Toward a global network for persistent organic pollutants in air: results from the GAPS study

The Global Atmospheric Passive Sampling (GAPS) study aims to demonstrate the feasibility of using passive samplers to assess the spatial distribution of persistent organic pollutants on a worldwide basis. The GAPS network includes more than 40 sites on 7 continents, mainly in background locations, with some representation of urban and agricultural areas. Here we present concentrations of organochlorine pesticides (OCPs), polychlorinated biphenyls (PCBs), and polybrominated diphenyl ethers (PBDEs) in polyurethane foam disk samplers, deployed from December 2004 to March 2005. Legacy OCPs such as alpha-HCH (hexachlorocyclohexane), Chlordanes (trans- and cis-Chlordane and trans-Nonachlor), Dieldrin, and dichlorodiphenyltrichloroethane isomers were detected at most sites with some high values that may be related to possible continued use and/or re-emissions related to historic use. Geometric mean (GM) air concentrations (pg/m3) were: 8.5 for sigmaHCH (sum of alpha- and gamma-isomers), 2.6 for sigmaChlordanes, 0.8 for Dieldrin, and 0.8 for p,p'-DDE. Current-use pesticides such as gamma-HCH (lindane) and especially Endosulfan I exhibited more variable and higher concentrations with GMs of 5 and 58, respectively. PCBs and PBDEs were elevated at urban/suburban sites consistent with their historical use pattern. GM concentrations (pg/m3) were 17 for PCBs and 4 for PBDEs. Sampling under GAPS will continue and will eventually allow seasonality effects and longer-term temporal and spatial trends to be evaluated.     

Hexachlorocyclohexanes (HCHs) in the Canadian Archipelago. 2. Air-water gas exchange of alpha- and gamma-HCH

Air and water were sampled in the Canadian Archipelago during summer on the Tundra Northwest 1999 (TNW-99) expedition and air was sampled at Resolute Bay (RB), Nunavut, to determine the gas exchange of alpha- and gamma-hexachlorocyclohexanes (HCHs) and the enantiomers of alpha-HCH. Air concentrations of sigmaHCH during TNW-99 and at RB were similar, averaging 55 and 53 pg m(-3), respectively. The net gas exchange direction was volatilization for alpha-HCH and near equilibrium or deposition for gamma-HCH, whereas actual fluxes depended on the fraction of open water. Enantiomer fractions, EF = (+)/[(+) + (-)] of alpha-HCH in air sampled from shipboard were significantly correlated to those in surface water for events with >90% open water, but were closer to racemic and not correlated to EFs in water for events with 0-50% open water. Levels of alpha-HCH in air at RB averaged 37 +/- 9 pg m(-3) from June to early July, and EFs were close to racemic (0.496 +/- 0.004). In mid-July the ice pack broke up around RB. From this point through August, air concentrations increased significantly to 53 +/- 5 pg m(-3), and the mean EF decreased significantly to 0.483 +/- 0.009. Air concentrations of gamma-HCH at RB did not differ significantly before (8.0 +/- 3.7 pg m(-3)) and after (6.6 +/- 0.76 pg m(-3)) ice breakup. Results show that alpha-HCH enantiomers are sensitive tracers for following the impact of ice cover loss on gas exchange in the Arctic.     

Using passive air samplers to assess urban-rural trends for persistent organic pollutants and polycyclic aromatic hydrocarbons. 2. Seasonal trends for PAHs, PCBs, and organochlorine pesticides

