Long-range transported atmospheric pollutants in snowpacks accumulated at different altitudes in the Tatra Mountains (Slovakia)

Persistent organic pollutants (POPs), including polychlorobiphenyls (PCB), endosulfans, hexachlorocyclohexanes (HCHs), hexachlorobenzene (HCB), polybromodiphenyl ethers (PBDEs), and polycyclic aromatic hydrocarbons (PAHs), were analyzed in snowpack samples collected along an altitudinal gradient (1683-2634 meters above sea level) in the High Tatra Mountains (Slovakia). All analyzed compounds were found at all altitudes, pointing to their global distribution. The presence of PBDEs, particularly BDE 209, in the snowpack samples is especially relevant, as it reflects the air transport capacity of this low volatile, very hydrophobic pollutant to remote mountain regions. The most abundant compounds at all altitudes were PAHs, with mean values ranging from 90 to 300 ngL(-1), 1 order of magnitude higher than concentrations of other compounds. PCBs (sum of PCB 28, 52, 101, 118, 153, 138, and 180) and BDE 209 were the dominant organohalogen pollutants, with concentrations from 550 to 1600 pg L(-1) and from 670 to 2000 pgL(-1), respectively. Low brominated PBDEs, endosulfans, HCHs and HCB were consistently found in all samples at lower concentrations. The concentrations of these compounds correlated positively with altitude (i.e., negatively with temperature), which is consistent with cold-trapping effects. The regression coefficients were positive and statistically significant (p < 0.05) for all compounds except BDE 209, endosulfan sulfate, HCB and α-HCH. Contrariwise, the concentrations of BDE 209 and endosulfan sulfate exhibited a statistically significant positive correlation with total particle amount, which agrees with long-range atmospheric transport associated to aerosols according to the physical-chemical properties of these compounds. Snow specific surface area, which determines the maximum amount of each organic compound that can be sorbed by snow, proved utile for describing the distribution of the more volatile compounds, namely α-HCB and HCB, in the snowpack.     

Atmospheric semivolatile organochlorine compounds in European high-mountain areas (central Pyrenees and high Tatras)

Atmospheric samples from two European high-mountain areas showed similar composition of semivolatile organochlorine compounds (SOC), such as polychlorobiphenyls (PCBs), DDTs, endosulfans, hexachlorobenzene (HCB), and hexachlorocyclohexanes (HCHs). Nearly all compounds were predominantly found in the gas phase and only the less volatile such as some PCBs (e.g., 149, 118, 153, 138, and 180) were found in higher abundance in the particulate phase. HCB, 49-85 pg m(-3), is the dominant SOC. This compound is only found in the gas phase exhibiting uniform concentrations irrespective of season and air mass origin. SOC of present use, like HCHs and endosulfans, were found in higher concentrations in the warm periods, 32-46 and 4-10 pg m(-3) in the gas + particulate phases, respectively, reflecting their seasonal pattern of use in many European countries. PCB and 4,4'-DDE, 39-42 and 4-6 pg m(-3) in the gas + particulate phases, respectively, also showed a seasonal trend despite neither the former nor the precursor of the latter (4,4'-DDT) being manufactured with their use drastically restricted since the 1980s. The seasonal differences are mainly due to a higher occurrence of air masses with strong continental inputs in the warm than in the cold periods. In this respect, samples whose air masses traveled at the high troposphere (backward air mass trajectories >6000 m) have been observed to carry considerably smaller PCB and 4,4'-DDE loads (9.3 +/- 2.8 and 0.4 +/- 0.05 pg m(-3), respectively) than overall average.     

