Detailed study of factors controlling atmospheric concentrations of PCNs

Atmospheric concentrations of polychlorinated naphthalenes (PCNs) (108 samples in total) were measured at two rural/ semirural sites in England and one remote site on the west coast of Ireland in the years 2001 and 2000, respectively. Detailed analysis of the factors affecting concentrations is performed. At Mace Head (MH) Ireland, concentrations of sigmaPCNs ranged between 1.7 and 55 pg m(-3) with a mean of 15 pg m(-3) and were controlled primarily by advection. sigmaPCNs concentrations at Hazelrigg (HR), northwest England, ranged between 31 and 310 pg m(-3) with a mean of 110 pg m(-3), and at Chilton (CH), southwest England, ranged between 31 and 180 pg m(-3) with a mean of 85 pg m(-3). Data from the HR site shows that PCN concentrations have not declined between the early 1990s and 2001, while PCB concentrations have declined. The ratio of the sigmaPCNs/ sigmaPCBs was close to or greater than 1 at all sites. From air mass back trajectories, it is clear that local/regional sources influenced concentrations of PCNs at all sites, particularly at MH. At the two English sites during the summer, concentrations of PCNs were strongly influenced by temperature, indicating that air-surface exchange processes play an important role. Advection became more influential during winter, particularly at CH, where a different homologue profile was observed in some samples when air masses approached from the southwest and PCN concentrations increased. The average mixture profile of PCNs in air was similar to that observed in other studies and different from that in Halowax 1014.     

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.     

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.     

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.     

Brominated flame retardants and dechlorane plus in the marine atmosphere from Southeast Asia toward Antarctica

The occurrence, distribution, and temperature dependence in the marine atmosphere of several alternative brominated flame retardants (BFRs), Dechlorane Plus (DP) and polybrominated diphenyl ethers (PBDEs) were investigated during a sampling cruise from the East Indian Archipelago toward the Indian Ocean and further to the Southern Ocean. Elevated concentrations were observed over the East Indian Archipelago, especially of the non-PBDE BFR hexabromobenzene (HBB) with concentrations up to 26 pg m(-3) which were found to be related to continental air masses from the East Indian Archipelago. Other alternative BFRs- pentabromotoulene (PBT), pentabromobenzene (PBBz), and 2,3-dibromopropyl-2,4,6-tribromophenyl ether (DPTE)-were elevated, too, with concentrations up to 2.8, 4.3, and 2.3 pg m(-3), respectively. DP was detected from 0.26 to 11 pg m(-3) and bis-(2-ethylhexyl)-tetrabromophthalate (TBPH) ranged from not detected (nd) to 2.8 pg m(-3), respectively. PBDEs ranged from nd to 6.6 pg m(-3) (Σ(10)PBDEs) with the highest individual concentrations for BDE-209. The approach of Clausius-Clapeyron (CC) plots indicates that HBB is dominated by long-range atmospheric transport at lower temperatures over the Indian and Southern Ocean, while volatilization processes and additional atmospheric emissions dominate at higher temperatures. In contrast, BDE-28 and -47 are dominated by long-range transport without fresh emissions over the entire cruise transect and temperature range, indicating limited fresh emissions of the meanwhile classic PBDEs.     

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.     

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.     

Passive sampling survey of polybrominated diphenyl ether flame retardants in indoor and outdoor air in Ottawa, Canada: implications for sources and exposure

