Petr Kukučka

Outdoor passive air monitoring of semi volatile organic compounds (SVOCs): a critical evaluation of performance and limitations of polyurethane foam (PUF) disks

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.

PCBs and OCPs on a East-to-West Transect: The Importance of Major Currents and Net Volatilization for PCBs in the Atlantic Ocean

Air-water exchange gradients of selected polychlorinated biphenyl (PCB) congeners across a large section of the tropical Atlantic suggested net volatilization of PCBs to the atmosphere. Only for the higher chlorinated PCB 153 and hexachlorobenzene (HCB) were gradients near equilibrium detected. The use of passive samplers also enabled the detection of dichlorodiphenyltrichloroethane (DDT) and its transformation products across the tropical Atlantic, indicating net deposition. There were clear differences between the southern and northern hemisphere apparent in terms of atmospheric concentrations: Once the ship moved from the southern into the northern hemisphere air, concentrations of HCB and other organochlorine pesticides increased several-fold. For large swaths of the tropical Atlantic Ocean, neither PCB nor organochlorine pesticide dissolved concentrations varied much longitudinally, probably due to efficient mixing by ocean currents. In selected samples, dissolved concentrations reflected the influence of river plumes and major ocean currents far away from the continents. Dissolved concentrations of PCBs 28, 52, 101, 118, and HCB increased in the Amazon plume and the Gulf Stream. While the Amazon plume flushed only a few kg of PCBs and HCB, the Gulf Stream is potentially delivering tons of PCBs into the North Atlantic annually.

Particle Size Distribution of Halogenated Flame Retardants and Implications for Atmospheric Deposition and Transport

This study investigates the distribution of polybrominated diphenyl ethers (PBDEs), hexabromocyclododecane (HBCD) and a group of novel flame retardants (NFRs) on atmospheric aerosols. Two high volume cascade impactors were used to collect particulate fractions of ambient air over a one year period at urban and rural sites. The majority of FRs were found on the finest aerosols (<0.95 μm). Concentrations of HBCD were higher than those of ΣPBDEs. Moreover, we noted seasonality and spatial differences in particle size distributions, yet a large portion of the observed differences were due to differences in particulate matter (PM) itself. When normalized by PM, the size distributions of the FRs exhibited much greater heterogeneity. Differences existed between the FR distributions by molecular weight, with the higher molecular weight FRs (e.g., BDE-209, Dechlorane Plus) distributed more uniformly across all particulate size fractions. The seasonal, spatial, and compound-specific differences are of crucial importance when estimating dry and wet deposition of FRs as smaller aerosols have longer atmospheric residence times. Estimated wet and dry deposition of four representative FRs (BDE-47, BDE-209, HBCD, and Dechlorane Plus) using size-segregated aerosol data resulted in lower deposition estimates than when bulk aerosol data were used. This has implications for estimates of long-range atmospheric transport and atmospheric residence times, as it suggests that without size-specific distributions, these parameters could be underestimated for FRs.

Concentrations, Fluxes and Residence Time of PBDEs Across the Tropical Atlantic Ocean

Little is known about the fate of polybrominated diphenylethers (PBDEs) across the Oceans. Air and water were sampled using both active and passive polyethylene samplers on an east-west transect across the tropical Atlantic Ocean in 2009 and analyzed for PBDEs. Typical particle-bound concentrations of PBDEs in the surface water were low, at <1 pg L(-1). Truly dissolved concentrations from passive samplers were ∼0.5 pg L(-1) for BDE 47 and around 0.1 pg L(-1) for BDEs 28, 99, and 100 (results from active samples were compromised). In the atmosphere, particle-bound BDE 209 dominated overall concentrations (median 1.2 pg m(-3)), followed by BDE 99 (0.13 pg m(-3)). Gas-phase concentrations based on passive samplers were 1-8 pg m(-3) for BDE 47 and ≤ 4 pg m(-3) for BDE 99. Net air-water exchange gradients strongly favored gas-phase deposition of PBDEs into the water. Net gas-phase deposition fluxes ranged from tens of pg m(-2) day(-1) for BDEs 28 and 85 to around 1 ng m(-2) day(-1) for BDE 47, 99, and 209. Settling fluxes of particle-bound PBDEs in the atmosphere and surface water were around 50 pg m(-2) day(-1) for BDE 47 and <10 pg m(-2) day(-1) for the other congeners.

