PBDEs in the atmosphere of three locations in western Europe

Atmospheric concentrations of PBDEs (108 samples in total) were measured at 2 rural/semirural sites in England and 1 remote site on the west coast of Ireland in the years 2001 and 2000, respectively. Detailed analysis of the factors affecting concentrations is performed. The United Kingdom (UK) has been a major producer and user of PBDEs. Concentrations of sigmaPBDEs at Mace Head (MH), Ireland ranged between 0.22 and 5.0 pg m(-3) with a mean of 2.6 pg m(-3) and were controlled primarily by advection. sigmaPBDEs concentrations at Hazelrigg (HR), northwest England, ranged between 2.8 and 37 pg m(-3) with a mean of 12 pg m(-3) and at Chilton (CH), southwest England between 3.4 and 33 pg m(-3) with a mean of 11 pg m(-3). The average mixture of PBDEs in air was similar to that of commercial penta-BDE products. Movement of air over local/regional sources influenced concentrations of PBDEs at all sites, particularly at MH. At the two English sites during the summer, concentrations of PBDEs were strongly influenced bytemperature, indicating that air-surface exchange processes play an important role. Advection became more influential during winter, particularly at CH, where a different congener profile was observed in some samples as ambient air temperatures decreased and PBDE concentrations increased. It is hypothesized that this was due to increased emissions from diffuse combustion sources.     

Polychlorinated naphthalenes in the Global Atmospheric Passive sampling (GAPS) study

Air concentrations of polychlorinated naphthalenes (PCNs) were measured as part of the Global Atmospheric Passive Sampling (GAPS) study to assess their spatial distribution on a worldwide basis for the first sampling period between December 2004 and March 2005. Results from more than 40 sites on seven continents show that PCNs are widespread, and highest levels are detected in urban/industrial locations consistent with other air sampling studies. The geometric mean air concentration of sigmaPCN is 1.6 pg/m3, ranging from below detection limit to 32 pg/m3. With technical PCN mixtures largely no longer produced, combustion inputs may be contributing increasingly to contemporary PCN air burden globally. Enrichment of combustion-related congeners, e.g., PCN-52/60, -50, -51,-54, and -66/67, is observed in the congeneric compositions of air at nearly all sites compared to relatively minor contribution of these congeners in technical PCN formulations. Further evidence of current combustion sources influencing global PCN levels is a higher relative abundance of combustion-related congeners quantified by sigmaPCNcombustion/sigmaPCN. The relative contribution by combustion sources and emissions from technical PCN mixtures is expected to vary among sites since it depends on the combustion sources and the technical mixture used in a particular country or region.     

Polychlorinated naphthalenes in Great lakes air: assessing spatial trends and combustion inputs using PUF disk passive air samplers

Passive air samplers made from polyurethane foam (PUF) disks housed in stainless steel chambers were deployed over four seasons during 2002-2003, at 15 sites in the Laurentian Great lakes, to assess spatial and temporal trends of polychlorinated naphthalenes (PCNs). Sampling rates, determined using depuration compounds pre-spiked into the PUF disk prior to exposure, were, on average, 2.9 +/- 1.1 m3 d(-1), consistent with previous studies employing these samplers. PCN air concentrations exhibited strong urban-rural differences-typically a few pg m(-3) at rural sites and an order of magnitude higher at urban sites (Toronto, 12-31 pg m(-3) and Chicago,13-52 pg m(-3)). The high concentrations at urban sites were attributed to continued emissions of historically used technical PCN. Contributions from combustion-derived PCNs seemed to be more important at rural locations where congeners 24 and 50, associated with wood and coal burning, were elevated. Congener 66/67, associated with incineration and other industrial thermal processes, was elevated at two sites and explained by nearby and/or upwind sources. Probability density maps were constructed for each site and for every integration period were shown to be a useful complement to seasonally integrated passive sampling data to resolve source-receptor relationship for PCNs and other pollutants.     