The polybrominated diphenyl ethers (PBDEs) are widely used as flame retardants in plastics of soft furnishings, TV sets and computers, and insulation in the indoor environment. The penta-BDEs--now banned in most parts of Europe but still used in North America--are additive flame retardants that may be released to the indoor environment via volatilization or as dusts. In this study, to investigate general population PBDE exposure, air was sampled in 74 randomly selected homes in Ottawa, Canada and at seven outdoor sites during the winter of 2002--3, using polyurethane foam (PUF) disk passive air samplers. The passive sampling rate (2.5 m3 day(-1)) was determined through a pilot study employing active and passive samplers side-by-side at selected indoor locations. Indoor air concentrations of PBDEs were log-normally distributed with a geometric mean of 120 pg m(-3) and a median of 100 pg m(-3), approximately 50 times higher than the range of outdoor air concentrations (<0.1-4.4 pg m(-3)). The maximum daily human exposure via the inhalation pathway based on median PBDE levels found in this survey was estimated to be 1.9 ng day(-1) (female) and 2.0 ng day(-1) (male), representing 4.1% (f) and 4.4% (m) of overall daily intake.     

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.     

Flame retardants in the atmosphere near the Great Lakes

As part of the Integrated Atmospheric Deposition Network (IADN), air samples were collected at five sites around the Great Lakes (two urban, two rural, and one remote) every 12 days during 2005-2006, and the concentrations of polybrominated diphenylethers (PBDEs), 1,2-bis(2,4,6-tribromophenoxy)-ethane (TBE), Dechlorane Plus (DP), and decabromodiphenyl ethane (DBD PE) were measured. The highest mean concentrations of total PBDEs were found at the urban sites in Chicago and Cleveland (65 +/- 4 and 87 +/- 8 pg/m3, respectively), and the lowest at the remote site in Eagle Harbor (5.8 +/- 0.4 pg/m3). With the exception of Chicago, the atmospheric concentrations of BDE-47 and 99 (summed over the gas and particle phases) are decreasing rapidly with half-lives of approximately 2 years, but the concentrations of BDE-209 are not decreasing at any of the five sites. The atmospheric partial pressures of BDE-47 and 99 showed a strong Clausius-Clapeyron relationship with reciprocal atmospheric temperature. TBE, DBDPE and DP were detected at all sites, but with the exception of Chicago, there were insufficient data to determine temporal trends for these compounds. The influence of human population density and synoptic atmospheric transport patterns was explored to explain the relatively high concentrations of BDE-209 in Cleveland.     

Atmospheric concentrations of polybrominated diphenyl ethers at near-source sites

Concentrations of polybrominated diphenyl ethers (PBDEs) were determined in air samples from near suspected sources, namely an indoors computer laboratory, indoors and outdoors at an electronics recycling facility, and outdoors at an automotive shredding and metal recycling facility. The results showed that (1) PBDE concentrations in the computer laboratorywere higherwith computers on compared with the computers off, (2) indoor concentrations at an electronics recycling facility were as high as 650,000 pg/m3 for decabromodiphenyl ether (PBDE 209), and (3) PBDE 209 concentrations were up to 1900 pg/m3 at the downwind fenceline at an automotive shredding/metal recycling facility. The inhalation exposure estimates for all the sites were typically below 110 pg/kg/day with the exception of the indoor air samples adjacent to the electronics shredding equipment, which gave exposure estimates upward of 40,000 pg/kg/day. Although there were elevated inhalation exposures at the three source sites, the exposure was not expected to cause adverse health effects based on the lowest reference dose (RfD) currently in the Integrated Risk Information System (IRIS), although these RfD values are currently being re-evaluated by the U.S. Environmental Protection Agency. More research is needed on the potential health effects of PBDEs.     

Diurnal fluctuations in polybrominated diphenyl ether concentrations during and after a severe dust storm episode in Kuwait City, Kuwait

Concentrations of polybrominated diphenyl ethers (PBDEs) were quantified in four-hour integrated air samples obtained serially over a five day period in May 2007 in Kuwait City during and after a severe dust storm. The ∑PBDE concentrations ranged from 51 to 1307 pg m(-3) for the first two days of sampling and 20 to 148 pg m(-3) for the rest of the sampling period. The first two days of sampling occurred during a severe dust storm episode when the total suspended particulates (TSP) in air exceeded 1000 μg/m(3) with concentrations peaking during the day and decreasing at night. During this dust episode, the peak nighttime PBDE concentration was 30 times higher than the minimum daytime concentration. Although ∑PBDE concentrations peaked at night during the first two sampling days, the fluctuations in the BDE 47:99 ratio tracked changes in ambient temperature remarkably well, following a clear diurnal pattern. The fraction of congeners in the gas phase varied inversely with solar flux and was lower on days with a high number of hours of sunshine, suggesting that photolytic degradation of gas-phase PBDEs was occurring.     

