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.     

Levels of polybrominated diphenyl ethers and hexabromocyclododecane in the atmosphere and tree bark from Beijing, China

Air samples in four seasons at one site and tree bark samples from four districts were determined to investigate seasonal variation and regional distribution of polybrominated diphenyl ethers (PBDEs) and hexabromocyclododecane (HBCD) in Beijing, China. The total concentrations of PBDEs (∑PBDE) and HBCD (∑HBCD) were in the range of 57-470 and 20-1800 pg m⁻³ in the atmosphere, respectively. The ∑PBDE and ∑HBCD concentrations were significantly influenced by the total suspended particulate matter in atmosphere. The total concentrations of PBDEs and HBCD in tree bark samples were in the range of 99-3700 and 26-3400 ng g⁻¹ lipid weight. It was found that regional distribution of PBDEs and HBCD was related to the function of each district. In addition, the study found that weeping willow bark was an ideal atmospheric PBDEs and HBCD passive sampler. Finally, atmospheric levels of BDE-209 and HBCD at tree bark sampling districts were estimated via applying an established bark/air partitioning model, which had been verified by the measured concentrations in tree bark and atmosphere in Beijing.     

Polybrominated diphenyl ethers in various atmospheric environments of Taiwan: their levels, source identification and influence of combustion sources

In this study, ambient air samples from different atmospheric environments were examined for both PBDE and PCDD/F characteristics to verify that combustion is a significant PBDE emission source. The mean ± SD atmospheric PBDE concentrations were 165 ± 65.0 pg Nm⁻³ in the heavy steel complex area and 93.9 ± 24.5 pg Nm⁻³ in the metals complex areas, 4.7 and 2.7 times higher than that (35.3 ± 15.5 pg Nm⁻³) in the urban areas, respectively. The statistically high correlation (r = 0.871, p < 0.001) found between the atmospheric PBDE and PCDD/F concentrations reveals that the combustion sources are the most likely PBDE emission sources. Correspondence analysis shows the atmospheric PBDEs of the heavy steel and metals complex areas are associated with BDE-209, -203, -207, -208, indicative of combustion source contributions. Furthermore, the PBDEs in urban ambient air experience the influence of the evaporative releases of the commercial penta- and octa-BDE mixtures, as well as combustion source emissions. By comparing the PBDE homologues of indoor air, urban ambient air, and stack flue gases of combustion sources, we found that the lighter brominated PBDEs in urban ambient air were contributed by the indoor air, while their highly brominated ones were from the combustion sources, such as vehicles. The developed source identification measure can be used to clarify possible PBDE sources not only for Taiwanese atmosphere but also for other environmental media in other countries associated with various emission sources in the future.     

Pollution characterization and diurnal variation of PBDEs in the atmosphere of an E-waste dismantling region

Diurnal air samples were collected from the E-waste dismantling region Guiyu and the underwear industry region Chendian. This was the first report to present the diurnal variation of PBDEs in the atmosphere. The average concentrations of 11 PBDE congeners were 11,742 pg m⁻³ in the daytime, and 4830 pg m⁻³ at night in Guiyu, while the concentrations were lower in Chendian with 376 pg m⁻³ in the daytime, and 237 pg m⁻³ at night. BDE-209 accounted for 22% and 31.3% of the total PBDEs in Guiyu and Chendian, respectively. The diurnal variation trends of BDE-47, -99, -153, -183, and -209 were also analyzed in detail in the two regions.     

Method optimization to measure polybrominated diphenyl ether (PBDE) concentrations in soils of Bratislava, Slovakia

We modified an analytical method to determine polybrominated diphenyl ethers (PBDEs) in urban soils of Bratislava (Slovakia). Gel permeation chromatography (GPC) introduced as a clean-up step for soil extracts substantially reduced matrix enhancements when PBDEs were measured with gas chromatography-negative chemical ionization-mass spectrometry (GC-NCI-MS). The resulting method proved to be accurate, precise, and showed low detection limits. The sum of 15 PBDE concentrations in surface horizons of Bratislava soils ranged from 87 to 627 pg g⁻¹. PBDE concentrations were mostly higher in surface than deeper horizons probably because of atmospheric deposition and lack of substantial vertical transport. Lower brominated PBDEs undergo more soil-atmosphere exchanges or are more scavenged and transferred with litter fall to the soil organic matter than higher brominated ones as suggested by the correlation between lower brominated PBDEs and soil organic C (C_org) concentrations.     