Current combustion-related sources contribute to polychlorinated naphthalene and dioxin-like polychlorinated biphenyl levels and profiles in air in Toronto,Canada

Polychlorinated naphthalenes (PCNs) and mono- and non-ortho substituted PCBs were analyzed in air from two sites in Toronto, Ontario, Canada to determine whether current combustion-related sources contribute to the levels and profiles of PCNs found in urban air. High-volume air samples were collected periodically at the University of Toronto (UT, a downtown site) and in north Toronto at the Meteorological Service of Canada (MSC). SigmaPCN concentrations ranged from 31 to 78 pg m(-3) at UT and from 7 to 84 pg m(-3) at MSC with concentrations lower at MSC than UT for paired samples. Ambient air congener profiles contrasted between the two sites with MSC profiles indicating inputs from combustion-related sources when compared to combustion fly ash and technical PCN and PCB mixture profiles. Combustion markers, including CN-44, -29, and -54, the more toxic CN-66 and -67 congeners, and non-ortho PCBs, were enriched in air at MSC on a mass percent basis in several samples. As a result, CN-66/67 contributed proportionally more to dioxin toxic equivalents at MSC than at UT. Downtown air PCN profiles resembled those of technical PCN and PCB mixtures, reflecting evaporative emissions from past uses, while PCN levels and profiles at MSC, a more industrialized location, are also influenced by current combustion sources, contributing as much as an estimated 54% of sigmaPCN in samples collected.     

Levels of PCDD/Fs, PCBs, and PCNs in soils and vegetation in an area with chemical and petrochemical industries

The concentrations of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/PCDFs), polychlorinated biphenyls (PCBs), and polychlorinated naphthalenes (PCNs) have been determined in soil and wild chard samples collected in an area of Tarragona County (Catalonia, Spain) with an important number of chemical and petrochemical industries. Samples were also collected in urban/residential zones, as well as in presumably unpolluted sites. In soils, the levels of PCDD/Fs ranged from 0.16 ng I-TEQ/kg (unpolluted sampling points) to 2.65 ng I-TEQ/kg (industrial zone), and those of sigmaPCBs ranged from 657 to 12038 ng/ kg in these same zones. In turn, sigmaPCNs ranged from 32 (unpolluted sites) to 180 ng/kg (residential/urban sites). In contrast to soil concentrations, there were not significant differences among collection zones in the levels of PCDD/Fs, PCBs, and PCNs found in chard. However, PCB and PCN concentrations in chard samples collected at the unpolluted sampling points were higher than the respective concentrations in soils. In general terms, the current concentrations of the organic pollutants analyzed in this study are similar or lower than data from previous reports in other countries.     

Seasonal and spatial variation of polychlorinated naphthalenes and non-/mono-ortho-substituted polychlorinated biphenyls in arctic air

Archived extracts of weekly air samples collected at remote arctic monitoring stations at Alert and Tagish, Canada, and Dunai Island, Russia, in 1994-1995 were combined into 4-week composites and analyzed for levels and seasonal trends of polychlorinated naphthalenes (PCNs) and non- and mono-ortho-substituted polychlorinated biphenyls (PCBs). Mean annual sigmaPCN concentrations were 0.69, 0.82, and 0.38 pg/m3 at Alert, Dunai, and Tagish, respectively. PCNs exhibited a seasonal trend at Alert and Dunai, with higher levels occurring during winter when air masses originating over Eurasia influence the high arctic and coincide with the haze period. Episodic, trans-Pacific transport impacted PCN concentrations at Tagish. A seasonal trend was not evident for the non-/mono-o-PCBs. The contrary PCN and non-/mono-o-PCB trends indicate that the sources of these two compound classes to arctic air differ, and that atmospheric transport from source regions has a greater influence on PCN levels than for non-/ mono-o-PCBs. PCNs apparently originating from combustion sources contribute to levels in winter, as indicated by the presence of combustion marker congeners, but evaporative emissions from source regions are likely the dominant source. PCNs contributed 71 and 75% of dioxin toxic equivalents (TEQ) relative to the non-/mono-o-PCBs at Alert and Dunai and 30% at Tagish during the winter months, demonstrating the toxicological importance of PCNs as a compound class relative to PCBs.     