Size-dependent dry deposition of airborne polybrominated diphenyl ethers in urban Guangzhou, China

Gaseous and size-segregated particulate PBDEs (specifically BDE-47, -99, -183, -207, and -209) in the air were measured in urban Guangzhou at 100 and 150 m above the ground in daytime and at night in August and December 2010, to assess dry deposition of these contaminants accurately with regards to influences of meteorological factors but without confounding surface effects. Particulate PBDEs were more abundant at night than in daytime, and slightly higher in winter than in summer, likely from varying meteorological conditions and atmospheric boundary layers. More than 60% of particulate-phase PBDEs was contained in particles with an aerodynamic diameter (D(p)) below 1.8 μm, indicating long-range transport potential. The average daily particle dry deposition fluxes of PBDEs in August ranged from 2.6 (BDE-47) to 88.6 (BDE-209) ng m(-2) d(-1), while those in winter ranged from 2.0 (BDE-47) to 122 (BDE-209) ng m(-2) d(-1). Deposition fluxes of all PBDE congeners were significantly higher in daytime than at night for both months, due to the effect of diurnal variability of meteorological factors. In addition, mean overall particle deposition velocities of individual BDE congeners ranged from 0.11 to 0.28 cm s(-1). These values were within a factor of 2 of assumed values previously used in southern China and the Laurentian Great Lakes, suggesting that such assumptions were reasonable for sites with similar particulate size distributions and PBDE sources. Dry deposition velocities of PBDEs were lower at night than those in the daytime, probably reflecting higher mechanical and thermal turbulence during daytime. Dry deposition of particulate-bound PBDEs is influenced by short-term temporal variability from meteorological factors, and also by particulate size fractions.     

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.     

Spray irrigation of treated municipal wastewater as a potential source of atmospheric PBDEs

Spray irrigation facilities utilizing treated municipal wastewater are a potential source of polybrominated diphenyl ethers (PBDEs) to the atmosphere. PBDEs are used as flame retardants in many household items and have been found in wastewaters and biosolids. Evidence of PBDE release from spray irrigation facilities was discovered during a multiyear project to measure semivolatile organic chemical concentrations in air. Four BDE congeners (47, 99, 100, and 154) were monitored at three remote/ rural locations in Maryland and Delaware from 2001 to 2003. Average concentrations at two of the sites (BDE-47, 10-17 pg/m3; BDE-99, 5.3-7.7 pg/m3) reflect background levels. Average concentrations at the third location were 5-10 times higher (BDE-47, 175 pg/m3; BDE-99, 26 pg/m3) and were significantly correlated (p < 0.0001) with temperature indicating local source(s). Several spray irrigation facilities are located south and west of the third site, the prevailing wind direction during the spring and summer when most samples were collected. The fine mist released from the irrigation equipment may enhance release to the atmosphere via air-water gas exchange from water droplets. Temporal trends indicate that aerial concentrations of PBDEs in this area are increasing at an exponential rate; the atmospheric doubling times for the different congeners range from 1.1 to 1.7 yrs.     

