Petra Přibylová

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.

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.

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.

Melting Himalayan glaciers contaminated by legacy atmospheric depositions are important sources of PCBs and high-molecular-weight PAHs for the Ganges floodplain during dry periods

Melting glaciers are natural redistributors of legacy airborne pollutants, affecting exposure of pristine proglacial environments. Our data shows that melting Himalayan glaciers can be major contributors of polychlorinated biphenyls (PCBs) and high-molecular-weight polycyclic aromatic hydrocarbons (PAHs) for surface water in the Gangetic Plain during the dry season. Glacial emissions can exceed in some cases inputs from diffuse sources within the catchment. We analyzed air, deposition and river water in several sections along the Ganges River and its major headwaters. The predominant glacial origin of these contaminants in the Himalayan reach was demonstrated using air-water fugacity ratios and mass balance analysis. The proportion of meltwater emissions compared to pollutant discharge at downstream sections in the central part of the Gangetic Plain was between 2 and 200%. By remobilizing legacy pollutants from melting glaciers, climate change can enhance exposure levels over large and already heavily impacted regions of Northern India.

Tracking polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs) in sediments and soils from the southwest of Buenos Aires Province, Argentina (South eastern part of the GRULAC region).

PCBs and PBDEs (7 and 10 congeners, respectively) were analyzed in four coastal surface sediments collected from the northern shore of Bahía Blanca estuary and in nine soils from different locations of Bahía Blanca city and the surrounding region (Southwest of Buenos Aires Province, Argentina). Sediment samples showed PCBs(Σ7) concentrations ranged from 0.61 to 17.6ngg-1 (dry weight=dw) and PBDEs(Σ10) from 0.16 to 2.02ngg-1 dw, whereas in soil samples ranged from 0.04 to 1.67ngg-1 dw for PCBs(Σ7) and 0.04 to 10.7ngg-1 dw for PBDEs(Σ10). The highest concentrations of both chemicals were detected in the urban and industrial/port areas showing a dominance of the higher chlorinated PCB congeners: in sediments for PCB-180 (56±33%) and PCB-153 (11±6%); and in soils for PCB-138 (23±3%), PCB-153 (22±2%) and PCB-180 (18±7%). In contrast, lower chlorinated PCB congeners were predominant at more distant sites; in sediments for congeners PCB-28 (33±4%) and PCB-52 (14.5±0.2%); and in soils PCB-28 (56±14%) and PCB-52 (33±19%). PBDE-209 (high brominated PBDE) showed the highest relative abundance in both sample types i.e., sediment (94±7%) and soil (80±12%). These findings can be considered lower or similar when compared with other sites of the world, and are likely associated with anthropogenic activities in their surrounding area, which has experienced a fast industrial growth in the last decade. This is the first investigation of PBDEs levels in the whole study area and of PCBs in soils from the Bahía Blanca city and surrounding region. This article provides new and useful information on POP levels in the South eastern part of the GRULAC region.

Polybrominated Diphenyl Ethers (PBDEs) in Concepción Bay, central Chile after the 2010 Tsunami

PBDEs (10 congeners) were analyzed using GC-MS in superficial sediments and organisms of the Concepción Bay after the 2010 Tsunami. From all congeners analyzed PBDE-47, -99, -100 and -209 were the most frequently detected. Concentrations (ngg(-1) d.w.) in sediments for ΣPBDE-47, -99, -100 were low (0.02-0.09). However, PBDE-209 showed significantly higher values ∼20ngg(-1) d.w. This result were ∼10 times lower than those reported in a previous study of the 2010 Tsunami. The high result might be influenced by the massive urban debris dragged by the 2010 Tsunami. In organisms, concentrations of PBDE-47, -99, -100 (∼0.4ngg(-1) d.w.) were higher than those found in sediments (∼0.04ngg(-1) d.w.). Differences in PBDE pattern were also observed between different levels of the trophic food chain (primary and secondary consumers). This is the first attempt to assess the current status of Concepción Bay after the 2010 Tsunami.

Regional modelling of polycyclic aromatic hydrocarbons : WRF/Chem-PAH model development and East Asia case studies

Polycyclic aromatic hydrocarbons (PAHs) are hazardous pollutants, with increasing emissions in pace with economic development in East Asia, but their distribution and fate in the atmosphere are not yet well understood. We extended the regional atmospheric chemistry model WRFChem (Weather Research Forecast model with Chemistry module) to comprehensively study the atmospheric distribution and the fate of low-concentration, slowly degrading semivolatile compounds. The WRF-Chem-PAH model reflects the state-of-the-art understanding of current PAHs studies with several new or updated features. It was applied for PAHs covering a wide range of volatility and hydrophobicity, i.e. phenanthrene, chrysene and benzo[a]pyrene, in East Asia. Temporally highly resolved PAH concentrations and particulate mass fractions were evaluated against observations. The WRF-Chem-PAH model is able to reasonably well simulate the concentration levels and particulate mass fractions of PAHs near the sources and at a remote outflow region of East Asia, in high spatial and temporal resolutions. Sensitivity study shows that the heterogeneous reaction with ozone and the homogeneous reaction with the nitrate radical significantly influence the fate and distributions of PAHs. The methods to implement new species and to correct the transport problems can be applied to other newly implemented species in WRF-Chem.

Spatial gradients of polycyclic aromatic hydrocarbons (PAHs) in air, atmospheric deposition, and surface water of the Ganges River basin

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 2500km, during two seasons (pre-monsoon and monsoon). The concentration of ∑PAHs ranged between 2.2 and 182.2ngm-3 in air, between 186 and 8810ngm-2day-1 in atmospheric deposition, and between 0.05 and 65.9ngL-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.

Characterizing spatial diversity of passive sampling sites for measuring levels and trends of semivolatile organic chemicals

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.

Bioindication of PBDEs and PCBs by native and transplanted moss Pleurozium schreberi

PBDEs and PCBs are toxic, persistent organic pollutants (POPs), and the use of PCBs is forbidden, but they are still present in many environments and biota. 90-day assays were conducted with the moss Pleurozium schreberi transplanted from an uncontaminated control site to ten sites (rural and urban) selected in one of the most polluted regions of Upper Silesia in Poland. Native P. schreberi mosses were collected from the same ten polluted sites. Concentrations of PBDEs (28, 47, 66, 85, 99, 100, 153, 154, 183 and 209) and PCBs (28, 52, 101, 118, 138, 153, 180) were determined in all native and transplanted P. schreberi from all sites. Native P. schreberi contained the highest ΣPBDE and ΣPCB levels (63.6ngg-1 and 4.47pgg-1, respectively) when collected in the vicinity of a steel smelter. After 90 days of the experiment native and transplanted P. schreberi contained the highest concentrations of the same BDE 209 congener (88-91% of total PBDEs in the native mosses and 85-90% of the total PBDE burden in the transplants). The native and transplanted mosses from the industrial sites after 90 days of exposure contained significantly higher concentrations of all the examined PBDE and PCB congeners (except for 153 and 180) than mosses from rural sites. PBDE and PCB values were higher in native than in transplanted mosses after 90 days of exposure in both rural and industrial sites.