Polychlorinated naphthalenes, -biphenyls, -dibenzo-p-dioxins, and -dibenzofurans in double-crested cormorants and herring gulls from Michigan waters of the Great Lakes

Concentrations of polychlorinated dibenzo-p-dioxins (PCDDs), dibenzofurans (PCDFs), naphthalenes (PCNs), and biphenyls (PCBs) were measured in eggs of double-crested cormorants and herring gulls collected from Michigan waters of the Great Lakes. Concentrations of PCNs in eggs of double-crested cormorants and herring gulls were in the ranges of 380-2400 and 83-1300 pg/g, wet wt, respectively. Concentrations of 2,3,7,8-substituted PCDDs and PCDFs were 10-200 times less than those of PCNs in eggs whereas those of total PCBs (380-7900 ng/g, wet wt) were 3-4 orders of magnitude greater. While the profile of PCB isomers and congeners between double-crested cormorants and herring gulls was similar, the PCN isomer profile differed markedly between these two species. PCN congeners 66/67 (1,2,3,4,6,7/1,2,3,5,6,7) accounted for greater than 90% of the total PCN concentrations in herring gulls, whereas their contribution to total PCN concentrations in double-crested cormorants ranged from 18 to 40% (mean, 31%). The ratios of concentrations of PCDDs to PCDFs were greater in herring gulls than in double-crested cormorants collected from the same locations, suggesting the ability of the former to metabolize PCDF congeners relatively rapidly. 2,3,7,8-Tetrachlorodibenzo-p-dioxin (TCDD) equivalents (TEQs) contributed by PCNs in double-crested cormorant and herring gull eggs were 2-3% of the sum TEQs of PCBs, PCDDs, PCDFs, and PCNs. PCB congener 126 (3,3',4,4',5-PeCB) accounted for 57-72% of the total TEQs in double-crested cormorant and herring gull eggs.     

Estimation and characterization of polychlorinated naphthalene emission from coking industries

Occurrence of polycyclic aromatic hydrocarbons (PAHs) during the coking process has been widely recognized. The formation of polychlorinated naphthalenes (PCNs) from PAHs during some thermal related processes has been confirmed in many studies. Thus, the coking process is assumed to be a potential source of PCNs. However, intensive investigations on PCN emissions during the coking process are lacking. In order to evaluate PCN emissions from the coking process, an intensive study comprising 11 typical coke plants was undertaken. PCNs were qualified and quantified by isotope dilution HRGC/HRMS techniques. The concentrations of PCNs in stack gas samples collected from the investigated coke plants were in the range of 1.6-91.8 ng Nm(-3) (0.08-4.23 pg TEQ Nm(-3)). The emission factors of PCNs were found to be in the range of 0.77-1.24 ng TEQ per ton of coke production. The estimated annual toxic emissions of PCNs from the global coking industry vary from 430 to 692 mg TEQs. Characteristics of the PCN profiles were dominated by the lower chlorinated homologues, with mono-CN being the most abundant homologue. According to the PCN distribution and correlations of PCN homologues, it was speculated that chlorination is possibly the dominant pathway of PCN formation during the coking process.     

Atmospheric polychlorinated naphthalenes in Ghana

A nationwide monitoring of atmospheric POPs (persistent organic pollutants) was conducted in Ghana between May and July 2010, applying polyurethane foam (PUF) disk passive air samplers (PAS). Reported here are preliminary findings on PCNs, an industrial organic contaminant currently under review for possible listing under the global chemical treaty. The present results constitute the first set of nationwide data on air PCNs from a West African country. Contrary to expectation, air PCNs levels were quite high in Ghana, at an average of 49 ± 5.4 pg/m(3). The coastal (southern) zone of Ghana appeared the most impacted, with crude open burning of waste, industrial emissions, and the harbor environment identified among possible emission factors. Tri- and tetra-CNs (the lowly chlorinated homologues) predominated in the atmosphere, altogether constituting approximately 90% of total PCN homologues composition. Increased volatilization under tropical conditions was presumed a key factor that contributed to this high atmospheric input of lowly chlorinated homologues. We further observed a significant level of fractionation of PCN homologues across the breadth of the country. The percentage composition of the lowly chlorinated homologues increased northwards, probably because of their transportation in the direction of prevailing winds. From congener profile analysis, PCN-45/36 is proposed as a possible source marker for emissions preempted by uncontrolled waste burning activities. Dioxin-like toxicity of air PCNs in Ghana was estimated to range 0.49-5.6 fg TEQ/m(3). This study brought to the fore the emerging problems of nonagricultural organohalogens that covertly might be confronting the environment in African nations like Ghana.     