This is the second of two papers demonstrating the feasibility of using passive air samplers to investigate persistent organic pollutants along an urban-rural transect in Toronto. The first paper investigated spatial trends for polychlorinated biphenyls (PCBs) and organochlorine pesticides (OCPs). This second paper investigates the seasonality of air concentrations for polycyclic aromatic hydrocarbons (PAHs), PCBs, and OCPs along this transect. Air samplers, consisting of polyurethane foam (PUF) disks housed in stainless steel domed chambers, were deployed for three 4-month integration periods from June 2000 to July 2001. The seasonal variations of derived air concentrations for PAHs, PCBs, and OCPs reflected the different source characteristics for these compounds. PAHs showed a strong urban-rural gradient with maximum concentrations at urban sites during the summer period (July-October). These high summer values in Toronto were attributed to increases in evaporative emissions from petroleum products such as asphalt. PCBs also exhibited a strong urban-rural gradient with maximum air concentrations (approximately 2-3 times higher) during the spring period (April-June). This was attributed to increased surface-air exchange of PCBs that had accumulated in the surface layer over the winter. alpha-HCH was fairly uniformly distributed, spatially and temporally, as expected. This pattern and the derived air concentration of approximately 35 to approximately 100 pg m(-3) agreed well with high volume air data from this region, adding confidence to the operation of the passive samplers and showing that site-to-site differences in sampling rates was not an issue. For other OCPs, highest concentrations were observed during the spring period. This was associated with either (i) their local and/or regional application (gamma-HCH, endosulfan) and (ii) their revolatilization (chlordanes, DDT isomers, dieldrin, and toxaphene). Principal component analysis resulted in clusters for the different target chemicals according to their chemical class/source type. The results of this study demonstrate how such a simple sampling technique can provide both spatial and seasonal information. These data, integrated over seasons, can be used to evaluate contaminant trends and the potential role of large urban centers as sources of some semivolatile compounds to the regional environment, including the Great Lakes ecosystem.     

Passive air sampling of polychlorinated biphenyls and organochlorine pesticides at the Korean Arctic and Antarctic research stations: implications for long-range transport and local pollution

To assess levels and patterns of polychlorinated biphenyls (PCBs) and organochlorine pesticides (OCPs) in polar regions, XAD-resin based passive air samplers were deployed for one year at the Korean polar research stations at Ny-Alesund, Norway (2005-2006) and King George Island, Antarctica (2004-2005). Backward trajectories suggest that these stations are affected by long-range transport from source regions in Northern Europe and Russia and the southern tip of South America, respectively. Relatively high levels of PCB-11, averaging 60 pg x m(-3), were observed in Antarctica, suggesting an unusual source of PCB-11 to the Southern Hemisphere. Reflecting the hemispheric distribution of global PCB emissions, the average level of sigma205PCB (excluding three mono-CBs and PCB-11) was five times higher in the Arctic (95 pg x m(-3)) than in the Antarctic (19 pg x m(-3)). Levels of sigma9PCB at Ny-Alesund were similarto those reported for other Arctic sites, while levels at King George Island were lower than at other sites on the Antarctic Peninsula but 1 order of magnitude higher than background levels measured at a more remote Antarctic site. Light homologues were predominant in all samples (except for one Arctic sample), consistent with the hypothesis of global fractionation and predictions of long-range transport potential. Dominance of heavy PCBs on the roof of the main building at Ny-Alesund and a concentration gradient with distance from the main building at King George Island strongly indicated the influence of local sources. OCP levels were also influenced by long-range transport but not by local sources. This study highlights the feasibility of using passive air sampling to assess both long-range transport and local pollution in remote regions.     

Three-year atmospheric monitoring of organochlorine pesticides and polychlorinated biphenyls in polar regions and the South Pacific

XAD-2 resin based passive air samplers (PAS) were deployed for three one-year periods at the Korean polar and South Pacific research stations at Ny-?lesund (2005-2009), King George Island (2005-2007), and Chuuk (2006-2009) to investigate long-range transport, local sources, and temporal trends of organochlorine pesticides (OCPs) and polychlorinated biphenyls (PCBs). The highest hexachlocyclohexane (HCH) concentration (35.2-78.9 pg·m(-3)) over the entire sampling period was detected at Ny-?lesund, in the Arctic. α-HCH was the dominant OCP (31.1-67.1 pg·m(-3)), contributing about 50% of the total OCP load. Additionally, a high and consistent α/γ-HCH ratio was observed at Ny-?lesund. HCHs might reach Arctic sites more easily than other OCPs from surrounding countries through long-range atmospheric transport (LRAT). Interestingly, high levels of the current-use OCP endosulfan-particularly endosulfan-I--were detected at almost all sampling sites, including in Antarctica, ranging 12.2-88.5, 17.7-130, and ND-59.7 pg·m(-3) at King George Island, Ny-?lesund, and Chuuk, respectively. Specific OCP and PCB patterns, such as low trans/cis-chlordane ratios and a prevalence of lighter PCB congeners, were observed in all three regions (excepting one site at Ny-?lesund and one site in the South Pacific affected by local sources) during all sampling periods. This indicates that these Polar and remote South Pacific sites are mainly influenced by LRAT. Over the entire sampling period, a decreasing trend of HCHs (α- and γ-HCH) and an increasing trend of endosulfan-I were observed at the Ny-?lesund sites.     

