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Nitrated monoaromatic hydrocarbons (NMAHs) are ubiquitous in the environment and an important part of atmospheric humic-like substances (HULIS) and brown carbon. They are ecotoxic and with underresearched toxic potential for humans. NMAHs were determined in size-segregated ambient particulate matter collected at two urban sites in central Europe, Ostrava and Kladno, Czech Republic. The average sums of 12 NMAHs (Σ12NMAH) measured in winter PM10 samples from Ostrava and Kladno were 102 and 93 ng m−3, respectively, and 8.8 ng m−3 in summer PM10 samples from Ostrava. The concentrations in winter corresponded to 6.3–7.3% and 2.6–3.1% of HULIS-C and water-soluble organic carbon (WSOC), respectively. Nitrocatechols represented 67–93%, 61–73% and 28–96% of NMAHs in PM10 samples collected in winter and summer at Ostrava and in winter at Kladno, respectively. The mass size distribution of the targeted substance classes peaked in the submicrometre size fractions (PM1), often in the PM0.5 size fraction especially in summer. The bioaccessible fraction of NMAHs was determined by leaching PM3 samples in two simulated lung fluids, Gamble’s solution and artificial lysosomal fluid (ALF). More than half of NMAH mass is found bioaccessible, almost complete for nitrosalicylic acids. The bioaccessible fraction was generally higher when using ALF (mimics the chemical environment created by macrophage activity, pH 4.5) than Gamble’s solution (pH 7.4). Bioaccessibility may be negligible for lipophilic substances (i.e. log KOW > 4.5).

Concerns about the possible negative impacts of current use pesticides (CUPs) for both the environment and human health have increased worldwide. However, the knowledge on the occurrence of CUPs in soil and air and the related human exposure in Africa is limited. This study investigated the presence of 30 CUPs in soil and air at two distinct agricultural sites in South Africa and estimated the human exposure and related risks to rural residents via soil ingestion and inhalation (using hazard quotients, hazard index and relative potency factors). We collected 12 soil and 14 air samples over seven days during the main pesticide application season in 2018. All samples were extracted, purified and analyzed by high-performance liquid chromatography coupled with tandem mass spectrometry. In soils, nine CUPs were found, with chlorpyrifos, carbaryl and tebuconazole having the highest concentrations (up to 63.6, 1.10 and 0.212 ng g(-1), respectively). In air, 16 CUPs were found, with carbaryl, tebuconazole and terbuthylazine having the highest levels (up to 25.0, 22.2 and 1.94 pg m(-3), respectively). Spatial differences were observed between the two sites for seven CUPs in air and two in soils. A large dominance towards the particulate phase was found for almost all CUPs, which could be related to mass transport kinetics limitations (non-equilibrium) following pesticide application. The estimated daily intake via soil ingestion and inhalation of individual pesticides ranged from 0.126 fg kg(-1) day(-1) (isoproturon) to 14.7 ng kg(-1) day(-1) (chlorpyrifos). Except for chlorpyrifos, soil ingestion generally represented a minor exposure pathway compared to inhalation (i.e.

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. Keywords: Human intake, Indoor environment, Flame retardants, Legacy POPs, PAHs, Risk prioritization

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.

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 Sigma(17)NPAHs, from 32 to 2600 pg m-3 for Sigma(10)OPAHs and from 5.1 to 4300 pg m(-3) for Sigma O-2-heterocycles. The average particulate mass fraction (q) ranged from 0.01 +/- 0.02 (2-nitronaphthalene) to 0.83 +/- 0.22 (1-nitropyrene) for individual NPAHs and from

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

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 Sigma(10)OPAHs were 10.0 +/- 9.2 ng/m(3) in winter and 3.5 +/- 1.6 ng/m(3) in summer. The gradient to the regional background site exceeded 1 order of magnitude. Sigma(18)NPAH 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 approximate to 5% of the total ambient concentration of OPAHs and up to approximate 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.