Assessment of the spatial distribution of coplanar PCBs, PCNs, and PBDEs in a multi-industry region of South Korea using passive air samplers

Coplanar polychlorinated biphenyls (PCBs), polychlorinated naphthalenes (PCNs), and polybrominated diphenyl ethers (PBDEs) were sampled using polyurethane foam (PUF) disk passive air samplers (PAS) at 19 sites in a heavily industrialized region of South Korea for 6 months (January-July 2006). The levels and spatial distribution of these three chemical groups were investigated to identify potential sources and transport in the study area, which can be divided into five regions: a steel-manufacturing complex, a residential area near the steel complex, a rural area, a semi-industrial area, and a petrochemical-manufacturing complex. Air concentrations (pg x m(-3)) were estimated using an average sampling rate of 3.0 m3 x day(-1) and ranged as follows: coplanar PCBs (0.8-16), PCNs (1.7-35), and PBDEs (3.8-24). The levels of coplanar PCBs and PBDEs were found to be the highest in the steel complex, followed by the petrochemical complex and the semi-industrial area. In addition, a high level of PCNs was measured near a petrochemical-processing plant. However, the residential area near the steel complex and the rural area showed relatively low concentrations of these chemicals, suggesting that the steel and petrochemical industries are probably important sources in the study area, but these potential sources do not strongly influence the surrounding areas.     

Spatial and temporal variability in air concentrations of short-chain (C10-C13) and medium-chain (C14-C17) chlorinated n-alkanes measured in the U.K. atmosphere

Two studies were carried out on short-chain (C10-C13) and medium-chain (C14-C17) polychlorinated n-alkanes (sPCAs and mPCAs) in U.K. air samples. The first study entailed taking 20 24-h air samples with a pair of Hi-Vol air samplers at the Hazelrigg field station, near Lancaster University. These samples were carefully selected to coincide with times when air masses were predicted to have a fairly constant back trajectory for 24 h and to give a broad spectrum of different origins. The second study was a spatial survey of PCAs in the air at 20 outdoor sites in northern England and four indoor locations in Lancaster, using polyurethane foam (PUF) disk passive air samplers. Levels of the sPCAs in the Hi-Vol samples ranged from <185 to 3430 pg m(-3) (average 1130 pg m(-3)) and were higher than those previously measured at this site in 1997. Levels of the mPCAs ranged from <811 to 14500 pg m(-3) (average 3040 pg m(-3)); that is, they were higher than sPCAs. Both sPCA and mPCA air concentrations are of the same order of magnitude as PAH at this site. Back trajectory analysis showed that the history of the air mass in the 48 h prior to sampling had an important effect on the concentrations observed, with overland samples having higher levels than oceanic, implying that the U.K. is probably responsible for most of the PCAs measured in the U.K. atmosphere. Amounts of both sPCAs and mPCAs in the passive air samples followed a rural-urban gradient. PCAs appear to be released from multiple sources around the country, as a result of the diffusive, open industrial and construction use of the technical mixtures.     