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.     

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.     

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 Hexachlorocyclohexanes in the North Pacific Ocean and the adjacent Arctic region: spatial patterns, chiral signatures, and sea-air exchanges

During the 2003 Chinese Arctic Research Expedition (CHINARE2003) from the Bohai Sea to the high Arctic (37 degrees N to 80 degrees N) aboard the icebreaker Xuelong (Snow Dragon), air samples were collected for the analysis of hexachlorocyclohexanes (HCHs) in the North Pacific Ocean and adjacent Arctic region. The sigma HCHs (alpha-HCH + gamma-HCH) ranged from 2.3 to 95.1 pg/m3 with the highest levels observed in Far East Asia (32.5 pg/m3), followed by the North Pacific Ocean (17.0 pg/m3) and the Arctic (7.3 pg/ m3). Compared to previous studies in the same areas in 1990s, our measurements were approximately 1 order of magnitude lower. Because of disproportionate chemical reduction and physical fractioning during long-range transport, the ratios of alpha-HCH to gamma-HCH (alpha/gamma-HCH) showed a significant increasing trend from low to high latitudes, suggesting thatthe alpha/gamma-HCH range of 4-7 could not be used to identify sources of technical HCHs especially in remote areas. The ratios of (+)-alpha-HCH to the sum of (+)-alpha-HCH and (-)-alpha-HCH were on average much more biased from 0.5 compared to previous observations in mid-1990s, indicating the exchange of atmospheric alpha-HCH with those in the oceans, where (+)-alpha-HCH was selectively depleted in biological degradation processes. Estimated fugacity ratios based on available data for both alpha-HCH and gamma-HCH further implied their net volatilization from seawater to air in the Arctic Ocean.     

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.     

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.     

Urban versus remote air concentrations of fluorotelomer alcohols and other polyfluorinated alkyl substances in Germany

Neutral, volatile polyfluorinated alkyl substances (PFAS) were measured in environmental air samples at two different sites in Northern Germany in spring 2005. The sampling locations were chosen to cover a metropolitan and a rural site, the Hamburg city center, and Waldhof, a background monitoring site. An optimized and validated analytical protocol was used to analyze two sets of parallel high-volume air samples. For both sampling locations as well as for individual samples, field blanks were taken to monitor possible background contamination. Gas chromatography coupled to mass spectrometry using positive chemical ionization (GC/ PCI-MS) was used for quantitative analyses. This article describes the first air concentration data of volatile PFAS outside North America reported in the peer-reviewed literature. The wide distribution of fluorotelomer alcohols (FTOHs), fluorinated sulfonamides, and sulfonamidoethanols (FOSAs/FOSEs) in German environmental air is presented. Furthermore, two volatile PFAS, i.e., N-methyl fluorooctane sulfonamide (NMeFOSA) and 4:2 FTOH, were determined for the first time in environmental air. Minimum-maximum sigmaFTOH concentrations of 64-311 pg/m3 (remote) up to 150-546 pg/m3 (urban) and minimum-maximum sigmaFOSA + FOSE concentrations between 12 and 54 pg/m3 (remote) and 29 and 151 pg/m3 (urban) were determined. 8:2 FTOH and 6:2 FTOH were found to be the predominant POPs determined in Waldhof so far. Blank contamination was found to be negligible. A significant correlation was found with the ambient temperature for the partitioning of airborne FOSEs between the gaseous and particulate phase (R = 0.853), whereas FTOHs and FOSAs were almost exclusively found in the gaseous phase. Furthermore, highest airborne PFAS concentrations were determined at relatively high ambient temperatures. Correlation coefficients (R) for sigmaFTOH and sigmaFOSA + FOSE concentrations with temperature were 0.954 and 0.968, respectively. Finally, the PFAS concentrations determined in this study are set into context with levels of "classical" persistent organic pollutants (POPs) in the same region and PFAS data available for North America.     

