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.     

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.     

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.     

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.     

Particle-size distribution and gas/particle partitioning of atmospheric polybrominated diphenyl ethers in urban areas of Greece

Ambient concentrations, gas/particle partitioning and particle-size distribution of polybrominated diphenyl ethers (PBDEs) were investigated in two urban areas (Athens and Heraklion) of Greece. Atmospheric (gas + particle) concentrations of ∑PBDE varied from 21 to 30 pg m⁻³ in the center of Athens and from 4 to 44 pg m⁻³ in the suburbs of Heraklion. A predominance of particulate PBDEs was observed in Athens (71-76% in particles), whereas the opposite was evident in Heraklion (69-92% in gas phase). In both urban areas, PBDE particle-size distribution featured a distinct enrichment in smaller particles. A similar trend was also observed in aerosols of a background marine site. For all sampling sites, more than 46% of ∑PBDE was associated with particles of <0.57 μm in diameter. Our results imply that particulate PBDEs may have long atmospheric residence time and they may be capable of reaching the deeper parts of the human respiratory system.     

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.     

Passive air monitoring of PCBs and PCNs across East Asia: a comprehensive congener evaluation for source characterization

A comprehensive congener specific evaluation of polychlorinated biphenyls (PCBs) and polychlorinated naphthalenes (PCNs) in the atmosphere was conducted across East Asia in spring 2008, applying polyurethane foam (PUF) disk passive air sampler (PAS) as monitoring device. Mean concentrations derived for Japan, China and Korea were 184 ± 24, 1100 ± 118, and 156 ± 20 pg m⁻³ for ∑₂₀₂ PCBs, and 9.5 ± 1.5, 61 ± 6, and 16 ± 2.4 pg m⁻³ for ∑₆₃ PCNs, respectively. Relative to reported data from 2004, the present results suggest that air PCBs concentrations have not changed much in Japan and Korea, while it has increased by one order of magnitude in China. From principal component analysis, combustion emerged highly culpable in contemporary emissions of both PCBs and PCNs across the East Asian sub-region. Another factor derived as important to air PCBs was re-emissions/volatilization. Signals from PCBs formulations were also picked, but their general importance was virtually consigned to the re-emissions/volatilization tendencies. On the contrary, counterpart PCNs formulations did not appear to contribute much to air PCNs.     

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.     

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 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.     

Monitoring of environmental contaminants in raw bovine milk and estimates of dietary intakes of children in South Korea

Persistent organic pollutants (POPs) are ubiquitous residual contaminants in the environment and in the food chain. Milk is an important matrix for monitoring POP contamination. This study determined the concentrations of POPs including polybrominated diphenyl ethers (PBDEs), hexachlorobenzene (HCB), polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), and dioxin-like polychlorinated biphenyls (DL-PCBs) in raw bovine milk, and the data was used to estimate dietary intakes in South Korea. The average concentrations of PBDEs, HCB, PCDD/Fs, and DL-PCBs in raw milk were 0.29 ng g⁻¹ fat, 0.50 ng g⁻¹ fat, 0.27 pg TEQ g⁻¹ fat, and 0.33 pg TEQ g⁻¹ fat, respectively. No significant relationship was found between the concentrations of analytes and the regions sampled. The dietary intakes of PBDEs from the consumption of milk was calculated to be 0.26, 0.10, and 0.05 ng kg⁻¹ bw d⁻¹ for the group of ages 0–6, 7–12, and 13–19, respectively. The dietary intakes of HCB was calculated to be 0.44, 0.16, and 0.09 ng kg⁻¹ bw d⁻¹ for the group of ages 0–6, 7–12, and 13–19, respectively. The dietary intakes of PCDD/Fs and DL-PCBs was calculated to be 0.78, 0.29, and 0.16 pg TEQ kg⁻¹ bw d⁻¹ for the group of ages 0–6, 7–12, and 13–19, respectively. These results indicated that the residual levels of PBDEs, HCB, PCDD/Fs, and DL-PCBs in raw bovine milk were within safe levels.     

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.     

Vapor-phase concentrations of PAHs and their derivatives determined in a large city: Correlations with their atmospheric aerosol concentrations

Thirteen PAHs, five nitro-PAHs and two hydroxy-PAHs were determined in 55 vapor-phase samples collected in a suburban area of a large city (Madrid, Spain), from January 2008 to February 2009. The data obtained revealed correlations between the concentrations of these compounds and a series of meteorological factors (e.g., temperature, atmospheric pressure) and physical–chemical factors (e.g., nitrogen and sulfur oxides). As a consequence, seasonal trends were observed in the atmospheric pollutants. A “mean sample” for the 14-month period would contain a total PAH concentration of 13 835 ± 1625 pg m⁻³ and 122 ± 17 pg m⁻³ of nitro-PAHs. When the data were stratified by season, it emerged that a representative sample of the coldest months would contain 18 900 ± 2140 pg m⁻³ of PAHs and 150 ± 97 pg m⁻³ of nitro-PAHs, while in an average sample collected in the warmest months, these values drop to 9293 ± 1178 pg m⁻³ for the PAHs and to 97 ± 13 pg m⁻³ for the nitro-PAHs. Total vapor phase concentrations of PAHs were one order of magnitude higher than concentrations detected in atmospheric aerosol samples collected on the same dates. Total nitro-PAH concentrations were comparable to their aerosol concentrations whereas vapor phase OH-PAHs were below their limits of the detection, indicating these were trapped in airborne particles.     