Persistent organic pollutants in the equatorial atmosphere over the open Indian Ocean

Twelve air samples collected over the Indian Ocean by a high volume air sampler between August 2004 and August 2005 were analyzed for selected polychlorinated biphenyl (PCB) congeners and organochlorine pesticides. The region of the Indian Ocean and adjacent countries is likely to be acting as a source of selected POPs to the global environment. Data were compared with those reported for the last 30 years to examine historical trends of selected persistent organic pollutants (POPs) over the Indian Ocean. Compound concentrations were influenced by the proximity to land and air mass origins. Higher concentrations of atmospheric sigmaPCBs (50-114 pg m(-3)) were found on the remote islands of Chagos Archipelago and Gan, Maldives, and in the proximity of Jakarta, Indonesia, and Singapore. Military activities and unregulated waste combustion were identified as possible sources for atmospheric PCB contaminations at the more remote areas. The highest concentrations of organochlorine pesticides were found adjacent to the coastline of Sumatra and Singapore, where sigmaDDTs (dichlorodiphenyltrichloroethane) and sigmaHCHs (hexacyclohexanes) were as high as 30 and 100 pg m(-3), respectively. A comparison study for the last 30 years over six regions of the Indian Ocean showed that the concentrations of organochlorine pesticides have declined significantly, by a magnitude of two, since the mid 1970s, but were highest at the beginning of the 1990s. The time trend of PCB contamination in the atmosphere over the Indian Ocean is less apparent. The decline of atmospheric POPs over the Indian Ocean may be due to international regulation of the use of these compounds.     

Altitudinal transect of atmospheric and aqueous fluorinated organic compounds in Western Canada

Neutral perfluorinated alkyl substances (PFASs), which are thought to be volatile precursors of environmentally ubiquitous perfluorocarboxylates (PFCAs) and perfluorooctanesulfonate (PFOS), were quantified in XAD-2 resin based passive air samplers deployed along an altitudinal transect from 800 to 2740 m above sea level (asl) in Western Canada (based at N51degrees 20' W117degrees 00') over the spring and summer seasons of 2004. The amounts of fluorotelomer alcohols (FTOHs) and perfluorinated sulfonamido alcohols (FOSEs) sequestered in the samplers increased with altitude, being lowest at an elevation of 1300 m asl and highest at either the 2340 or the 2740 m asl sites. A variety of potential reasons for these gradients are discussed, including changes in sampler uptake kinetics and phase capacity caused by changes in atmospheric pressure,temperature, and wind speed. Vapor phase concentrations were estimated to range from 3.7 to 19 pg m(-3) for perfluorinated sulfonamides (FOSAs) and from below detection limits (25 pg m(-3)) to 88 pg m(-3) for FOSEs. Over a similar altitudinal range (800-2350 m asl), 9 L lake water samples were collected in stainless steel cans, extracted with solid phase extraction columns, and analyzed for PFCAs and PFOS. Aqueous concentrations in lake water, ranging from 0.07 to 1.0 ng L(-1) for single PFCAs and from 0.04 to 0.1 ng L(-1) for PFOS, were more constant with altitude and were not correlated with the amount of the precursor compounds in the atmosphere. The relative abundance of FTOHs in air and PFCAs in water supports atmospheric FTOH degradation as the source of PFCAs in the mountain lakes.     

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.     

Persistent organic pollutants in fish: biomonitoring and cocktail effect with implications for food safety

The impact of anthropogenic wastes of persistent organic pollutants (POPs) on the marine environment has increased in the last decades. POPs include polychlorinated biphenyls (PCBs) and organochlorine pesticides (OCs). To assess the levels of these POPs in the wild fish population, pelagic and benthopelagic predator fish species were selected as biomonitors. For detection and quantification of POPs in muscular tissues, a simple extraction through Accelerated-Solvent-Extraction (ASE) with an ‘in-line’ clean up purification approach was applied, followed by a GC–MS/MS analysis. Concentrations of sum DDT, sum HCH and endrin correlated with all PCB concentrations. Significant differences among fish species were found for all OCs and all PCBs except PCB 31 and 101. Blackspot seabream had the highest PCB concentrations; OCs were highest in tuna. Due to major concerns regarding fish population losses and the possible human chronic exposure to contaminated fish, studies addressing combined effects of multiple POPs (‘cocktail effect’) should be implemented. Our data motivate further experimental and observational studies in fish to define adequate baseline levels for cumulative human exposure and potential role of these contaminants for food safety.     