Organochlorine pesticides (OCPs) have been used to preserve the integrity of historical buildings or to protect collections of artefacts at potentially large volumes and often without detailed application records. Previous research has focused on the efficiency of remediation at contaminated sites (where identified), as well as improvement of preservation techniques and workplace health and safety. Few studies have assessed the human health risks from occupational exposure to OCPs in buildings of cultural and historical importance. Thus, potential risks may remain unidentified. In the present study, OCPs in indoor air were measured in a baroque theatre and a natural history museum in the Czech Republic, both of which had suspected past indoor application. In the theatre attic p,p'-dichlorodiphenyldichloroethylene (p,p'-DDE) levels in air were up to 190ngm-3, confirming past indoor use of p,p'-dichlorodiphenyltrichloroethane (p,p'-DDT). There was also evidence of γ-hexachlorocyclohexane (γ-HCH) use in the theatre (max γ-HCH in air of 56ngm-3). Yet, the cancer risk (CR) from occupational exposure via inhalation (Expi) to OCPs in the theatre was low (CR 1×10-4). Our results show the CR through Expi to OCPs in buildings, such as museums can still be significant enough to warrant mitigation measures, e.g., remediation.

Although Humic-LIke Substances (HULIS) are important contributors to the mass of organic aerosol in airborne particulate matter (PM), little is known about their chemical composition, while, their size-resolved optical properties have not been studied yet. Here, HULIS fractions were isolated from size-resolved aerosol samples (≤0.49, 0.49–0.95, 0.95–3 and 3–10 μm) collected in urban and suburban environments of four European cities during wintertime. The bulk (i.e., sum of all size fractions) concentration of HULIS ranged between 1.29 and 2.80 μg m−3 across sites with highest values in the ≤0.49 μm particle size fraction. The contribution of the carbon mass of HULIS (HULIS-C) to the water-soluble organic carbon content (WSOC) of PM was 32–43%, which is typical for urban sites affected by biomass burning. The Mass Absorption Efficiency (MAE), which characterizes the efficiency of absorbing solar energy per carbon mass of HULIS decreased with particle size, suggesting that the finest size fractions contain more light-absorbing chromophores, which could affect the light-absorbing ability of organic aerosols. The good correlation of HULIS with effective biomass tracers such as K+, as well as with secondary inorganic aerosol components, proposed that HULIS had both primary (i.e., biomass burning) and secondary sources. The Fourier Transfer Infrared coupled to Attenuation Total Reflectance (FTIR-ATR) spectra demonstrated prevalence of aromatic over carboxylic functional groups in most HULIS fractions, indicating contribution from coal combustion emissions in addition to fresh biomass burning aerosol. The new findings add to better understanding the sources and chemical structure of HULIS in urban and suburban environments.

Degradation of semivolatile organic compounds (SVOCs) occurs naturally in ambient air due to reactions with reactive trace gases (e.g., ozone, NOx). During air sampling there is also the possibility for degradation of SVOCs within the air sampler, leading to underestimates of ambient air concentrations. We investigated the possibility of this sampling artifact in commonly used active and passive air samplers for seven classes of SVOCs, including persistent organic pollutants (POPs) typically covered by air monitoring programs, as well as SVOCs of emerging concern. Two active air samplers were used, one equipped with an ozone denuder and one without, to compare relative differences in mass of collected compounds. Two sets of passive samplers were also deployed to determine the influence of degradation during longer deployment times in passive sampling. In active air samplers, comparison of the two sampling configurations suggested degradation of particle-bound polycyclic aromatic hydrocarbons (PAHs), with concentrations up to 2× higher in the denuder-equipped sampler, while halogenated POPs did not have clear evidence of degradation. In contrast, more polar, reactive compounds (e.g., organophosphate esters and current use pesticides) had evidence of losses in the sampler with denuder. This may be caused by the denuder itself, suggesting sampling bias for these compounds can be created when typical air sampling apparatuses are adapted to limit degradation. Passive air samplers recorded up to 4× higher concentrations when deployed for shorter consecutive sampling periods, suggesting that within-sampler degradation may also be relevant in passive air monitoring programs.