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. ∑7PCBs monthly averaged concentration varied from 31 to 76 pg m⁻³. Concentrations in the gas phase (21-72 pg m⁻³) were higher than those in the particulate phase (3-10 pg m⁻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 μg m⁻² yr⁻¹ ∑7PCBs yearly total wet deposition flux; 650-2400 pg L⁻¹ rainwater concentrations).     

Levels,profile and distribution of Dechloran Plus (DP) and Polybrominated Diphenyl Ethers (PBDEs) in the environment of Pakistan

No scientific data is available on emerging contaminants including Polybrominated Diphenyl Ethers (PBDEs) and Dechloran Plus (DP) levels in the environment in Pakistan. Levels of PBDEs and DP were determined in the soil, sediment and atmospheric samples along the stretch of River Ravi in Punjab Province. Average concentrations of ΣPBDEs in atmosphere, soils and sediments were 36 pg m⁻³, 40 ng g⁻¹ and 640 ng g⁻¹. BDE-209 was the most abundant PBDE congener, showing that deca-BDE accounts for most of the total PBDE emitted in the environment of Pakistan. Total DP levels were calculated as 88 pg m⁻³, 0.8 ng g⁻¹ and 1.9 ng g⁻¹ in air, soil and sediment samples, respectively. The lower average fractions of anti-DP showed significant differences to those of the technical mixtures, indicating the lack of DP production source in Pakistan.     

Evaluation of atmospheric sources of PCDD/Fs, PCBs and PBDEs around a steel industrial complex in northeast China using passive air samplers

The concern about emissions of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) polychlorinated biphenyls (PCBs), and polybrominated diphenyl ethers (PBDEs) from steel industrial parks has increased in the past decades. In this study, polyurethane foam (PUF)-disk based passive air samples were collected in and around a big steel industrial park of Anshan, Northeast China from June 2008 to March 2009. The levels, seasonal variations and potential sources of PCDD/Fs, PCBs and PBDEs in the atmosphere around the steel industrial complex were investigated, and potential contribution of these three groups of persistent organic pollutants (POPs) from iron and steel production was also assessed. The air concentrations of ∑₁₇PCDD/Fs (summer: 0.02-2.77 pg m⁻³; winter: 0.20-9.79 pg m⁻³), ∑₁₉PCBs (summer: 23.5-155.8 pg m⁻³; winter: 14.6-81.3 pg m⁻³) and ∑₁₃PBDEs (summer: 2.91-10.7 pg m⁻³; winter: 1.10-3.89 pg m⁻³) in this targeted industrial park were relatively low in comparison to other studies, which implied that the industrial activities of iron and steel had not resulted in serious contamination to the ambient air in this area. On the whole, the air concentrations of PCDD/Fs in winter were higher than those of summer, whereas the concentrations of PCBs and PBDEs showed opposite trends. The result from principal component analysis indicated that coal combustion might be the main contributor of PCDD/F sources in this area.     

Polyfluorinated compounds in the atmosphere along a cruise pathway from the Japan Sea to the Arctic Ocean

Neutral polyfluorinated alkyl substances (PFASs) were measured in high-volume air samples collected on board the research vessel Snow Dragon during the 4th Chinese National Arctic Expedition from the Japan Sea to the Arctic Ocean in 2010. Four volatile and semi-volatile PFASs (fluorotelomer alcohols (FTOHs), fluorotelomer acids (FTAs), perfluoroalkyl sulfonamides (FASAs), and sulfonamidoethanols (FASEs)) were analyzed respectively in the gas and particle phases. FTOHs were the dominant PFASs in the gas phase (61-358 pg m⁻³), followed by FTAs (5.2-47.9 pg m⁻³), FASEs (1.9-15.0 pg m⁻³), and FASAs (0.5-2.1 pg m⁻³). In the particle phase, the dominant PFAS class was FTOHs (1.0-9.9 pg m⁻³). The particle-associated fraction followed the general trend of FASEs > FASAs > FTOHs. Compared with other atmospheric PFAS measurements, the ranges of concentrations of ∑FTOH in this study were similar to those reported from Toronto, north America (urban), the northeast Atlantic Ocean, and northern Germany. Significant correlations between FASEs in the gas phase and ambient air temperature indicate that cold surfaces such as sea-ice, snowpack, and surface seawater influence atmospheric FASEs.     