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.     

PCDDs/PCDFs in ambient air (<1 fg m(-3)) - the CTDEP long term sampling (30 d) method

The Connecticut Department of Environmental Protection (CTDEP) commenced monitoring for PCDDs/PCDFs (polychlorinated dibenzodioxins and polychlorinated dibenzofurans) in ambient air in 1987 and adopted the long term (30 d) sampling approach in 1993. The CTDEP method represents the first use of isotopically labeled PCDDs/PCDFs as field surrogates to monitor the behavior of native PCDDs/PCDFs present in actual ambient air samples. This feature first introduced in 1987 was later adopted by US EPA in revisions to sampling methods for PCDDs/PCDFs in ambient air (EPA Method TO9A) as well as development of EPA Reference Method 23 for measurement of PCDDs/PCFDs in stationary source emissions. Results are provided here for a total of twenty-three (23) samples (reported as pairs) representing twelve (12) 30 d sampling events conducted at a site located in metropolitan Hartford CT. Samples were collected in winter months during calendar years 2002-2008. PCDDs/PCDFs concentration data (pg m⁻³) are reported as both congener sums (Cl₄-Cl₈) and 2378-substitued congeners. Total PCDDs/PCDFs concentrations for these twelve (12) sampling events ranged from 0.68 pg m⁻³ (2003) to 4.18 pg m⁻³ (2004) with a mean concentration of 2.04 pg m⁻³.Method performance was monitored through use of collocated samples, in field isotopically labeled compounds, isotopically labeled laboratory applied internal standards and field blank samples. Method performance consistently exceeded goals established in USEPA Method TO9A for these same parameters. Average recoveries of in field labeled PCDDs/PCDFs ranged from 97.5% to 104.2%. Average (mean) recoveries for each of the ten (10) isotopically labeled internal standards ranged from 77.0% (¹³C-OCDF) to 95.5% (¹³C-2,3,7,8-TCDF). Method precision defined as % RPD data for collocated sampler pairs ranged from 8% to 14% for PCDDs and from 5% to 12% for PCDFs. The mean RPD for all PCDDs/PCDFs combined is 9.6%. Field monitoring results demonstrate method sensitivity for all PCDDs/PCDFs congeners and 2378-substituted congeners to be well below concentrations typically found for these compounds in ambient air (all reported data represent measured concentrations). Quantities (pg) found in field blanks represent the major determinant to achieving further enhancements in method sensitivity for selected congeners (OCDD < 42 fg m⁻³; 1,2,3,4,6,7,8-HpCDD < 5.7 fg m⁻³; and 1,2,3,4,6,7,8-HpCDF < 2.1 fg m⁻³). The CTDEP method represents a highly sensitive and reliable technique for monitoring of PCDDs/PCDFs congeners and other persistent organic pollutants (POPs) at ultra trace levels in ambient air (fg m⁻³).     

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.     

Atmospheric mercury pollution at an urban site in central Taiwan: mercury emission sources at ground level

Total gaseous mercury (Hg) (TGM), gaseous oxidized Hg (GOM), and particulate-bound Hg (PBM) concentrations and dry depositions were measured at an urban site in central Taiwan. The concentrations were 6.14 ± 3.91 ng m⁻³, 332 ± 153, and 71.1 ± 46.1 pg m⁻³, respectively. These results demonstrate high Hg pollution at the ground level in Taiwan. A back trajectory plot shows the sources of the high TGM concentration were in the low atmosphere (<500 m) and approximately 50% of the air masses coming from upper troposphere (>500 m) were associated with low TGM concentrations. This finding implies that Hg is trapped in the low atmosphere and comes from local Hg emission sources. The conditional probability function (CPF) reveals that the plumes of high TGM concentrations come from the south and northwest of the site. The plume from the south comes from two municipal solid waste incinerators (MSWIs). However, no significant Hg point source is located to the northwest of the site; therefore, the plumes from the northwest are hypothesized to be related to the combustion of agricultural waste. Dry deposition fluxes of Hg measured at this site considerably exceeded those measured in North America. Overall, this area is regarded as a highly Hg contaminated area because of local Hg emission sources.     

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.