Polycyclic aromatic hydrocarbons (PAHs) and some of their nitrated derivatives, NPAHs, are seemingly ubiquitous in the atmospheric environment. Atmospheric lifetimes may nevertheless vary within a wide range, and be as short as a few hours. The sources and sinks of NPAH in the atmosphere are not well understood. With a Lagrangian field experiment and modeling, we studied the conversion of the semivolatile PAHs fluoranthene and pyrene into the 2-nitro derivatives 2-nitrofluoranthene and 2-nitropyrene in a cloud-free marine atmosphere on the time scale of hours to 1 day between a coastal and an island site. Chemistry and transport during several episodes was simulated by a Lagrangian box model i.e., a box model coupled to a Lagrangian particle dispersion model, FLEXPART-WRF. It is found that the chemical kinetic data do capture photochemical degradation of the 4-ring PAHs under ambient conditions on the time scale of hours to 1 day, while the production of the corresponding NPAH, which sustained 2-nitrofluoranthene/fluoranthene and 2-nitropyrene/pyrene yields of (3.7 ± 0.2) and (1.5 ± 0.1)%, respectively, is by far underestimated. Predicted levels of NPAH come close to observed ones, when kinetic data describing the reactivity of the OH-adduct were explored by means of theoretically based estimates. Predictions are also underestimated by 1-2 orders of magnitude, when NPAH/PAH yields reported from laboratory experiments conducted under high NOx conditions are adopted for the simulations. It is concluded that NPAH sources effective under low NOx conditions, are largely underestimated., Grant Agency of the Czech Republic (P503 16-115375); Izmir Institute of Technology Research Fund (2013IYTE-14); Max Planck Society; European Union (262254); Ministry of Education, Youth & Sports - Czech Republic (LM2015051/CZ.02.1.01/0.0/0.0/16_013/0001761)

Polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs) and organochlorine pesticides (OCPs) are ubiquitous and toxic contaminants. Their atmospheric deposition fluxes on the regional scale were quantified based on simultaneous sampling during 1 to 5 years at 1 to 6 background/rural sites in the Czech Republic and Austria. The samples were extracted and analysed by means of gas chromatography coupled to mass spectrometry. For all seasons and sites, total deposition fluxes for Σ15PAHs ranged 23–1100 ng m−2 d−1, while those for Σ6PCBs and Σ12OCPs ranged 64–4400 and 410–7800 pg m−2 d−1, respectively. Fluoranthene and pyrene were the main contributors to the PAH deposition fluxes, accounting on average for 19% each, while deposition fluxes of PCBs and OCPs were dominated by PCB153 (26%) and γ-hexachlorobenzene (30%), respectively. The highest deposition flux of Σ15PAHs was generally found in spring, while no seasonality was found for PCB deposition. For deposition fluxes for Σ12OCPs, no clear spatial trend was found, confirming the perception of long-lived regional pollutants. Although most OCPs and PCBs hardly partition to the particulate phase in ambient air, on average, 42% of their deposition fluxes were found on filters, confirming the perception that particle deposition is more efficient than dry gaseous deposition. Due to methodological constraints, fluxes derived from bulk deposition samplers should be understood as lower estimates, in particular with regard to those substances which in ambient aerosols mostly partition to the particulate phase. Electronic supplementary material The online version of this article (10.1007/s11356-019-05464-9) contains supplementary material, which is available to authorized users.

In situ extraction of steroid hormones from waste water using adsorption-based integrative passive samplers represents a promising approach for their monitoring in water at ultra-trace concentrations. Three passive samplers, namely a POCIS, a Chemcatcher fitted with an Empore SDB-RPS disk, and an Empore SDB-RPS disk-based sampler with enhanced water flow, were calibrated in situ in treated municipal wastewater for the purpose of monitoring five estrogens (17-β-estradiol, 17-α-estradiol, 17-α-ethinylestradiol, estrone and estriol) at sub ng per litre concentrations. Uptake of steroids to samplers during 14-day exposure in wastewater was compared with steroid concentrations in daily collected composite water samples. Sampling rates were obtained from a numerical solution of first order uptake kinetics equations describing the uptake of compounds into a passive sampler over time. Mass transfer of steroids in the Chemcatcher fitted with naked Empore disks was more than two times faster than in the POCIS sampler. The uptake capacity of the applied Empore disk was not sufficient for integrative uptake of all tested steroids during the entire 14-day exposure. Time-weighted average concentrations of steroids estimated at concentrations in units of ng L−1 using the in situ-calibrated samplers were within a factor of two from values obtained using composite water samples.

