Atmospheric concentrations, occurrence and deposition of persistent organic pollutants (POPs) in a Mediterranean coastal site (Etang de Thau, France).

Atmospheric concentrations and deposition fluxes of PCDD/F and PCB have been evaluated over a 1-year period in a Mediterranean coastal lagoon (Etang de Thau, France). Indicative PBDE air concentrations in the hot season are also reported in this work. ∑2,3,7,8-PCDD/Fs and ∑18PCBs (gas+particulate) air concentrations ranged from 67 to 1700 fg m(-3) and from 13 to 95 pg m(-3), respectively whereas ∑8PBDEs (gas+particulate) summer time levels varied from 158 to 230 pg m(-3). The PCDD/F and PCB atmospheric occurrence over Thau lagoon and subsequent inputs to the surface waters are determined by an assemble of factors, being the seasonality of atmospheric concentration, the air mass origin and meteorological conditions important drivers. Total (wet+dry) ∑2,3,7,8-PCDD/Fs and ∑18PCBs deposition fluxes to Thau Lagoon waters are 117 and 715 pg m(-2)d(-1), respectively.

Atmospheric occurrence and deposition of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) in the open Mediterranean Sea.

The overall objective of this work is to provide the first evaluation of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) occurrence and deposition to Mediterranean open seawater. sigma2,3,7,8-PCDD/F air (gas+aerosol) concentrations over the Mediterranean Sea ranged from 60 to 1040 fg m(-3). The highest value (1555 fg m(-3)) was measured in a reference sample taken in the SW Black Sea. No consistent trend regarding the diel cycle of PCDD/Fs was observed. PCDD/Fs transported to the open sea waters from continental areas and across the Atlantic as well as ship emissions may be significant sources to the open Mediterranean. Seawater concentrations in the Mediterranean ranged from 42 to 64 fg L(-1). The sigma2,3,7,8-PCDD/F dry deposition fluxes in the Marmara and Black Seas (210 kg year(-1)) are from 2 to 55 times higher than dry fluxes in the Mediterranean Sea (4-156 kg year(-1)). Analysis of estimated diffusive air-water fluxes and air/water fugacity ratios show that a net volatilization of some PCDD congeners is feasible. However, evidence of a net absorption flux for the rest of PCDD/F is found. When both atmospheric deposition processes are considered together the open Mediterranean Sea is a net sink of PCDD/F, due to the importance of dry deposition fluxes of aerosol-bound PCDDFs.

Polychlorinated biphenyls (PCBs) in the atmosphere of sub-alpine northern Italy.

The main objective of this work was to assess the atmospheric concentrations and seasonal variations of selected POPs in a sub-alpine location where few data are available. A monitoring and research station was set up at the JRC Ispra EMEP site (Italy). We present and discuss a one-year data set (2005-2006) on PCB air concentrations. Sigma 7PCBs monthly averaged concentration varied from 31 to 76 pgm(-3). Concentrations in the gas phase (21-72 pgm(-3)) were higher than those in the particulate phase (3-10 pgm(-3)). Advection of air masses and re-volatilization from local sources seem to play a dominant role as drivers of PCB atmospheric concentrations in the area. Indications of seasonal variation affecting PCB congener patterns and the gas/particulate partitioning were found. Modeling calculations suggest a predominant importance of the wet deposition in this region (1 microgm(-2)yr(-1) Sigma 7PCBs yearly total wet deposition flux; 650-2400 pgL(-1) rainwater concentrations).

An integrated approach to assess the PCDD/F emissions of the coal fired stoves combining emission measurements and ambient air levels modelling.

Very high emissions of PCDD/Fs up to 1300 microg TEQ per ton of coal were measured during combustion of commercial high chlorine content coal in a stove. A pronounced effect of the temperature profile in the chimney on PCDD/F emissions was identified, suggesting formation in the chimney. Emissions of PCDD/Fs were one order of magnitude higher with an insulated chimney than with a non-insulated one. Insulation of the chimney did not influence the emissions of regulated pollutants and PAHs. Under laboratory conditions, the thermal properties of the chimney usually differ from those in residential dwellings. For that reason it is concluded that PCDD/F emission measurements performed under laboratory conditions may not be representative for derivation of emission factors in emission inventory compilations. Thus the emission factor of 1300 microg TEQ per ton of coal (40000 microg TEQ/TJ) represents the maximum value for individual stove emissions. Complementary air dispersion modelling and congener profile based receptor modelling performed in the Krakow area, Poland confirm a high contribution of the residential combustion to the ambient air PCDD/F levels in that area and indicate an emission factor for coal combustion in stoves in the order of 100 microg TEQ per ton (3000 microg TEQ/TJ).