Atmospheric organochlorine pesticide (OCP) levels in a metropolitan city in Turkey

Air concentrations of organochlorine pesticides (OCPs) were measured at four different sites in Bursa, Turkey to determine current levels. For this purpose, about 35 samples were collected from June 2008 to June 2009 using a high volume air sampler (HVAS) equipped with particle and gas-phase units. Ten OCP compounds (alpha-, beta-, gamma-, delta-hexachlorocyclohexane, Heptachlor epoxide, Endrin, Endosulfan beta, Endrin aldehyde, p,p′-DDT and Methoxychlor) were reported within the scope of this study. The average concentrations of total (particle + gas) ∑OCPs were 550.9 ± 277.6 pg m⁻³ (coastal), 1030.7 ± 453.5 pg m⁻³ (urban/traffic), 519.7 ± 277.5 pg m⁻³ (semi-rural) and 722.8 ± 351.8 pg m⁻³ (urban/residential). The individual OCP concentrations were in line with reported concentrations. The maximum particle and gas-phase concentrations were determined for Endosulfan beta and beta-HCH for all sites, respectively. Available gas/particle partitioning models were applied in order to investigate the compatibility of the experimental data and the significant relationships were observed.     

Polybrominated diphenyl ethers in food and associated human daily intake assessment considering bioaccessibility measured by simulated gastrointestinal digestion

The concentrations of PBDEs in 299 vegetable and animal-based food samples of 31 species, collected in Shanghai, China, and the bioaccessibility of PBDEs in part of the samples were determined. The PBDE concentrations ranged from 0 to 1245.4 pg g⁻¹ with animal-based food containing more PBDEs than vegetables. The bioaccessibility of PBDEs, determined by a method simulating human gastrointestinal digestion process, were from 2.6% to 39.9% in vegetables, and from 5.2% to 105.3% in animal-based food. For animal-based food, good correlations were observed between the bioaccessibility of PBDEs and the fat content, thus the fat content in animal-based food was able to be used to estimate the bioaccessibility of PBDEs. The total daily intake of PBDEs via ingestion of vegetables and animal-based food for an average Shanghai resident was estimated as 13 235.7 and 13 668.0 pg d⁻¹, respectively, but the amounts available for human absorption were reduced to 2674.4 and 4316.6 pg d⁻¹ after the PBDE bioaccessibility was considered. Finally, the contributions of different food groups to the total daily intake of PBDEs were evaluated. The results revealed that, when not considering the bioaccessibility of PBDEs, vegetables were the leading contributor (49.2%), followed by fish (34.0%). However, the sequence was reversed after the PBDE bioaccessibility was taken into account. The results indicated that human exposure to PBDEs via food ingestion might have been significantly overestimated and the exposure assessment could be misleading if the bioaccessibility of PBDEs was not considered.     

Waste water treatment plants as sources of polyfluorinated compounds, polybrominated diphenyl ethers and musk fragrances to ambient air

To investigate waste water treatment plants (WWTPs) as sources of polyfluorinated compounds (PFCs), polybrominated diphenyl ethers (PBDEs) and synthetic musk fragrances to the atmosphere, air samples were simultaneously taken at two WWTPs and two reference sites using high volume samplers. Contaminants were accumulated on glass fiber filters and PUF/XAD-2/PUF cartridges, extracted compound-dependent by MTBE/acetone, methanol, or hexane/acetone and detected by GC-MS or HPLC-MS/MS. Total (gas + particle phase) concentrations ranged from 97 to 1004 pg m⁻³ (neutral PFCs), <MQL to 13 pg m⁻³ (ionic PFCs), 5781 to 482,163 pg m⁻³ (musk fragrances) and <1 to 27 pg m⁻³ (PBDEs) and were usually higher at WWTPs than at corresponding reference sites, revealing that WWTPs can be regarded as sources of musk fragrances, PFCs and probably PBDEs to the atmosphere. Different concentrations at the two WWTPs indicated an influence of WWTP size or waste water origin on emitted contaminant amounts.     