Orographic cold-trapping of persistent organic pollutants by vegetation in mountains of western Canada

Conifer needles from mountain areas of Alberta and British Columbia, Canada, were collected from sites that ranged in altitude from 770 to 2200 masl and were analyzed for polychlorinated biphenyls (PCBs) and organochlorine pesticides (OCs) to determine if they are progressively concentrated in colder, more elevated mountain areas, where temperatures decrease as elevation increases. Concentrations of OCs in needles ranged from 43 to 2430 pg g(-1), 55-17500 pg g(-1), and 11-2930 pg g(-1) (dry weight), for total hexachlorocyclohexanes (HCHs), PCBs, and endosulfans, respectively. The more volatile OCs, with subcooled liquid vapor pressures (PL) > 0.1 Pa at 25 degrees C, increased at higher altitudes, whereas the less volatile OCs were either unrelated or inversely correlated with altitude. These spatial patterns were similar for species of spruce (Picea engelmannii and glauca) and pine (Pinus contorta and albicaulis). Back trajectories revealed that air masses arriving at these sites traveled over Asia and the Pacific Ocean before reaching the Rocky Mountains. Results from this study demonstrate that alpine ecosystems accumulate these chemicals to the same degree that is observed in polar environments that are known to receive contaminants by long-range transport.     

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.     

Coplanar polychlorinated biphenyls (PCB) in indoor air

Indoor air levels of coplanar polychlorinated biphenyls (mono- and non-ortho substituted PCB) of various buildings were determined. As a consequence of the presence of joint sealings containing PCB, total PCB concentrations in indoor air up to 4,200 ng/m3 were detected (data based on a survey including 29 sampling sites). In a PCB contaminated industrial building, total indoor air PCB levels up to 13,000 ng/m3 were measured. Typical PCB congeners in indoor air include PCB 28, PCB 52, and PCB 101. Concentrations of coplanar (dioxin-like) PCB have been determined for six different sites. The most abundant coplanar PCB congener in indoor air is PCB 118, followed by PCB 105, PCB 123, and PCB 77 in various order. Levels of coplanar PCB, expressed as toxicity equivalents (TEG), do correlate well with the total indoor air PCB concentration: a total PCB level of 1,000 ng/m3 corresponds to a concentration of coplanar PCB of 1.2 pg TEQ/m3. Based on this correlation and on an indoor air PCB level of 6,000 ng/m3 (tentative guideline value for PCB in indoor air in Switzerland based on a daily exposure of 8 h), the maximum daily intake of coplanar PCB via indoor air was estimated to be 0.6 pg TEQ/kg body weight.     

Semivolatile organochlorine compounds in the free troposphere of the Northeastern Atlantic

Polychlorobiphenyls (PCBs), hexachlorobenzene (HCB), hexachlorocyclohexanes, and DOTs were analyzed over 1 entire year period in the air of a high altitude remote site (2367 m above sea level) located in Teide (Tenerife, Canary Islands, 28 degrees N16 degrees W) in the Eastern North Atlantic region. Twenty samples were collected providing information on the concentrations of these semivolatile organochlorine compounds (SOCs) in the free troposphere since the stable and persistenttemperature inversion in the subtropics defines a clear separation from the marine boundary layer. More than 80% of total SOCs were in the gas phase. HCB was the individual SOC in higher concentration, 51 pg m(-3), well above than the other SOCs identified, 1-11 pg m(-3). Sum PCB concentrations were 78 pg m(-3). These concentrations range among the lowest described in atmospheric samples. The collected air originated from four main sectors, high and middle latitudes in the north Atlantic, Europe, and Africa, as determined from isentropic backward air mass trajectories. No significant differences were observed for the concentrations of these compounds between air masses showing a high uniform SOC composition of the free troposphere. Only the more volatile PCB congeners, #18 and #28, exhibited significant differences between air masses from northern and southern latitudes. A seasonal temperature dependence for the less volatile PCB congeners, five or more chlorine subtituents, was also observed. Free tropospheric concentrations of all SOCs except HCB were lower than those measured near sea level for reference. PCB concentrations at the two altitudes exhibited consistent differences according to degree of chlorination. The stronger decrease of the more volatile compounds with altitude might reflect higher photodegradation.     