Hexachlorocyclohexanes and endosulfans in urban, rural, and high altitude air samples in the Fraser Valley, British Columbia: evidence for trans-Pacific transport

High-volume air samples collected over the period Aug. 14-30, 2001, in the Lower Fraser Valley, BC, Canada, were used to assess urban/rural differences of organochlorine pesticides (OCPs) for ground level samples and to attempt to directly measure events of trans-Pacific inputs through the mid-troposphere. Hexachlorocyclohexanes (alpha- and gamma-isomers; 2-25 pg m(-3)) and endosulfan1 and -2 (5-150 pg m(-3)) were detected in all ground level samples. Seven air samples were collected during mid-troposphere flights (approximately 4400 m altitude) over the Lower Fraser Valley. These flights occurred concurrently with ground level sampling. Trajectory analysis identified three events of substantial mid-troposphere, trans-Pacific flow where 10-day back trajectories stemmed from potential source regions in Asia. These events were also characterized by higher air concentrations of alpha-HCH at 4400 m as compared to the ground level stations. This represents the first event-based, aircraft measurement of advection inputs of OCPs in the mid-troposphere of the west coast of North America.     

A general indication of the Contemporary background levels of PCDDs, PCDFs, and coplanar PCBs in the ambient air over rural and remote areas of the United States

Long-term measurements of the atmospheric concentrations of PCDDs, PCDFs, and coplanar PCBs were taken in rural and remote areas of the United States by the National Dioxin Air Monitoring Network (NDAMN). A total of 21 quarterly sampling moments occurred from June, 1998 to December, 2002 at 34 locations geographically distributed throughout the United States. Sampling sites were located in rural and remote areas to obtain background air concentrations of dioxin-like compounds. Results were reported as the toxic equivalent (TEQ) of the mix of PCDDs/ PCDFs (TEQDF) and the mix of coplanar PCBs (TEQPCB). At the studied rural sites the mean annual TEQDF for each of the NDAMN sampling years was 10.43, 11.39, 10.40, and 10.47 fg m(-3) for 1999, 2000, 2001, and 2002, respectively. There was no statistically significant difference in the rural mean TEQDF air concentrations across the sampling years (at 0.05 level of significance), although the mean concentration in sampling year 2000 increased 10% relative to the other sampling years. The 95th percent confidence interval of TEQDF air concentrations in rural areas of the United States is from 6.4 to 15.4 fg m(-3), indicating there is a 95% probability that the true mean falls within this range. Mean annual atmospheric concentrations (TEQDF) at the remote sites were 1.41, 0.99, 0.7, and 1.07 fg m(-3) in 1999, 2000, 2001, and 2002, respectively, The 95th percent confidence interval of TEQDF air concentrations suggest that the true mean annual atmospheric TEQDF concentration in remote areas of the United States is between 0.1 and 3 fg m(-3). The remote sites have average air TEQDF concentrations that are approximately 10 times lower than those of the rural sites. For the rural sites, there was close agreement in the mean annual air concentrations of coplanar PCBs (TEQPCB) among the years 1999, 2000, 2001, and 2002 (i.e., 0.62, 0.69, 0.59, and 0.7 fg m(-3), respectively). However, as is the case with PCDDs/PCDFs, there was a marked increase (i.e., approximately equal to 13%) in the annual rural mean air concentration in 2000 as compared to the other sampling years. The confidence intervals across the NDAMN sampling years suggests a 95% probability that mean TEQPcB atmospheric concentrations in rural and remote areas of the United States are within the range of 0.5-0.9 fg m(-3) and 0.1-0.5 fg m(-3), respectively. The congener distributional patterns of PCDDs/PCDFs in air were relatively constant at all locations, and match the profile of urban air. We propose the hypothesis that urban areas are regional sources of PCDDs/PCDFs and are affecting atmospheric levels in rural and remote areas of the United States.     