Detection of Dechlorane Plus and brominated flame retardants in marketed fish in Japan

Fish samples purchased from Japanese markets were analyzed for Dechlorane Plus (DP)(syn-, anti-), polybrominated diphenyl ether (PBDE), and hexabromocyclododecane (HBCD)(α, γ). Twenty fish were analyzed using gas chromatography-mass spectrometry for DP and PBDE, and using liquid chromatography-tandem mass spectrometry for HBCD. DP was detected in 18 samples and ∑DP concentrations were <0.2-14.2 pg g⁻¹ wet wt. Among the DP isomers, anti-DP was the dominant residue observed in this study. PBDE was detected in all samples. Concentrations of ∑PBDE ranged from 2.2 to 878 pg g⁻¹ wet wt. HBCD was detected in 18 samples, and ∑HBCD concentrations were <0.02-21.9 ng g⁻¹ wet wt. In fish landed near the East China Sea and the Sea of Japan, we detected relatively high concentrations of DP, PBDE, and HBCD. These results indicate that the seawaters around East Asia are contaminated with flame retardants. This study demonstrates the presence of DP in fish marketed in Japan for the first time.     

Dry deposition and soil-air gas exchange of polychlorinated biphenyls (PCBs) in an industrial area

Ambient air and dry deposition, and soil samples were collected at the Aliaga industrial site in Izmir, Turkey. Atmospheric total (particle + gas) ∑₄₁-PCB concentrations were higher in summer (3370 ± 1617 pg m⁻³, average + SD) than in winter (1164 ± 618 pg m⁻³), probably due to increased volatilization with temperature. Average particulate ∑₄₁-PCBs dry deposition fluxes were 349 ± 183 and 469 ± 328 ng m⁻² day⁻¹ in summer and winter, respectively. Overall average particulate deposition velocity was 5.5 ± 3.5 cm s⁻¹. The spatial distribution of ∑₄₁-PCB soil concentrations (n = 48) showed that the iron-steel plants, ship dismantling facilities, refinery and petrochemicals complex are the major sources in the area. Calculated air-soil exchange fluxes indicated that the contaminated soil is a secondary source to the atmosphere for lighter PCBs and as a sink for heavier ones. Comparable magnitude of gas exchange and dry particle deposition fluxes indicated that both mechanisms are equally important for PCB movement between air and soil in Aliaga.     

Levels of PCDD/Fs,PCBs and PBDEs in breast milk of women living in the vicinity of a hazardous waste incinerator: Assessment of the temporal trend

The concentrations of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs) were determined in breast milk from women living in the vicinity of a hazardous waste incinerator (HWI) in Catalonia, Spain. The results were compared with the levels obtained in previous surveys carried out in the same area in 1998 (baseline study), 2002 and 2007. The current total concentrations of 2,3,7,8-chlorinated PCDD/Fs in breast milk ranged from 18 to 126 pg g⁻¹ fat (1.1–12.3 pg WHO₂₀₀₅-TEQ_PCDD/F), while the total levels of PCBs ranged from 27 to 405 pg g⁻¹ fat (0.7–5.3 pg WHO₂₀₀₅-TEQ_PCB). In turn, PBDE concentrations (sum of 15 congeners) ranged 0.3–5.1 g g⁻¹ fat, with a mean value of 1.3 ng g⁻¹ fat. A general decrease in the concentrations for PCDD/Fs, both planar and total PCBs, and PBDEs in breast milk was observed. The levels of PCDD/Fs, PCBs, and PBDEs in milk of women living in urban zones were higher than those corresponding to industrial zones (41%, 26%, and 8%, respectively). For PCDD/Fs and PCBs, the current decreases are in accordance with the reduction in the dietary intake of these pollutants that we have also observed in recent studies carried out in the same area of study.     