The global distribution of PCBs and organochlorine pesticides in butter

In this study we explored the use of butter as a sampling matrix to reflect the regional and global scale distribution of PCBs and selected organochlorine pesticides/metabolites in air. This was because persistent organic pollutants (POPs) concentrate in dairy fats, where concentrations are controlled by feed intake (primarily from pasture/silage), which is in turn primarily controlled by atmospheric deposition. Butter sigmaPCB concentrations varied by a factor of approximately 60 in 63 samples from 23 countries. They were highest in European and North American butter and lowest in southern hemisphere (Australian, New Zealand) samples, consistent with known patterns of historical global usage and estimated emissions. Concentrations in butter reflected differences in the propensity of PCB congeners to undergo long range atmospheric transport from global source regions to remote areas and the relatively even distribution of HCB in the global atmosphere. Concentrations of p,p'-DDT, p,p'-DDE, and HCH isomers all varied over many orders of magnitude in the butter samples, with highest levels in areas of current use (e.g. India and south/central America for DDT; India, China, and Spain for HCH). We conclude that butter is sensitive to local, regional, and global scale spatial and temporal atmospheric trends of many POPs and may therefore provide a useful sampling medium for monitoring purposes. However, to improve the quantitative information derived on air concentrations requires an awareness of climatic and livestock management factors which influence air-milk fat transfer processes.     

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.     

Atmospheric HCH concentrations over the Marine Boundary Layer from Shanghai, China to the Arctic Ocean: role of human activity and climate change

From July to September 2008, air samples were collected aboard the research expedition icebreaker XueLong (Snow Dragon) as part of the 2008 Chinese Arctic Research Expedition Program. Hexachlorocyclohexane (HCH) concentrations were analyzed in all of the samples. The average concentrations (± standard deviation) over the entire period were 33 ± 16, 5.4 ± 3.0, and 13 ± 7.5 pg m?3 for α-, β- and γ-HCH, respectively. Compared to previous studies in the same areas, total HCH (ΣHCH, the sum of α-, β-, and γ-HCH) levels declined by more than 10 × compared to those observed in the 1990s, but were approximately 4 × higher than those measured by the 2003 China Arctic Research Expedition, suggesting the increase of atmospheric ΣHCH recently. Because of the continuing use of lindane, ratios of α/γ-HCH showed an obvious decrease in North Pacific and Arctic region compared with those for 2003 Chinese Arctic Research Expedition. In Arctic, the level of α-HCH was found to be linked to sea ice distribution. Geographically, the average concentration of α-HCH in air samples from the Chukchi and Beaufort Seas, neither of which contain sea ice, was 23 ± 4.4 pg m?3, while samples from the area covered by seasonal ice (～75°N to ～83°N), the so-called "floating sea ice region", contained the highest average levels of α-HCH at 48 ± 12 pg m?3, likely due to emission from sea ice and strong air-sea exchange. The lowest concentrations of α-HCH were observed in the pack ice region in the high Arctic covered by multiyear sea ice (～83°N to ～86°N). This phenomenon implies that the re-emission of HCH trapped in ice sheets and Arctic Ocean may accelerate during the summer as ice coverage in the Arctic Ocean decreases in response to global climate change.     