Atmospheric input of POPs into Lake Maggiore (Northern Italy): PBDE concentrations and profile in air, precipitation, settling material and sediments.

Large lakes are sinks for many chemical pollutants but the role of the atmosphere in delivering PBDEs (polybrominated diphenyl ethers) is not well known. In this study we estimated inputs of PBDEs from the atmosphere to Lake Maggiore and the delivery via settling material to accumulated bottom sediments. Sampling consisted of one simultaneous week of air and bulk deposition during Spring 2005, an integrated 4-month period of collected settling material (via sediment trap), and superficial bottom sediments near the sediment trap deployment and tributary mouths of the lake. Concentration of total PBDEs (Sigma 8) in the sediments ranged between 0.06 and 27 ng g(-1), and two different patterns were observed. One pattern was dominated by BDE-47 and BDE-99 and a second by BDE-209. The latter pattern suggested input from local source(s). Total PBDEs in air were 107 pg m(-3) with a pattern dominated by BDE-47. The bulk deposition rate of total PBDEs for precipitation was measurated to be 17.6 ng m(-2) day(-1) where BDE-209 exhibited the highest concentration. For aquatic settling material the flux was 3.57 ng m(-2) day(-1) and was dominated by congeners BDE-47 and BDE-99. The bulk deposition and settling material fluxes were in the same range for the less brominated congeners, while for the hepta- and deca-brominated PBDEs the fluxes in the settling material were one order of magnitude lower. This suggests different sedimentation processes among congeners and/or the presence of local sources that influence the relative distribution in water column.

Atmospheric input of POPs into Lake Maggiore (Northern Italy): PCDD/F and dioxin-like PCB profiles and fluxes in the atmosphere and aquatic system.

The delivery and accumulation of PCDD/Fs and dioxin-like PCBs (DL-PCBs) as recorded in sediments from the Lake Maggiore (LM) in Northern Italy and the influence of the atmosphere in contaminating this subalpine ecosystem were studied. PCDD/Fs (17 congeners) and DL-PCBs (12 congeners) concentrations, congener profiles and fluxes in air, bulk deposition, aquatic settling material and surface sediments are presented. Our strategy was to obtain surface sediment from areas near riverine inputs and in the depositional basins, settling material in sediment traps at one site and air, aerosol and bulk deposition profiles. PCDD/F concentrations in air of 25 WHO-TEQ fg m(-3) and DL-PCBs of 7 WHO-TEQ fg m(-3) were measured. Bulk atmospheric deposition yielded 140 and 28 WHO-TEQ pg m(-2) per week for dioxins/furans and DL-PCBs, respectively. Aquatic settling material exhibited concentrations of 11 WHO-TEQ pg g(-1) for PCDD/Fs and 2 WHO-TEQ pg g(-1) for DL-PCBs. Weekly settling material fluxes of 50 WHO-TEQ pg m(-2) and 10 WHO-TEQ pg m(-2) were obtained for PCDD/Fs and DL-PCBs, respectively. PCDD/Fs concentrations in surface sediments varied from 0.1 to 17 WHO-TEQ pg g(-1) whereas values ranged from 0.03 to 6 WHO-TEQ pg g(-1) for DL-PCBs. The concentrations obtained in the environmental compartments studied suggest a situation of low level contamination. PCDD/Fs and DL-PCBs congener profiles in atmospheric air, bulk deposition, aquatic settling matter and surface sediment point to an important if not dominant contribution from atmospheric deposition to Lake Maggiore, especially derived from wet deposition of aerosol-bound PCDD/Fs and DL-PCBs. Flux estimates support this hypothesis.