Polychloronaphthalenes and other dioxin-like compounds in Arctic and Antarctic marine food webs

Here we report accumulation patterns of polychlorinated naphthalenes (PCNs), polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), polychlorinated biphenyls (PCBs), and pesticides (HCB, p,p'DDE) in polar organisms (polar bear from Alaskan Arctic and krill, sharp-spined notothen, crocodile icefish, Antarctic silverfish, Adélie penguin, South polar skua, and Weddell seal from the Ross Sea, Antarctica). PCNs, found in most of the samples, ranged from 1.5 pg/g in krill to 2550 pg/g in South polar skua on a wet weight basis. Lower chlorinated PCNs were the predominant congeners in organisms except skua and polar bear that showed similar PCN homologue patterns. PCDD/F concentrations were <90 pg/g wet wt in polar organisms; PCDD congeners showed peculiar accumulation patterns in different organisms. Correlation existed between PCN and PCB concentrations. PCB, HCF, and p,p'DDE levels were the highest in skua liver (11,150 ng/g wet wt, 345 ng/g wet wt, and 300 ng/g wet wt, respectively). Contribution of PCNs to 2,3,7,8-tetrachlorodibenzo-p-dioxin equivalents (TEQ) was negligible (<0.1%) because of the lack of most toxic congeners. The highest TEQ was found in South polar skua liver (45 pg/g, wet weight). This is the first study to document the occurrence of PCNs in Antarctic organisms. High levels of dioxin-like chemicals in skua suggest the importance of intake via diet and migration habits, thus POP detection can be useful to trace migration behavior. Moreover, POP concentrations in penguin and skua eggs prove their transfer from the mother to eggs.     

Occurrence and biomagnification of polychlorinated naphthalenes and non- and mono-ortho PCBs in Lake Ontario sediment and biota

Biota and surface sediments collected from Lake Ontario were analyzed for polychlorinated naphthalenes (PCNs) and non- and mono-ortho-substituted polychlorinated biphenyls (n/ m-o-PCBs) to compare bioaccumulation behavior of these classes of dioxin-like chemicals in a food web from the Great Lakes. Mean sigmaPCN concentrations (tri-octaCN) ranged from 14 +/- 9 pg/g in plankton to 3500 +/- 3200 pg/g (wet weight) in lake trout while sediments contained from 21 to 38 ng/g (dry weight). Principal components analysis of PCN congener patterns indicated that chlorine substitution determined which congeners favored accumulation (e.g., CN-42, -52, -60, -66, -67, and -73), while others may be subject to metabolism. The bioaccumulative congeners exhibited similar trophic magnification factors (TMFs; 1.23-1.42) and biomagnification factors (BMFs; 5.5-8.6) to the n/m-o-PCBs for the trout/weighted diet relation, although BMFs for a benthic feeding relationship (slimy sculpin/Diporeia) indicated that the n/m-o-PCBs were more bioavailablethroughthe benthic pathway. PCNs contribute significantly to the burden of dioxin-like compounds in Lake Ontario biota, contributing between 12 and 22% of total PCN + PCB TEQ in lake trout and up to 69% in benthic organisms.     

Air-surface exchange of polybrominated diphenyl ethers and polychlorinated biphenyls

Air and leaf-litter samples were collected from a rural site in southern Ontario under meteorologically stable conditions in the early spring, prior to bud burst, over a three-day period to measure the simultaneous diurnal variations in polybrominated diphenyl ethers (PBDEs) and polychlorinated biphenyls (PCBs). PBDEs are used in a wide range of commercial products as flame retardants and are being assessed internationally as potential persistent organic pollutants. Total PBDE concentrations in the air ranged between 88 and 1250 pg m(-3), and were dominated primarily by the lighter congeners PBDEs 17, 28, and 47, and concentrations of total PCBs ranged between 96 and 950 pg m(-3), and were dominated by the lower chlorinated (tri- to tetra-) congeners. Slopes of Clausius-Clapeyron plots indicate that both PCBs and PBDEs are experiencing active air-surface exchange. Fugacities were estimated from concentrations in the air and leaf-litter and suggest near equilibrium conditions. Following the three-day intensive sampling period, 40 air samples were collected at 24-hour intervals in an attempt to evaluate the effect of bud burst on atmospheric concentrations. Total PBDE concentrations in the daily air samples ranged between 10 and 230 pg m(-3), and were dominated by the lighter congeners PBDE 17, 28, and 47, whereas concentrations of total PCBs ranged between 30 and 450 pg m(-3) during this period. It is hypothesized thatthe high PBDE concentrations observed at the beginning of the sampling period are the result of an "early spring pulse" in which PBDEs deposited in the snowpack over the winter are released with snowmelt, resulting in elevated concentrations in the surface and air. Later in the sampling period, following bud burst, PBDE concentrations in air fell to 10 to 20 pg m(-3), possibly due to the high sorption capacity of this freshly emerging foliage compartment.     