Air and seawater pollution and air-sea gas exchange of persistent toxic substances in the Aegean Sea: spatial trends of PAHs, PCBs, OCPs and PBDEs

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.

Differences in spatiotemporal variations of atmospheric PAH levels between North America and Europe: data from two air monitoring projects.

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.

Contamination of Antarctic snow by polycyclic aromatic hydrocarbons dominated by combustion sources in the polar region

Environmental context Is long-range transport from populated and industrialised areas to blame for pollution of remote regions? We report that, for the worlds most remote region, Antarctica, and one prominent class of global pollutants, polycyclic aromatic hydrocarbons, long-range transport from other continents has not contributed significantly to recent snow contamination. Rather, the major sources are regional scientific stations and ocean transport, mostly tourism. Abstract Firn samples attributed to the period between 2002 and 2005 were collected from a snow pit on the Ekstrom Shelf Ice in the Weddell Sea (70°43.8′S, 8°25.1′W). Low-volume meltwater samples (5 mL) were extracted by solid-phase microextraction (SPME) and analysed for polycyclic aromatic hydrocarbons (PAHs) by gas chromatography-mass spectrometry. The recovery of the analytical method for the 4–6 ring PAHs was low. PAH concentrations in snow were found within the range of 26–197 ng L–1. The most prevailing substances were determined to be naphthalene, 1- and 2-methylnaphthalene, acenaphthylene, acenaphthene and phenanthrene, with naphthalene accounting for an overall mean of 82% of total PAH. Potential emission sources of PAHs in snow were studied using back-trajectory statistics and available emission data of combustion sources in and around Antarctica. The distance to the sources (ships and research stations) in this region was found to control the snow PAH concentrations. There was no indication for intercontinental transport or marine sources.

Source identification, spatio-temporal distribution and ecological risk of persistent organic pollutants in sediments from the upper Danube catchment

Riverine sediments, collected on a monthly basis during a period of one year, from five sites in a mixed land use region of the Czech Republic were analysed for chlorinated and brominated persistent organic pollutants (POPs). The region is located in the upper catchment of the Danube River. The POPs concentrations were as follows: 11-930 pg g(-1) polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDDs/Fs), 170-980 pg g(-1) dioxin-like polychlorinated biphenyls (dl-PCBs), 34-13,700 pg g(-1) polychlorinated naphthalenes (PCNs), 5.7-29,200 pg g(-1) polybrominated diphenylethers (PBDEs) and 0.21-351 ng g(-1) hexabromocyclododecanes (HBCDs). Concentrations expressed as toxic equivalents (TEQs), for PCDD/F+dl-PCB+PCN (TEQPCDD/F+dl-PCB+PCN) ranged from 0.37 to 19 pg g(-1). The results revealed a clear spatial separation between sites based on concentration and congener profile. There were also some obvious temporal patterns of selected POPs, which were related to river flow (seasonality) and organic carbon (TOC) of the sediment. Potential sources of POPs include local municipalities (flame retardants), some diffuse sources (PCNs and PCDDs/Fs) and potential point sources (PBDEs). Risk assessment based on risk quotients (RQ) revealed limited to medium ecological risk from PBDEs. TEQPCDD/F+dl-PCB+PCN were low relative to other European rivers, hence the risk to aquatic organisms was considered to be low. PCNs contributed significantly to overall TEQ in several cases.

Distribution of legacy and emerging semivolatile organic compounds in five indoor matrices in a residential environment

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.

Soil burdens of persistent organic pollutants - Their levels, fate and risk : Part II. Are there any trends in PCDD/F levels in mountain soils?

Good quality data apt for an assessment of temporal trends of polychlorinated dibenzo-p-dioxins and furans (PCDDs/Fs) in soils are difficult to obtain since there is a general lack of information on their residues in soils. Variability of soil profiles, non-homogeneity of samples, and often also inconsistency of applied sampling procedures further complicate this problem. To assess spatial and temporal trends of contamination, three soil sampling campaigns have been performed over the period of 12 years at the mountain forest sites in the Czech Republic. Relation between the air, needle and soil contaminations was addressed in addition to time-related variability of soil. It has been confirmed that soil is a good matrix for evaluation of spatial distribution of persistent organic pollutants (POPs) but difficult for establishment of temporal trends. A slow rate of the soil-forming processes and their site-specificity was generally the major source of uncertainties.