Analysis of polychlorinated biphenyls in concurrently sampled Chinese air and surface soil

Polychlorinated biphenyl (PCB) concentrations were measured in a concurrent air and surface soil sampling program across China. Passive air samples were collected for approximately 3 months from mid-July to mid-October, 2005 using polyurethane foam (PUF) disk type samplers at 97 sites and surface soil samples were collected in a subset of 51 sites in the same year. As expected, the air concentrations (pg m(-3)) were highest at urban sites (mean of 350 +/- 218) followed by rural (230 +/- 180) and background sites (77 +/- 50). The PCB homologue composition was similar across China, with no distinction among site types, and reflected the profile of Chinese transformer oil with a greater proportion of lower molecular weight (LMW) congeners, particularly the tri-PCBs. This differs from the profile in Chinese soil that was shifted toward the higher molecular weight (HMW) congeners and likely attributed to numerous years of deposition and accumulation in this reservoir. The PCB profile in surface soil also reflects an "urban fractionation effect" with preferential deposition of HMW congeners near sources. The profile of PCBs in Chinese air was shown to be different than reported for Europe and for the Great Lakes Area (GLA) in North America. European and GLA air samples show a distinction between urban and rural/V background sites, with urban sites dominated by tetra- and penta-PCBs, whereas rural and background sites are shifted toward LMW congeners. European and GLA samples also exhibit much higher PCB concentrations at urban sites. This may be attributed to the use of PCBs in building materials in European and North American cities. In China, the difference between urban and rural/background sites is less pronounced. Strong soil-air correlations were found for the LMW PCBs at the background and rural sites, and for the HMW PCBs at the urban sites, a strong evidence of the urban fractionation effect. To our knowledge, this is the first national-scale study in China investigating PCBs in both air and surface soil samples.     

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.     

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.     

Modeling persistent organic pollutant (POP) partitioning between tree bark and air and its application to spatial monitoring of atmospheric POPs in mainland China

A mathematical model describing the bark/air partitioning of persistent organic pollutants (POPs) was established taking into consideration the accumulation processes of POPs from air into bark and compound-, species-, and site-specific air-to-bark accumulation factors. It allows the assessment of the concentrations of atmospheric POPs based on those recorded in tree bark. The spatial distribution of atmospheric POPs including 18 polycyclic aromatic hydrocarbons (Sigma18PAHs), 5 organic chlorinated pesticides (Sigma5OCPs), 10 polychlorinated biphenyls (Sigma10PCBs), and 17 brominated flame retardants (Sigma17BFRs) were investigated by analyzing 163 bark samples from 68 sites across mainland China. The atmospheric POPs were estimated to be 4.1-399 ng/m3 air, and 11.3-553, 4.5-130, and 0.9-624 pg/m3 air with geometric means of 71 ng/m3 air, and 99,26, and 25 pg/m3 airfor Sigma18PAHs, Sigma5OCPs, Sigma10PCBs, and Sigma17BFRs, respectively, based on those recorded in the tree barks of 5.1-1770, 0.05-12.9, 0.21-21.6, and 0.02-48.3 ng/g bark on dry weight basis, with geometric means of 295, 1.47, 3.12, and 2.79 ng/g bark. These results generally indicated that contamination by atmospheric POPs is more serious in eastern and mid China than that in western China.     

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.     

Semivolatile organic compounds in window films from lower Manhattan after the September 11th World Trade Center attacks

The September 11th World Trade Center (WTC) terrorist attacks resulted in the large-scale release of contaminants that were deposited on the environment of New York City (NYC). Six weeks after the attacks, samples of an organic film on window surfaces were collected and analyzed for polybrominated diphenyl ethers (PBDE), polychlorinated biphenyls (PCB), polychlorinated naphthalenes (PCN), polycyclic aromatic hydrocarbons (PAH), and organochlorine pesticides (OCPs). Concentrations dropped by an order of magnitude within 1 km of the WTC and reached background concentrations by 3.5 km. Concentrations within 1 km of the WTC averaged 3280 ng/m2 for sigmaPBDE, 900 ng/m2 for sigmaPCB, 33 ng/m2 for sigmaPCN, and 77100 ng/m2 for sigmaPAH. Congener profiles of the sites nearest the WTC suggested a combination of combustion and evaporative sources of all compounds, whereas the background sites exhibited profiles consistent with evaporative sources. PBDE profiles showed enrichment in lower molecular weight congeners near the WTC, suggesting that these congeners were formed as a result of the combustion conditions. Homologue fractions of PCN combustion markers were approximately 2-9 times greater at near WTC sites compared to background NYC. Gas-phase air concentrations were back-calculated from measured film concentrations using the film-air partition coefficient (KFA), and calculated air concentrations followed spatial trends observed in films.