Temperature dependence of the air concentrations of polychlorinated biphenyls and polybrominated diphenyl ethers in a forest and a clearing

Polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs) were quantified in 67 high volume air samples taken concurrently in a forest and a clearing in southern Ontario, Canada from October 2001 to November 2002. Air concentrations were comparable between the two sites. Gaseous PCBs ranged from 6.4 to 150 pg x m(-3), and gaseous PBDEs ranged from below method detection limit (BDL) to 55 pg x m(-3) (with two extreme events up to 290 pg x m(-3)). Particulate PBDEs ranged from BDL to 40 pg x m(-3). Gaseous concentrations of PCBs and PBDEs were highly temperature dependent, suggesting a relatively strong influence of re-evaporation. Air concentrations of highly chlorinated PCBs in the forest were more temperature dependent than those in the clearing, whereas no difference was observed for the less-chlorinated PCBs. Forest filtering may have enriched highly chlorinated PCBs in the forest soil relative to the soil in the clearing, resulting in a higher contribution of re-evaporation for highly chlorinated PCBs at the forest. Compared to measurements conducted a decade earlier at a nearby site, PCB air concentrations were generally less temperature dependent, indicative of a reduction in the contribution of re-evaporation in the region. Furthermore, a significant correlation was found between temperature dependence and degree of chlorination, which had not been apparent in the previous study. This is presumably because depuration from soils occurred slower for highly chlorinated PCBs, resulting in their relatively higher abundance in terrestrial surfaces and, therefore, higher contribution from re-evaporation. Contrasting with the PCBs, the temperature dependence of PBDE air concentrations did not differ between congeners or between forest and clearing site. This could be a result of different usage and emission history: PCBs were banned approximately three decades ago, whereas PBDEs are currently still in use. Consequently, the influence of primary emissions on air concentrations is expected to be more important for PBDEs than for PCBs.     

Wastewater treatment plant and landfills as sources of polyfluoroalkyl compounds to the atmosphere

Polyfluoroalkyl compounds (PFCs) were determined in air around a wastewater treatment plant (WWTP) and two landfill sites using sorbent-impregnated polyurethane foam (SIP) disk passive air samplers in summer 2009. The samples were analyzed for five PFC classes (i.e., fluorotelomer alcohols (FTOHs), perfluorooctane sulfonamides (FOSAs), sulfonamidoethanols (FOSEs), perfluoroalkyl sulfonic acids (PFSAs), and perfluoroalkyl carboxylic acids (PFCAs)) to investigate their concentration in air, composition and emissions to the atmosphere. ∑PFC concentrations in air were 3-15 times higher within the WWTP (2280-24?040 pg/m(3)) and 5-30 times higher at the landfill sites (2780-26?430 pg/m(3)) compared to the reference sites (597-1600 pg/m3). Variations in the PFC pattern were observed between the WWTP and landfill sites and even within the WWTP site. For example, FTOHs were the predominant PFC class in air for all WWTP and landfill sites, with 6:2 FTOH as the dominant compound at the WWTP (895-12?290 pg/m(3)) and 8:2 FTOH dominating at the landfill sites (1290-17?380 pg/m(3)). Furthermore, perfluorooctane sulfonic acid (PFOS) was dominant within the WWTP (43-171 pg/m(3)), followed by perfluorobutanoic acid (PFBA) (55-116 pg/m(3)), while PFBA was dominant at the landfill sites (101-102 pg/m(3)). It is also noteworthy that the PFCA concentrations decreased with increasing chain length and that the emissions for the even chain length PFCAs outweighed emissions for the odd chain length compounds. Furthermore, highly elevated PFC concentrations were found near the aeration tanks compared to the other tanks (i.e., primary and secondary clarifier) and likely associated with increased volatilization during aeration that may be further enhanced through aqueous aerosol-mediated transport. ∑PFC yearly emissions estimated using a simplified dispersion model were 2560 g/year for the WWTP, 99 g/year for landfill site 1, and 1000 g/year for landfill site 2. These results highlight the important role of WWTPs and landfills as emission sources of PFCs to the atmosphere.     

