, sporadic pollutant sources. Thus, these differences can also be useful for assessing and refining emission inventories. [ABSTRACT FROM AUTHOR]

Abstract: Positive matrix factorization (PMF) was applied on a large dataset of polycyclic aromatic hydrocarbon (PAH) concentrations determined in air at the central European background monitoring site Košetice, Czech Republic. The long-term (1996–2009) PAH median concentration in Košetice is about 6 times higher during winter than summer months. As the source apportionment of these pollutants is accompanied by concerns regarding the loss of the source signature during atmospheric transport, PMF was run on two winter PAH concentration data subsets stratified according to different ambient levels of oxidants. It is suggested, that the typical ambient air PAH pattern is largely preserved on a regional transport scale in winter in central Europe. However, the allocation of PMF model factors to particular PAH source categories (e.g., road traffic, residential wood combustion, residential and industrial coal combustion) could not be achieved due to (a) a high similarity of reference PAH profiles among each other and (b) variability in ambient reference PAH profiles. It is suggested, that the commonly studied set of EPA PAHs is not source category specific and thus not suitable for source apportionment. PAH source apportionment using more specific PAH and non-PAH markers is recommended. [ABSTRACT FROM AUTHOR]

Background concentrations of selected persistent organic pollutants (polychlorinated biphenyls, hexachlorobenzene, p,p'-DDT including metabolites) and polyaromatic hydrocarbons in soils of the Czech Republic were predicted in this study, and the main factors affecting their geographical distribution were identified. A database containing POP concentrations in 534 soil samples and the set of specific environmental predictors were used for development of a model based on regression trees. Selected predictors addressed specific conditions affecting a behavior of the individual groups of pollutants: a presence of primary and secondary sources, density of human settlement, geographical characteristics and climatic conditions, land use, land cover, and soil properties. The model explained a high portion of variability in relationship between the soil concentrations of selected organic pollutants and available predictors. A tree for hexachlorobenzene was the most successful with 76.2% of explained variability, followed by trees for polyaromatic hydrocarbons (71%), polychlorinated biphenyls (68.6%), and p,p'-DDT and metabolites (65.4%). The validation results confirmed that the model is stable, general and useful for prediction. The stochastic model applied in this study seems to be a promising tool capable of predicting the environmental distribution of organic pollutants. [ABSTRACT FROM AUTHOR]

Oxidation of aromatic and saturated aliphatic hydrocarbons (c = 10-3-10-5 mol L-1) by the hydroxyl radicals, photochemically produced from hydrogen peroxide (c = 10-1-10-5 mol L-1), in frozen aqueous solutions was investigated in the temperature range of -20 to -196 °C. While aromatic molecules (benzene, phenol, naphthalene, naphthalen-2-ol, or anthracene) underwent primarily addition-elimination reactions to form the corresponding hydroxy compounds, saturated hydrocarbons (cyclohexane, butane, methane) were oxidized to alcohols or carbonyl compounds via hydrogen abstraction and termination reactions. The results suggest that these photoreactions, taking place in a highly concentrated liquid or solidified layers covering the ice crystals, are qualitatively similar to those known to occur in liquid aqueous solutions; however, that probability of any bimolecular reaction in the environment ultimately depends on organic contaminant concentrations and oxidants availability at specific locations of the ice matrix, temperature, wavelength, and photon flux. They, moreover, support hypotheses that oxidation of organic impurities in the snowpack can produce volatile hydroxy and carbonyl compounds, which may consequently be released to the atmosphere. [ABSTRACT FROM AUTHOR]

Polyurethane foam (PUF) passive air samplers (PAS) are widely used for measurements of persistent organic pollutants (POPs) and other semi-volatile organic compounds (SVOCs) in large-scale monitoring networks as well as in case studies around the globe. Calibration of PUF-PAS is performed by field-based calibration studies or passive sampler uptake models. Both are typically performed and/or validated in temperate zones, however the sampling rates are more widely applied, including in tropical and polar zones. Here, we present field-based calibration results for MONET PUF-PAS from a subtropical and tropical site (Nairobi, Kenya and Accra, Ghana) based on side-by-side deployment of PUF-PAS and active air samplers (AAS), as well as model PAS uptake from available passive sampler uptake models. By comparing these results with a similar calibration from a temperate site (Brno, Czech Republic), we show that higher ambient temperatures result in higher effective sampling rates for intermediate molecular weight SVOCs (logK OA of 7–11) as a result of lower particle-bound fractions, and in lower sample volumes for lighter SVOCs (logK OA <7) as a result of a shorter time to equilibrium. This highlights the importance of adjusting passive sampling rates according to site-specific air temperatures. Model-based calibrations provided sampling volumes in agreement with the field-based calibration except for high K OA compounds, but the source of the discrepancy appears to be the model parameterization of the specific PUF-PAS sampler type rather than temperature-induced differences. Overall, the results suggest that while careful consideration should be taken when extrapolating calibration information from temperate to tropical zones, field or model-based calibrations are appropriate, and greater attention should be given to ensuring passive sampler models are correctly parameterized for the sampling configuration used. • Uptake performance of PUF-PAS differ in subtropical/tropical and temperate climate zones. • Temperature differences affect particle-bound fractions and thus sampling rates for PUF-PAS. • Higher temperatures shorten the time to equilibrium for low K OA compounds. • PAS calibration models must be correctly parameterized for specific sampler configurations. [ABSTRACT FROM AUTHOR]