Passive and active air samplers as complementary methods for investigating persistent organic pollutants in the Great Lakes Basin

Data obtained using passive air samplers (PAS) are compared to active high-volume air sampling data in order to assess the feasibility of the PAS as a method, complementary to active high-volume air sampling (AAS), for monitoring levels of organochlorine (OC) pesticides, polychlorinated biphenyls (PCBs), and polybrominated diphenyl ethers (PBDEs) in the Laurentian Great Lakes. PAS were deployed at 15 of the Integrated Atmospheric Deposition Network (IADN) sites on a quarterly basis between July 2002 and June 2003, and PAS and AAS results are compared. Levels for the OC pesticides are typically highest in agricultural areas, with endosulfan I dominating air concentrations with values ranging between 40 and 1090 pg x m(-3), dieldrin values between 15 and 165 pg x m(-3), and gamma-HCH values between 13 and 100 pg x m(-3). alpha-HCH was seen to be relatively uniform across the Great Lakes Basin with values ranging between 15 and 73 pg x m(-3). Large urban centers, such as Chicago and Toronto, have the highest levels of PCBs and PBDEs that range between 400 and 1200 pg x m(-3) and 10 and 70 pg x m(-3), respectively. Comparison of the AAS and the PAS data collected during this study shows good agreement, within a factor of 2 or 3, suggesting that the two sample methods produce comparable results. It is suggested that PAS networks, while providing data that are different in nature from AAS, can provide a cost-effective and complementary approach for monitoring the spatial and temporal trends of persistent organic pollutants.     

Sources, emissions, and fate of polybrominated diphenyl ethers and polychlorinated biphenyls indoors in Toronto, Canada

Indoor air concentrations of polybrominated diphenyl ethers (PBDEs) and polychlorinated biphenyls (PCBs) measured in 20 locations in Toronto ranged 0.008-16 ng·m(-3) (median 0.071 ng·m(-3)) and 0.8-130.5 ng·m(-3) (median 8.5 ng·m(-3)), respectively. PBDE and PCB air concentrations in homes tended to be lower than that in offices. Principal component analysis of congener profiles suggested that electrical equipment was the main source of PBDEs in locations with higher concentrations, whereas PUF furniture and carpets were likely sources to locations with lower concentrations. PCB profiles in indoor air were similar to Aroclors 1248, 1232, and 1242 and some exterior building sealant profiles. Individual PBDE and PCB congener concentrations in air were positively correlated with colocated dust concentrations, but total PBDE and total PCB concentrations in these two media were not correlated. Equilibrium partitioning between air and dust was further examined using log-transformed dust/air concentration ratios for which lower brominated PBDEs and all PCBs were correlated with K(OA). This was not the case for higher brominated BDEs for which the measured ratios fell below those based on K(OA) suggesting the air-dust partitioning process could be kinetically limited. Total emissions of PBDEs and PCBs to one intensively studied office were estimated at 87-550 ng·h(-1) and 280-5870 ng·h(-1), respectively, using the Multimedia Indoor Model of Zhang et al. Depending on the air exchange rate, up to 90% of total losses from the office could be to outdoors by means of ventilation. These results support the hypotheses that dominant sources of PBDEs differ according to location and that indoor concentrations and hence emissions contribute to outdoor concentrations due to higher indoor than outdoor concentrations along with estimates of losses via ventilation.     

Concentrations and spatial variations of polybrominated diphenyl ethers and other organohalogen compounds in Great Lakes air

Air samples were analyzed from urban, rural, and remote sites near the Great Lakes to investigate the occurrence, concentrations, and spatial and temporal differences of polybrominated diphenyl ethers (PBDE) in air. The concentrations of PBDEs were compared to those of other organohalogen compounds such as PCBs and organochlorine pesticides. The samples were collected in 1997-1999 as part of the Integrated Atmospheric Deposition Network (IADN). To minimize the variability of the data, we selected only samples taken when the atmospheric temperature was 20 +/- 3 degrees C. PBDEs were found in all samples, indicating that these compounds are widely distributed and that they can be transported through the atmosphere to remote areas. The total concentrations of PBDEs were similar to some of the organochlorine pesticides such as sigmaDDT and ranged from 5 pg/m3 near Lake Superior to about 52 pg/m3 in Chicago. In fact, the spatial trend was well correlated to those of PCBs. Our results indicate a relatively constant level from mid-1997 to mid-1999. At 20 +/- 3 degrees C, about 80% of the tetrabromo homologues are in the gas phase and about 70% of the hexabromo homologues are associated with the particle phase. Thus, particle-to-gas partitioning in the atmosphere is an important process for these compounds.     