Passive-sampler derived air concentrations of persistent organic pollutants on a north-south transect in Chile

Passive air samplers consisting of polyurethane foam (PUF) disks, were deployed in six locations in Chile along a north-south transect to investigate gas-phase concentrations of polychlorinated biphenyls (PCBs), organochlorine pesticides (OCPs), and polybrominated diphenyl ethers (PBDEs). The study provides new information on air concentrations of these persistent organic pollutants (POPs) which is lacking in this region. It also provides insight into potential sources and long-range transport (LRT). The samplers were deployed for a 2-month period in five remote sites and one site in the city of Concepción. Mean concentrations (pg m(-3)) for sigmaPCB were 4.7 +/- 2.7 at remote sites and 53 +/- 13 in Concepción. PCB levels at remote sites were related to proximity to urban source regions and/or air back trajectories. With the exception of endosulfan I, mean concentrations (pg m(-3)) of OCPs at background sites were consistently low: 5.4 +/- 1.4 for alpha-HCH, 7.0 +/- 1.1 for gamma-HCH, 2.5 +/- 0.5 for TC, 2.5 +/- 0.6 for CC, 1.9 +/- 1.2 for dieldrin, and less than 3.5 for toxaphene. Endosulfan I showed a decreasing concentration gradient from 99 to 3.5 pg m(-3) from the north to south of Chile. Concentrations of OCPs in the Concepción City were generally 10-20 times higher than at the background sites suggesting continued usage and/or re-emission from past use. For instance, at remote sites, the alpha/gamma ratio (0.76) was typical of background air, while the ratio in Concepción (0.12) was consistent with fresh use of gamma-HCH. Levels of sigmaPBDEs were below the detection limit of 6 pg m(-3) at all sites.     

Spatial distribution of polybrominated diphenyl ethers in southern Ontario as measured in indoor and outdoor window organic films

Organic films were collected from indoor and outdoor window surfaces, along an urban-rural transect extending northward from Toronto, Ontario, Canada, and analyzed for 41 polybrominated diphenyl ether congeners (PBDE). For exterior films, urban sigmaPBDE concentrations were approximately 10x greater than rural concentrations, indicating an urban-rural gradient and greater PBDE sources in urban areas. Urban films ranged from 2.5 to 14.5 ng/m2 (mean = 9.0 ng/ m2), excluding the regional "hotspot" Electronics Recycling Facility, compared to 1.1 and 0.56 ng/m2 at the Suburban and Rural sites. Interior urban films (mean = 34.4 ng/m2) were 3 times greater than rural films (10.3 ng/m2) and were representative of variations in building characteristics. Indoor films were 1.5-20 times greater than outdoor films, consistent with indoor sources of PBDEs and enhanced degradation in outdoor films. Congener profiles were dominated by BDE-209 (51.1%), consistent with deca-BDE as the main source mixture, followed by congeners from the penta-BDE mixture (BDE-99:13.6% and -47:9.4%) and some octa-BDE (BDE-183:1.5%). Congener patterns suggest a degradative loss of lower brominated compounds in outdoor films versus indoor films. Gas-phase air concentrations were back-calculated from film concentrations using the film-air partition coefficient (K(FA)). Mean calculated air concentrations were 4.8 pg/m3 for outdoor and 42.1 pg/m3 for indoor urban sites, indicating that urban indoor air is a source of PBDEs to urban outdoor air and the outdoor regional environment.     