As a consequence of long-range transported pollution, air–sea exchange can become a major source of persistent organic pollutants in remote marine environments. The vertical gradients in the air were quantified for 14 species, i.e. four parent polycyclic aromatic hydrocarbons (PAHs), three polychlorinated biphenyls (PCBs), three organochlorine pesticides (OCPs) and two polybrominated diphenylethers (PBDEs) in the gas-phase at a remote coastal site in the southern Aegean Sea in summer. Most vertical gradients were positive (Δc∕Δz > 0), indicating downward (net depositional) flux. Significant upward (net volatilisational) fluxes were found for three PAHs, mostly during daytime, and for two OCPs, mostly during night-time, as well as for one PCB and one PBDE during part of the measurements. While phenanthrene was deposited, fluoranthene (FLT) and pyrene (PYR) seem to undergo flux oscillation, hereby not following a day–night cycle. Box modelling confirms that volatilisation from the sea surface has significantly contributed to the night-time maxima of OCPs. Fluxes were quantified based on eddy covariance. Deposition fluxes ranged from −28.5 to +1.8 µg m−2 day−1 for PAHs and −3.4 to +0.9 µg m−2 day−1 for halogenated compounds. Dry particle deposition of FLT and PYR did not contribute significantly to the vertical flux.

An inter-laboratory study was organised for the monitoring of emerging aquatic pollutants (pharmaceuticals, pesticides, steroids, brominated diphenyl ethers and others) using passive samplers. Thirty laboratories participated in the sampler comparison exercise. Various samplers designs were exposed at a single sampling site to treated waste water. The organisers deployed in parallel multiple samplers of a single type, which were distributed for evaluation of the contribution of the different analytical procedures to the data variability. Between laboratory variation of results from passive samplers was about factor 5 larger than within laboratory variability. Similar results obtained for different passive samplers analysed by individual laboratories and also low within laboratory variability indicate that the passive sampling process is causing less variability than the analysis. Concentrations in composite water samples were within the range obtained by passive samplers. In future a significant improvement of analytical precision and calibration of adsorption based passive samplers is needed. (C) 2015 Elsevier B.V. All rights reserved.

The central and eastern Mediterranean is a receptor area for persistent organic pollutants (POPs) emitted in western, central and eastern Europe, particularly during summer. Atmospheric concentrations of PCBs, DDXs, PBDEs, penta- and hexachlorobenzene were measured during a ship-borne survey in the summer of 2010. The concentration of PCBs (sum of 7 congeners) was 3.61 (2.08-7.72) pg m(-3), of which 6.7% was associated with the particulate phase. The mean concentration of DDT isoi-ners and their metabolites, DDE and DDD, was 2.60 (0.46-7.60) pg m(-3) (particulate mass fraction theta = 0.097), of penta- and hexachlorobenzene 0.22 (

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. 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. 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−1. 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 kg1, 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. 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.

Concentrations of polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs), organochlorine pesticides (OCPs), and polybrominated diphenyl ethers (PBDEs) in air and soil, their fugacities, and the experimental soil-air partitioning coefficient (KSA) were determined at two background sites in the Gt. Hungarian Plain in August 2013. The concentrations of the semivolatile organic compounds (SOCs) in the soil were not correlated with the organic carbon content but with two indirect parameters of mineralization and aromaticity, suggesting that soil organic matter quality is an important parameter affecting the sorption of SOCs onto soils. Predictions based on the assumption that absorption is the dominant process were in good agreement with the measurements for PAHs, OCPs, and the low chlorinated PCBs. In general, soils were found to be a source of PAHs, high chlorinated PCBs, the majority of OCPs and PBDEs, and a sink for the low chlorinated PCBs and γ-hexachlorocyclohexane. Diurnal variations in the direction of the soil-air exchange were found for two compounds (i.e., pentachlorobenzene and p,p'-dichlorodiphenyldichloroethane), with volatilization during the day and deposition in the night. The concentrations of most SOCs in the near-ground atmosphere were dominated by revolatilization from the soil.

Concentrations of 20 perfluorinated alkyl substances (PFASs) were measured in dust samples from 41 homes in Canada, the Czech Republic, and United States in the spring-summer of 2013. The most frequently detected compounds were perfluorohexanoic acid (PFHxA) and perfluorooctane sulfonate (PFOS). PFOS and perfluorooctanoic acid (PFOA) had the highest concentrations of PFASs in all countries. PFOS median concentrations for the three countries were between 9.1 and 14.1 ng/g, and PFOA medians ranged between 8.2 and 9.3 ng/g. In general, concentrations in North America were higher than in the Czech Republic, which is consistent with usage patterns. No differences were found for perfluorooctane sulfonamides/sulfonamidoethanols (FOSA/Es) levels due to the low number of detections. Homologue profiles suggest that the shift from longer to shorter chain PFASs is more advanced in North America than in Europe. Significant relationships were found among individual homologues and between PFAS concentrations in dust and type of floor, number of people living in the house, and building age. Keywords: Perfluorinated compounds, PFASs, House dust, Indoor environment

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.