Polybrominated diphenyl ethers (PBDEs) and alternative brominated flame retardants in air and seawater of the European Arctic

The spatial distribution of polybrominated diphenyl ethers (PBDEs) and several alternative non-PBDE, non-regulated brominated flame retardants (BFRs) in air and seawater and the air-seawater exchange was investigated in East Greenland Sea using high-volume air and water samples. Total PBDE concentrations (Ó₁₀PBDEs) ranged from 0.09 to 1.8 pg m⁻³ in the atmosphere and from 0.03 to 0.64 pg L⁻¹ in seawater. Two alternative BFRs, Hexabromobenzene (HBB) and 2,3-dibromopropyl-2,4,6-tribromophenyl ether (DPTE), showed similar concentrations and spatial trends as PBDEs. The air-seawater gas exchange was dominated by deposition with fluxes up to −492 and −1044 pg m⁻² day⁻¹ for BDE-47 and DPTE, respectively. This study shows the first occurrence of HBB, DPTE and other alternative flame retardants (e.g., pentabromotoluene (PBT)) in the Arctic atmosphere and seawater indicating that they have a similar long-range atmospheric transport potential (LRAT) as the banned PBDEs.     

Polybrominated diphenyl ethers (PBDEs) in soils along a rural-urban-rural transect: sources, concentration gradients, and profiles

This study reports concentrations of PBDEs in surface soil samples collected along a 140 km transect across Kuwait to assess the role of urban centers as sources of persistent organic pollutants to the surrounding environment. The ΣPBDE concentrations varied by a factor of ∼250 and ranged from 289 to 80,078 pg g⁻¹ d.w. The concentrations of PBDEs in Kuwait City were significantly higher (p < 0.01) than those collected from sites outside the city supporting the hypothesis that urban centers are sources of PBDEs. The congener profiles were dominated by BDE-209, accounting for 93% of the PBDEs in the soil samples. The concentrations of all congeners (except BDE-209) were highly correlated with percent organic carbon (%OC) (p > 0.05) when the data from Kuwait City was omitted from the analysis. These findings suggest that soil concentrations outside the urban centers were close to equilibrium with the atmosphere.     

Polybrominated diphenyl ethers (PBDEs) and hexabromocyclododecane (HBCD) in seven different marine bird species from Iceland

Data on distribution, concentration and trends of polybrominated diphenyl ethers (PBDEs) and hexabromocyclododecanes (HBCDs) is scarce in biota from the sub-Arctic region of the Atlantic. The present study is an investigation on PBDE and HBCD concentrations in eggs from seven marine bird species from Iceland, i.e. common eider (Somateria mollissima), arctic tern (Sterna paradisaea), guillemot (Uria aalge), fulmar (Fulmarus glacialis), lesser black-backed gull (Larus fuscus), great black-backed gull (Larus marinus) and great skua (Stercorarius skua). Concentrations of sum PBDEs ranged from 44 ng g⁻¹ fat in eider eggs to 2400 ng g⁻¹ fat in great skua eggs. The contribution of different PBDE congeners to the sum concentration differed between species. Concentration of HBCDs (sum of α−,β⁻ and γ−HBCD) ranged from 1.3 ng g⁻¹ fat in arctic tern eggs to 41 ng g⁻¹ fat in great black-backed gull. PCA on PBDE and HBCD shows different trends between the two BFR groups, further indicating different sources/usage. Investigations on any potential health or population effects of environmental pollutants on the great skua are advised since both the PBDE and HBCD concentrations are high.     

Polychlorinated biphenyls (PCBs) and Polybrominated Diphenyl Ethers (PBDEs) in surface sediments from Monastir Bay (Tunisia,Central Mediterranean): Occurrence,distribution and seasonal variations

An assessment of PCB and PBDE contamination of surface sediments in Monastir Bay was carried out in two contrasted seasons of the year. Samples were collected from 5 sites and analyzed for the ∑₇ marker PCBs (i.e. PCBs 28, 52, 101, 118, 138, 153 and 180) and ∑₄ PBDE congeners (PBDEs 47, 99, 119 and 153) by GC/ECD. Concentrations of both PCBs and PBDEs showed seasonal variations. PCB concentrations were in the range of 3.1–9.3 ng g⁻¹ and 1.1–8.1 ng g⁻¹ in wet and dry season respectively, and sediments were considered moderately contaminated with PCBs. All PCBs analyzed were detected in surface sediments. PCB 153 and 52 congeners showed the highest relative abundance in both winter and summer. PBDE concentrations ranged from not detect to 0.1 ng g⁻¹, with only BDE-47 congener detected in sediments and only in winter. Analysis of spatial and seasonal variations indicated that PCB distribution is governed by hydrodynamics and temporal variability of inputs. While the PCB contamination appeared to be mainly land-based, PBDEs are suspected to originate from atmospheric deposition.