Perfluorinated chemicals in the arctic atmosphere

Twenty high-volume air samples were collected during a crossing of the North Atlantic and Canadian Archipelago in July 2005 to investigate air concentrations of fluorotelomer alcohols (FTOHs) and perfluoalkyl sulfonamido ethanols (PFASs). These commercial chemicals are widely used as surface treatments and are believed to be precursors for perfluorocarboxylic acids (PFCAs) and perfluorooctane sulfonate (PFOS) that accumulate in humans and biota, including those from remote arctic regions. The highest concentrations (sum of gas- and particle-phase) of FTOHs were for 8:2 FTOH (perfluoroctyl ethanol) (5.8-26 pg/m(3)), followed by 10:2 FTOH (perfluorodecyl ethanol) (1.9-17 pg/ m(3)) and 6:2 FTOH (perfluorohexyl ethanol) [BDL (below detection limit) to 6.0 pg/m(3)]. For the PFASs, MeFOSE (N-methyl perfluorooctane sulfonamido ethanol) was dominant and ranged from 2.6 to 31 pg/m(3); EtFOSE (N-ethyl perfluorooctane sulfonamido ethanol) ranged from BDL to 8.9 pg/m(3) and MeFOSEA (N-methyl perfluorooctane sulfonamide ethylacrylate) was BDL in all samples. Air parcel back-trajectories showed that the sampled air was largely representative of the arctic air mass. Air concentrations of target compounds were of the same order of magnitude as reported air concentrations in source regions. For instance, the mean 8:2 FTOH concentration was only a factor of about 3 lower than for three urban samples that were collected in Toronto for comparison. These findings confirm model results that predictthe efficient, long-range atmospheric transport and widespread distribution of FTOHs and related compounds in the arctic region. Mean particulate percentages for FTOHs and PFASs in the cruise samples (mean temperature, 5+/-4 degrees C) were BDL for 6:2 FTOH, 23% for 8:2 FTOH, 15% for 10:2 FTOH, 32% for MeFOSE, and 22% for EtFOSE. Further, the partitioning to particles for MeFOSE and EtFOSE was significantly correlated with inverse absolute temperature, whereas the FTOHs did not show this trend. The Toronto samples (mean temperature, -1+/-1 degree C) showed similar particulate percentages for MeFOSE and EtFOSE; however, the FTOHs were substantially less particle-bound. Although the mechanism for this partitioning is not understood, the results do indicate the need to better account for particle phase transport when modeling the atmospheric fate of these chemicals.     

Altitudinal and seasonal variations of persistent organic pollutants in the Bolivian Andes Mountains

Polyurethane foam disk passive air samplers were deployed over four periods of approximately 3 months along an altitudinal gradient (1820, 2600, 4650, and 5200 masl) on the east side of the Andean mountain range in Bolivia. The purpose of the study was to assess the gas-phase concentration and the altitudinal and seasonal trends of organochlorine pesticides and polychlorinated biphenyls (PCBs). Target compounds that were regularly detected included alpha- and gamma-hexachlorocyclohexane (HCH), endosulfans, and select PCB congeners. Endosulfans and HCH concentrations increased with altitude. Enrichment factors (concentration at the highest altitude divided by concentration at the lowest altitude) ranged from 10 to 20 for HCHs and 3 to 10 for endosulfans. Air parcel back trajectory analysis indicated that, in general, the high-altitude sites were exposed to a larger airshed and hence susceptible to long-range atmospheric transport from more distant regions. Seasonal differences were also observed with SigmaHCH concentrations peaking during periods 2 and 3 (March-September 2005). Airsheds (derived from the analysis of back trajectories) for periods 2 and 3 were less oriented along the Andes range (mountain air) with greater input from coastal regions. Endosulfans peaked during periods 1 and 2 (February-June 2005) and also exhibited the highest air concentrations of the target compounds, reaching approximately 1500 pg/m3 at the two highest elevation sites. PCB air concentrations at all sites were generally typical of global background values (<12 pg/m3) and showed no increase with altitude. This is the first study to measure air concentrations of persistent organic pollutants (POPs) in Bolivia and one of only a few studies to investigate altitudinal gradients of POPs.