PCDD/F and PCB multi-media ambient concentrations, congener patterns and occurrence in a Mediterranean coastal lagoon (Etang de Thau, France).

Ambient concentrations, congener patterns and multi-media distribution of PCDD/Fs and PCBs were determined in air, water, sediment and mussels in a semi-enclosed marine ecosystem (Thau lagoon, France). Sigma2,3,7,8-PCDD/F and sigma7ICES PCB air concentrations (0.2-1.4 and 31-57 pg m(-3), respectively) were typical of rural areas. Concentrations in the water column were very low for PCDD/Fs (163-476 fg L(-1)) and low for PCBs (138-708 pg L(-1)). PCDD/F and PCB concentrations found in surface sediment (0.15-1.6 and 2.5-33 ng g(-1) d.w., respectively) and mussel (13-21 pg g(-1) d.w. and 10-39 ng g(-1) d.w., respectively) were medium levels. PCDD/F congener patterns observed in air, water particulate phase and sediments were similar suggesting direct coupling among these compartments and atmospheric inputs of PCDD/Fs into the lagoon. Conversely, for the same set of samples, similar patterns were not observed for PCBs in the mentioned compartments.

Dioxins and dioxin-like PCBs in different fish from the river Elbe and its tributaries, Germany.

In a long-term program polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/Fs) as well as dioxin-like polychlorinated biphenyls (DL-PCBs) were analyzed in the muscle tissue of eels (Anguilla anguilla), bream (Abramis brama), European chub (Leuciscus cephalus) and ide (Leuciscus idus) from the river Elbe and its tributaries Mulde and Saale. The variation of the PCDD/F and DL-PCB concentrations in all fish samples is very large, whereby the DL-PCBs predominate in comparison to the PCDD/Fs. In the eels, the concentrations (pg WHO-TEQ/g ww) for the PCDD/Fs lie in the range of 0.48-22 and for the DL-PCBs between 8.5 and 59. In the whitefish, the concentration range is 0.48-12 for the PCDD/Fs and 1.2-14 for the DL-PCBs. Statistical analysis using relative congener patterns for PCDD/Fs allow spatial correlations to be examined for sub-populations of eels and whitefish. The results are compared to the maximum levels laid down in the European Commission Regulation (EC) No. 466/2001 and the action levels of the European Commission Recommendation 2006/88/EC. Eels caught directly after the major flood in August 2002 as well as eels near Hamburg (years 1996 and 1998) show high concentration peaks. Compared to the eels whitefish is less contaminated with PCDD/Fs and DL-PCBs.

Contamination of the alluvial plain, feeding-stuffs and foodstuffs with polychlorinated dibenzo-p-dioxins, polychlorinated dibenzofurans (PCDD/Fs), dioxin-like polychlorinated biphenyls (DL-PCBs) and mercury from the River Elbe in the light of the flood event in August 2002.

Meadow soils, feeding-stuffs and foodstuffs from the alluvial plain of the river Elbe were analyzed in respect of PCDD/Fs, DL-PCBs and mercury with a view to assessing the consequences of the extreme flood of August 2002. The PCDD/F concentrations in the soils range from 3 to 2100 ng WHO-TEQ/kg dm, and for the DL-PCBs the range was 0.32 to 28 ng WHO-TEQ/kg dm. On the basis of established threshold values >40% of the areas are only fit for restricted usage. Mercury concentrations range from 0.11 to 17 mg/kg dm, whereby the action value of 2 mg/kg dm is exceeded in about 50% of the soil samples. A cumulative memory effect from past floods rather than a recent contamination from August 2002 is documented. Soils taken from behind broken dykes showed significantly lower concentrations. Grass, hay and grass silage originating from pasture land in Lower Saxony were taken before and immediately after the flooding. PCDD/Fs range from 0.29 to 16 ng WHO-TEQ/kg, the maximum permitted value of 0.75 ng WHO-TEQ/kg was exceeded in about 50% of the samples. Muscle-tissue from cattle, sheep, lamb and a roe deer as well as untreated milk from individual cows returned values ranging from 0.76 to 5.9 pg WHO-PCDD/F-TEQ/g fat, and 10% of the samples returned values higher than the permitted maximum of 3 pg WHO-PCDD/F-TEQ/g fat. The action value of 2 pg WHO-PCDD/F-TEQ/g fat was exceeded in 33% of the samples. No direct connection between these results and the effects of the flood could be established. A major input path for PCDD/Fs is the tributary Mulde, which discharges contaminated sediments from its catchment area into the Elbe.

