Alice Dvorská

Košetice, Czech Republic - ten years of air pollution monitoring and four years of evaluating the origin of persistent organic pollutants

The regional observatory Kosetice is a central European background station. Unique continuous monitoring from 1988 on is held here. POP (persistent organic pollutant) concentration values of air samples from Kosetice taken between 1996 and 2005 were statistically processed. Values of Czech ambient air quality standards were not exceeded. Concentrations of polycyclic aromatic hydrocarbons reached two maxima, in 1996 and 2001-2002. Polychlorinated biphenyls concentrations reached the highest values in 1997 and 1998 and hexachlorocyclohexanes concentrations in 1998. DDTs, hexachlorobenzene and pentachlorobenzene were analysed as well. Long-range transport of pollutants between 2002 and 2005 was evaluated using the Potential Source Contribution Function hybrid receptor model. Indicated potential source areas of PCBs coincide with many well-known urban and industrialised areas, while the indicated potential source areas of HCHs and DDTs coincide with many agricultural and/or forested regions and the potential source areas of HCB comprise all land use types.

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.

On the contribution of biomass burning to POPs (PAHs and PCDDs) in air in Africa.

Forest, savannah, and agricultural fires in the tropics and subtropics are sources for widespread pollution and release many organic substances into the air and soil, including persistent organic pollutants, i.e., polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) and polycyclic aromatic hydrocarbons (PAHs). The significance of this source for the exposure of humans and the environment in Africa toward phenanthrene, fluoranthene, pyrene, benzo(a)pyrene, 2,3,7,8-tetrachlorodibenzo-p-dioxin, 1,2,3,4,6,7,8-heptachlorodibenzo-p-dioxin, and octachlorodibenzo-p-dioxin is studied using daily global emissions from vegetation fires observed by satellite and a global multicompartment chemistry-transport model. Near-ground atmospheric concentrations of model-predicted vegetation fire related concentrations of PAHs and PCDDs were in the 10-1000 and 10(-5)-10(-3) pg m(-3) ranges, respectively. Vegetation fires in Africa are found to emit 180 ± 25 kg yr(-1) of PCDD/Fs. By comparison with observations, it is found that fires explain 1-10% of the PCDD (5% of 2,3,7,8- tetrachlorodibenzo-p-dioxin) concentrations in the rural and background atmosphere of sub-Saharan Africa. The contribution of vegetation fires to exposure to PAH is probably >10%, but cannot be quantified due to lack of knowledge with regard to both emission factors and photochemistry. A sensitivity analysis suggests that the heterogeneous reaction of PAHs with ozone is effectively limiting atmospheric lifetime and long-range transport.

Obsolete pesticide storage sites and their POP release into the environment—an Armenian case study

Organochlorinated pesticides were widely applied in Armenia until the 1980s, like in all former Soviet Union republics. Subsequently, the problem of areas contaminated by organochlorinated pesticides emerged. Environmental, waste and food samples at one pesticide burial site (Nubarashen) and three former pesticide storage sites (Jrarat, Echmiadzin and Masis) were taken and analysed on the content of organochlorinated pesticides, polychlorinated dibenzo-p-dioxins and furans and dioxin-like polychlorinated biphenyls. Gradient sampling and diffusivity-based calculations provided information on the contamination release from the hot spots on a local scale. A risk analysis based on samples of locally produced food items characterised the impact of storage sites on the health of nearby residents. All four sites were found to be seriously contaminated. High pesticide levels and soil and air contamination gradients of several orders of magnitude were confirmed outside the fence of the Nubarashen burial site, confirming pesticide release. A storage in Jrarat, which was completely demolished in 1996 and contained numerous damaged bags with pure pesticides until 2011, was found to have polluted surrounding soils by wind dispersion of pesticide powders and air by significant evaporation of lindane and β-endosulfan during this period. Dichlorodiphenyltrichloroethane-contaminated eggs, sampled from hens roaming freely in the immediate surroundings of the Echmiadzin storage site, revealed a significant health risk for egg consumers above 1E−5. Although small in size and previously almost unknown to the public, storage sites like Echmiadzin, Masis and Jrarat were found to stock considerable amounts of obsolete pesticides and have a significant negative influence on the environment and human health. Multi-stakeholder cooperation proved to be successful in identifying such sites suspected to be significant sources of persistent organic pollutants.

Application of an unsteady state environmental distribution model to a decadal time series of PAH concentrations in Central Europe

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.

Sources and Distributions of Polycyclic Aromatic Hydrocarbons and Toxicity of Polluted Atmosphere Aerosols

Levels and sources, mass size and phase distributions of parent PAHs and the toxicity of ambient aerosols at urban and rural sites of central (Czech Republic) and south-eastern (Bosnia and Hercegovina) Europe, from 2006 to 2008, are investigated. PAH pollution levels are much higher in winter than in summer, obviously due to the seasonalities of emission strength, photochemical degradation and mixing. The levels are in the range of 10–100 ng m−3 at urban and rural sites, while strong concentration gradients exist towards background sites, in particular in summer, due to both dispersion and degradation during transport. Based on back-trajectory analysis of air masses travelling to a background site in the Czech Republic, regionally significant PAH source areas were localized in eastern and south-eastern Europe, while western European countries emit less. PAHs represent a mass fraction of ≈100–500 ppm of the inhalable particulate matter (i.e. <10 μm). Based on a size resolution of 6 fractions, unimodal PAH mass size distributions were found at urban and rural sites which peaked almost exclusively in the accumulation mode (0.1–1.0 μm). Mass median diameters were found higher for semivolatile PAHs than for non volatile PAHs, probably related to re-distribution of semivolatiles in the aerosol according to the surface size distribution. Genotoxicity and AhR-mediated (i.e. dioxin-like) activity were found in all size classes at urban and rural sites in similar magnitudes. Activities were found in general highest in the fine particulate matter (i.e. <1 μm). All biological effects tested were also found in extracts of the gas-phase. PAH TEQ and antiandrogenicity were even mostly associated with gaseous pollutants. The calculated TEQ mediated by parent PAHs corresponded by average to 7.5 and 95% of the dioxin-like activity in the particulate and gaseous fractions, respectively.