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.     

Temporal and spatial trends of organochlorine pesticides in Great Lakes precipitation

Organochlorine pesticide concentrations in precipitation samples collected from 1997 to 2003 at seven Integrated Atmospheric Deposition Network sites around the Great Lakes are reported. The 28-day volume weighted mean concentrations of several pesticides, including gamma-hexachlorocyclohexane (HCH), endosulfan, hexachlorobenzene, chlordane, and DDE, showed significant seasonal trends. For current-use pesticides (endosulfan and gamma-HCH), their concentrations peaked in late spring to summer just after their agricultural application. For the banned pesticides, higher concentrations were observed in the winter due to their enhanced partitioning to particles and scavenging by snow. Long-term decreasing trends were observed for several pesticides such as gamma-HCH and DDE. On the other hand, beta-HCH showed significant increasing concentrations as a function of time at Brule River, Eagle Harbor, and Sleeping Bear Dunes. Generally, Chicago had the highest concentration of chlordanes, dieldrin, and DDT, indicating that urban areas could be a source for these compounds to precipitation. For gamma-HCH and endosulfans, Point Petre had the highest concentrations due to the application of these pesticides in the surrounding areas.     

Atmospherc deposition of organochlorine compounds to remote high mountain lakes of Europe

Bulk deposition samples were taken near three mountain lakes located in the Pyrenees (Estany Redó), Alps (Gossenk?llesee), and Caledonian Mountains (Ovre Ne?dalsvatn) for evaluation of the atmospheric deposition load of organochlorine compounds (OC), namely, polychlorobiphenyls (PCBs), hexachlorocyclohexanes (HCHs), hexachlorobenzene (HCB), and endosulfans, in the remote European high mountain areas. The compounds of present use in agriculture, namely, endosulfans and gamma-HCH, exhibit large differences in mean deposition fluxes between the three sites. They occur in large amounts in Estany Redó (340 and 430 ng m(-2) month(-1) for endosulfans and gamma-HCH, respectively), reflecting the impact of agricultural activities in southern Europe. This lake showed also the highest proportion of the more labile endosulfan isomers (alpha and beta = 82%) whereas only the most recalcitrant species, endosulfan sulfate, was found in Ovre Ne?dalsvatn. In contrast, the OC whose use is now banned exhibit a more uniform geographic distribution with deposition fluxes of 31-40, 30-100, and 1.4-15 ng m(-2) month(-1) for alpha-HCH, PCBs, and HCB. Both compounds of present and past use exhibit a clear seasonal pattern, with higher deposition in the warm periods, which is consistent with enhanced volatilization at higher temperatures. In the case of the agricultural pesticides it may also reflect higher use during application periods. The OC distributions in the atmospheric deposition of the three sites are rather uniform and highly enriched in compounds with volatilities larger than 0.0032 Pa. However, more than 90% of these compounds are not retained in the lake waters or sediments. Comparison of OC composition in atmospheric and sedimentary deposition evidences a selective trapping of the less volatile compounds. Trapping efficiencies increase at decreasing air temperatures of the lacustrine systems.     

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.     

Selected organochlorine pesticides in the atmosphere of major Indian cities: levels, regional versus local variations, and sources