Dioxin contamination in food. Bayreuth, Germany, from September 28 to October 1, 2000.

Dioxin and PCB monitoring programs for food and feeding stuff in most countries of the world, including many European Countries are currently inadequate. Better control of food production lines and food processing procedures is needed to minimize entry of dioxin to the food chain and will help to avoid dioxin contamination accidents. This would also improve the ability to trace back a possible contamination to its source. European guidelines for monitoring programs should be established to ensure comparable and meaningful results. These guidelines should define the minimum requirements for the design of monitoring programs, analytical methods, and quality assurance. Though data from Northern Europe shows that the general population exposure to dioxin and PCB has decreased during the last ten years these compounds continue to be a risk of accidental contamination of the food chain. The most prominent recent example is the Belgian dioxin contamination of feeding stuff in 1999. The Belgian dioxin contamination was not detected due to dioxin monitoring programs but by their direct biological effects seen in animals. Four other cases of dioxin contamination have been detected in Europe since 1997 due to local monitoring programs. One of them (citrus pulp pellets 1998) was in a much larger scale than the Belgian dioxin contamination. The general population's exposure to dioxins and PCBs is still in the same range (1-4 pg WHO-TEQ/kg body weight and day) as the recently revised WHO tolerable daily intake (TDI). There is concern that short-term high level exposure to dioxins, furans, and PCB may cause biological effects on the human fetal development and further research is required. Further actions to control sources building on considerable advances already made in many countries may need to be supplemented by measures to prevent direct contamination of feeding stuff or food to reduce general population exposure further.

Deposition of semivolatile organic compounds to spruce needles : I. Calculation of dry and wet fluxes.

The deposition of atmospheric tetrachlorobenzene, pentachlorobenzene, hexachlorobenzene, α-HCH, γ-HCH, DDT, DDE and the PCB congeners 52, 101, 138, 153 and 180 to spruce needles (Picea abies) was estimated for a period of 9 months. Accumulation in spruce as a result of dry gaseous deposition, particle bound deposition and wet deposition was calculated on the basis of the corresponding deposition rates and the compounds' concentrations in the different atmospheric compartments. The comparison of the calculated values with the concentrations of the compounds measured in 9-month-old spruce needles showed that for many compounds each deposition pathway could explain a large part of the concentrations found in the needles.

Deposition of semivolatile organic compounds to spruce needles : I. Calculation of dry and wet fluxes.

The deposition of atmospheric tetrachlorobenzene, pentachlorobenzene, hexachlorobenzene,α-HCH,gg-HCH, DDT, DDE and the PCB congeners 52, 101, 138, 153 and 180 to spruce needles (Picea abies) was estimated for a period of 9 months. Accumulation in spruce as a result of dry gaseous deposition, particle-bound deposition and wet deposition was calculated on the basis of the corresponding deposition rates and the compounds' concentrations in the different atmospheric compartments. The comparison of the calculated values with the concentrations of the compounds measured in 9-month-old spruce needles showed that for many compounds each deposition pathway could explain a large pan of the concentrations found in the needles.

Deposition of semivolatile organic compounds to spruce needles : II. Experimental evaluation of the relative importance of different pathways.

The accumulation of atmospheric HCB, Lindane, DDT, DDE and the PCB congeners 52, 101, 138, 153 and 180 in spruce needles (Picea abies) was investigated at outdoor locations and in greenhouses supplied with ambient air. The air supply of the greenhouses was modified to dinstinguish between gaseous and particle-associated deposition of the compounds. Accumulation of the compounds occurred in all spruce except those grown in the greenhouse where the gaseous concentration of the compounds was reduced. Spruce grown in the greenhouse supplied with particle-free ambient air behaved similarity to those grown outdoors. Protecting the spruce located outdoors from rain did not affect the accumulation. The results show that under spring and summer conditions at a typical central European rural environment dry gaseous deposition is the dominant pathway of these compounds to needles.