Brominated flame retardants in the atmosphere of E-waste and rural sites in southern China: seasonal variation, temperature dependence, and gas-particle partitioning

The recycling of electrical and electronic waste(e-waste) in developing countries has attracted much attention as a significant source of brominated flame retardants (BFRs).Gaseous and particle-bound BFRs were measured in the atmosphere at e-waste and rural sites in southern China during 2007-2008. The annual average concentrations in the air were 3260 ± 3370 and 219 ± 192 pg/m3 for polybrominated diphenyl ethers (PBDEs) and were 546 ± 547 and 165 ± 144 pg/m3 for non-PBDE BFRs at the e-waste and rural sites,respectively. PBDEs had unusually high relative concentrations of di- and tribrominated congeners at the e-waste site. The Clausius-Clapeyron (CC) plots showed that the gaseous concentrations of less brominated BFRs (di- through hexa-BFRs) were strongly controlled by temperature-driven evaporation from contaminated surfaces (e.g., e-waste, soils, and recycled e-waste remains) except for winter. However, weak temperature dependence at the rural site suggests that regional or long-range atmospheric transport was largely responsible for the air concentrations. Gas-particle partitioning (KP) of PBDEs correlated well with the subcooled liquid vapor pressure (PL(o)) for most sampling events. The varied slopes of log KP versus log PL(o) plots for the e-waste site (-0.59 to -1.29) indicated an influence of ambient temperature and atmospheric particle properties on the partitioning behavior of BFRs. The flat slopes (-0.23 to -0.80) for the rural site implied an absorption-dominant partitioning. This paper suggests that e-waste recycling in Asian low-latitude regions is a significant source of less brominated BFRs and has important implications for their global transport from warm to colder climate     

Polybrominated diphenyl ethers in airborne particulates collected during a research expedition from the Bohai Sea to the Arctic

In July to September 2003, particulates in the oceanic atmosphere from the Bohai Sea to the high Arctic (37 degrees N to 80 degrees N) were collected aboard a research expedition icebreaker, Xuelong (Snow Dragon), under the 2003 Chinese Arctic Research Expedition Program (CHINARE 2003). These samples were analyzed to elucidate the atmospheric distributions of polybrominated diphenyl ethers (PBDEs) in the North Pacific Ocean and adjacent Arctic region. The levels of 11 PBDE congeners (BDE-28, -47, -66, -100, -99, -85, -154, -153, -138, -183, and -209; the sum was defined as sigma11PBDE) in the oceanic atmosphere of Far East Asia (34-48 degrees N/122-148 degrees E) ranged from 2.25 to 198.9 pg/m3 with a mean of 58.3 pg/m3. BDE-47, -99, -100, and -209 were the dominant congeners in all the samples, suggesting that the widely used commercial penta- and deca-BDE products were the original sources. The PBDE levels exhibited a decreasing trend from the mid- to high-latitudinal regions of the North Pacific Ocean, probably resulting from dilution, deposition, and decomposition of PBDEs during long-range transport of air masses. On the other hand, no apparent geographical pattern of PBDE distribution was observed within the Arctic, attributable to unstable air circulation and strong air mixing. Correlations among the PBDE congeners suggested that air masses collected from the North Pacific Ocean were relatively fresh, whereas those from the Arctic were aged as a result of photodecompoisiton. The higher average level (17.3 pg/m3) of PBDE congeners in the Arctic than those in the adjacent North Pacific Ocean (12.8 pg/m3) or other remote areas reported in the literature was attributed to the impact of the North American continent and temperature effects, which was consistent with the hypotheses of global fractionation.