India has extensive production and usage of organochlorine pesticides (OCPs) for agriculture and vector control. Despite this, few data are available on the levels and distribution of OCPs in the urban atmosphere of India. Passive and active air sampling was therefore conducted between Dec 2006 and March 2007 in 7 metropolitan cities: New Delhi, Kolkata, Mumbai, Chennai, Bangalore, Goa, and Agra. Concentrations (pg·m(-3)) were as follows: HCHs 890-17000 (mean: 5400 ± 4110); DDTs 250-6110 (1470 ± 1010); chlordanes 290-5260 (1530 ± 790); endosulfans 240-4650 (1040 ± 610); and hexachlorobenzene 120-2890 (790 ± 510). HCHs observed in India appear to be the highest reported across the globe. Chlordanes and endosulfans are lower than levels reported from southern China. Passive sampling enabled within- and between-city variations to be assessed. As expected, paired-sample t-test analysis revealed higher regional than local variation. Comparisons with the limited data available from studies conducted in 1989 suggest general declines of HCHs and DDTs for most regions. γ-HCH dominated the HCH signal, reflecting widespread use of Lindane in India, although the isomeric composition in Kolkata suggests potential technical HCH use. High o,p'-/p,p'-DDT ratios in northern India indicate recent DDT usage. High HCB levels in the industrial areas of New Delhi and Kolkata indicate ongoing sources. Correlation between trans- and cis-chlordane implies ongoing usage. Endosulfan sulfate generally dominated the endosulfan signal, but high values of α/β-endosulfan at Chennai, Mumbai and Goa suggest ongoing usage. Backward trajectories were computed using the NOAA HYSPLIT model to trace the air mass history. Result shows local/regional sources of OCPs within India.     

Polychlorinated biphenyls (PCBs) in air and seawater of the Atlantic Ocean: sources, trends and processes

Air and seawater samples were collected on board the RV Polarstern during a cruise from Bremerhaven, Germany to Cape Town, South Africa from October-November 2005. Broad latitudinal trends were observed with the lowest sigma27PCB air concentration (approximately 10 pg m(-3)) in the South Atlantic and the highest (approximately 1000 pg m(-3)) off the west coast of Africa. Sigma(ICES)PCBs ranged from 3.7 to 220 pg m(-3) in air samples and from 0.071 to 1.7 pg L(-1) in the dissolved phase seawater samples. Comparison with other data from cruises in the Atlantic Ocean since 1990 indicate little change in air concentrations over the remote open ocean. The relationship of gas-phase partial pressure with temperature was examined using the Clausius-Clapeyron equation; significant temperature dependencies were found for all PCBs over the South Atlantic, indicative of close air-water coupling. There was no temperature dependence for atmospheric PCBs overthe North Atlantic, where concentrations were controlled by advection of contaminated air masses. Due to large uncertainties in the Henry's Law Constant (HLC), fugacity fractions and air-water exchange fluxes were estimated using different HLCs reported in the literature. These suggest that conditions are close to air-water equilibrium for most of the ocean, but net deposition is dominating over volatilization in parts of the transect. Generally, the tri- and tetrachlorinated homologues dominated the total flux (> 70%). Total PCB fluxes (28, 52, 118, 138, and 153) ranged from -7 to 0.02 ng m(-2) day(-1).     

Vertical and temporal distribution of persistent organic pollutants in Toronto. 1. Organochlorine pesticides

From May to September 2005, five passive air samples were deployed over five, 1-month periods at five elevations on the CN Tower in Toronto, Canada, to investigate the vertical distribution, seasonality, and sources of organochlorine pesticides. A strong seasonality was observed between spring and the end of summer. Vertical profiles differed for different pesticide classes. For instance, alpha- and gamma-hexachlorocyclohexane exhibited higher concentrations (60-80 pg m(-3), respectively) near the ground during the spring and early summer, suggesting that surface-air exchange within the city or nearby Lake Ontario may be important sources. The vertical profile for chlordane isomers was variable, suggesting that both advective and local inputs are important. For dieldrin, no obvious trend with elevation was observed, suggesting that concentrations could reflect a regional air mass contamination. Strongest seasonality was observed for the endosulfans, a widely used pesticide in North America, that reached peak concentrations of 750-850 pg m(-3) during June/July. Advective inputs of endosulfan from regional or more distant agricultural regions can explain the relatively uniform concentrations with elevation throughout the study period. The approach used in this study demonstrates that monthly average vertical concentration profiles differ between pesticide groups and reflect their use as well as the relative magnitude of input from local versus regional sources.