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

Near-ground air (26 substances) and surface seawater (55 substances) concentrations of persistent toxic substances (PTS) were determined in July 2012 in a coordinated and coherent way around the Aegean Sea based on passive air (10 sites in 5 areas) and water (4 sites in 2 areas) sampling. The direction of air–sea exchange was determined for 18 PTS. Identical samplers were deployed at all sites and were analysed at one laboratory. hexachlorobenzene (HCB), hexachlorocyclohexanes (HCHs) as well as dichlorodiphenyltrichloroethane (DDT) and its degradation products are evenly distributed in the air of the whole region. Air concentrations of p,p′-dichlorodiphenyldichloroethylene (p,p′-DDE) and o,p′-DDT and seawater concentrations of p,p′-DDE and p,p′-DDD were elevated in Thermaikos Gulf, northwestern Aegean Sea. The polychlorinated biphenyl (PCB) congener pattern in air is identical throughout the region, while polybrominated diphenylether (PBDE)patterns are obviously dissimilar between Greece and Turkey. Various pollutants, polycyclic aromatic hydrocarbons (PAHs), PCBs, DDE, and penta- and hexachlorobenzene are found close to phase equilibrium or net-volatilisational (upward flux), similarly at a remote site (on Crete) and in the more polluted Thermaikos Gulf. The results suggest that effective passive air sampling volumes may not be representative across sites when PAHs significantly partitioning to the particulate phase are included., Granting Agency of the Czech Republic (312334); Czech Ministry of Education (LO1214--LM2011028); European Social Fund (CZ.1.07/2.3.00/30.0037); European Commission FP7 (262254 ACTRIS)

The most commonly used passive air sampler (PAS) (i.e. polyurethane foam (PUF) disk) is cheap, versatile, and capable of accumulating compounds present both in gas and particle phases. Its performance for particle associated compounds is however disputable. In this study, twelve sets of triplicate PUF-PAS were deployed outdoors for exposure periods of 1–12 weeks together with continuously operated active samplers, to characterize sampling efficiency and derive sampling rates (RS) for compounds belonging to 7 SVOC classes (including particle associated compounds). PUF-PAS efficiently and consistently sampled polychlorinated biphenyls (PCBs), organochlorine pesticides (OCPs), polycyclic aromatic hydrocarbons (PAHs), and eight novel brominated flame retardant (nBFR) compounds. Low accuracy and lack of sensitivity was observed for most polychlorinated dibenzo-p-dioxins/furans PCDD/Fs and polybrominated diphenyl ethers (PBDEs) (under the conditions of this study), with the exception of some congeners which may be used as qualitative markers for their respective classes. Application of compound specific RS was found crucial for all compounds except PCBs. Sampling efficiency of the particle associated compounds was often low.

Polycyclic aromatic hydrocarbon (PAH) concentration in air of the central and eastern Mediterranean in summer 2010 was 1.45 (0.30–3.25) ng m−3 (sum of 25 PAHs), with 8 (1–17)% in the particulate phase, almost exclusively associated with particles < 0.25 μm. The total deposition flux of particulate PAHs was 0.3–0.5 μ g m−2 yr−1. The diffusive air–sea exchange fluxes of fluoranthene and pyrene were mostly found net-depositional or close to phase equilibrium, while retene was net-volatilisational in a large sea region. Regional fire activity records in combination with box model simulations suggest that seasonal depositional input of retene from biomass burning into the surface waters during summer is followed by an annual reversal of air–sea exchange, while interannual variability is dominated by the variability of the fire season. One-third of primary retene sources to the sea region in the period 2005–2010 returned to the atmosphere as secondary emissions from surface seawaters. It is concluded that future negative emission trends or interannual variability of regional sources may trigger the sea to become a secondary PAH source through reversal of diffusive air–sea exchange. Capsule: In late summer the seawater surface in the Mediterranean has turned into a temporary secondary source of PAH, obviously related to biomass burning in the region.

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.