Spatial and temporal trends of POPs in Norwegian and UK background air: implications for global cycling

Data are presented for PCBs and HCB measured by passive air samplers (SPMDs) along a latitudinal transect from the south of the UK to the north of Norway during 1998-2000. This work is part of an ongoing air sampling campaign in which data were previously gathered for 1994-1996. Comparisons of the masses of chemicals sequestered by the SPMDs during these different time intervals are used to investigate spatial and temporal trends. Results are discussed in the context of sources, long-range atmospheric transport, fractionation/cold condensation, and global clearance processes controlling ambient levels of POPs. Spatial trends show a decrease in absolute sequestered amounts of PCBs with increasing latitude i.e., with increasing distance from the source area. However, relative sequestered amounts of the homologue groups (expressed as a ratio to penta-PCB) show a clear latitudinal trend, with the relative contribution of the lighter congeners increasing with increasing latitude, providing evidence of latitudinal fractionation. Absolute amounts of HCB increase with latitude, suggesting this compound is undergoing cold condensation. Sequestered amounts of PCBs generally decreased between the two sampling periods by a factor 2-5 over 4 years, suggesting half-lives on the order of 1.7-4 years. The relative rates of decline (1998-2000 data as a percentage of the 1994-1996 data) were compared for different congeners and latitudes. No clear latitudinal trends were found, with all sites/congeners showing a similar marked decline over time to ca. 30% of the former value. We discuss the interpretation of these observations and conclude they imply that the underlying trends of current ambient levels of PCBs in European background air are still largely controlled by primary emissions, rather than recycling/secondary emissions from the major environmental repositories such as soils or water bodies.     

Temporal and spatial trends of atmospheric polychlorinated biphenyl concentrations near the Great Lakes

Polychlorinated biphenyl (PCB) concentrations were measured in the atmosphere at six regionally representative sites near the five Great Lakes from 1990 to 2003 as part of the Integrated Atmospheric Deposition Network (IADN). Concentration data for several individual PCB congeners and for total PCBs were analyzed for temporal and spatial trends after correcting for the temperature dependency of the partial pressures. Atmospheric PCB concentrations are decreasing relatively slowly for tetra- and pentachlorinated congeners, an observation that is in agreement with primary emissions modeling. Relatively rapid decreases in PCB concentrations at the sites near Lakes Michigan and Ontario may reflect successful reduction efforts in Chicago and Toronto, respectively. Atmospheric PCB concentrations near Lakes Superior and Huron are now so low that the air and water concentrations may be close to equilibrium. Atmospheric PCB concentrations at sites near Lakes Michigan, Erie, and Ontario are relatively higher than those measured at sites near Lakes Superior and Huron. The highest PCB level was observed at the site near Lake Erie, most likely due to nearby urban activity. However, this relatively higher concentration is still 6-10 times lower than that previously reported at the Chicago site. A correlation between average gas-phase PCB concentration with local population indicates a strong urban source of PCBs. The temperature dependence of gas-phase PCB concentrations is similar at most sites except at Burnt Island on Lake Huron, where very low concentrations, approaching virtual elimination, prevent reliable temperature correlation calculations.     

Coupling passive air sampling with emission estimates and chemical fate modeling for persistent organic pollutants (POPs): a feasibility study for Northern Europe

Passive air samplers (polyurethane foam disks) were deployed at 23 background locations along a broadly west-east transect in 8 northern European countries and analyzed for PCBs, PBDEs, PAHs, and a range of organochlorine pesticides (HCB, DDTs, and DDEs). PCBs and PAHs were highest at the center of the transect (Denmark) and lowest in northern Norway. HCB was relatively uniformly distributed, reflecting its persistence and high degree of mixing in air. Higher DDE and DDT levels occurred in Eastern Europe and at several sites in Central Europe. PBDE levels were generally similar at all sites, but lower for some locations in Eastern Europe and Ireland. Emissions information for PCBs, HCB, and PBDEs was used as input for a multi-media chemical fate model, to generate predicted air concentrations and compare with these measured values. Different scenarios were highlighted by this exercise: (i) country and compound combinations where the national inventory gave predicted air concentrations in close agreement with those measured (e.g., PCBs in the UK); (ii) country and compound combinations where predicted concentrations were well below those measured, but where advection of emissions from elsewhere is likely to be important (e.g., PCBs in Norway); (iii) consistent underestimation of compound concentrations by the emissions modeling (i.e., HCB); and (iv) general overestimation of ambient concentrations (i.e., PBDEs). Air mass trajectory analysis showed the likely role of long-range atmospheric transport (LRAT) on national levels. In general, advection from the south and west of Europe appeared to contribute to ambient POPs levels for countries in the center and northeast of the transect. Guidelines are presented as to how countries that want to assess their POPs source inventories can do so with this relatively cheap initial screening approach.     

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.     

Field deployment of thin film passive air samplers for persistent organic pollutants: a study in the urban atmospheric boundary layer

This paper reports on the first field deployment of rapidly equilibrating thin-film passive air samplers under ambient conditions. The POlymer-coated Glass (POG) samplers have a coating of ethylene vinyl acetate (EVA) less than 1 microm thick applied to a glass surface. This can be dissolved off after exposure and prepared for the quantification of persistent organic pollutants (POPs) that have partitioned into the film during field exposure. In this study, POGs were deployed at various heights on the CN Tower in Toronto, Canada, to investigate the vertical distribution of selected compounds (PCBs, PAHs, organochlorine pesticides) in the atmospheric boundary layer of an urban area. The feasibility of the method to detect POPs from a few cubic meters of air was demonstrated, indicating the potential for rapid, low-volume sampling of air for ambient levels of POPs. PAH levels declined sharply with height, confirming ground-level emissions in urban areas as sources of these compounds; PCBs did the same, although less strongly. Different sampling events detected different vertical distributions of OC pesticides which could be related to local or distantsources, and variations in POPs on the samplers in these different events/heights demonstrate the dynamic nature of sources and atmospheric mixing of POPs.     

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.     

Bottlenose dolphins as indicators of persistent organic pollutants in the western North Atlantic Ocean and northern Gulf of Mexico

Persistent organic pollutants (POPs) including legacy POPs (PCBs, chlordanes, mirex, DDTs, HCB, and dieldrin) and polybrominated diphenyl ether (PBDE) flame retardants were determined in 300 blubber biopsy samples from coastal and near shore/estuarine male bottlenose dolphins (Tursiops truncatus) sampled along the U.S. East and Gulf of Mexico coasts and Bermuda. Samples were from 14 locations including urban and rural estuaries and near a Superfund site (Brunswick, Georgia) contaminated with the PCB formulation Aroclor 1268. All classes of legacy POPs in estuarine stocks varied significantly (p < 0.05) among sampling locations. POP profiles in blubber varied by location with the most characteristic profile observed in bottlenose dolphins sampled near the Brunswick and Sapelo estuaries along the Georgia coast which differed significantly (p < 0.001) from other sites. Here and in Sapelo, PCB congeners from Aroclor 1268 dominated indicating widespread food web contamination by this PCB mixture. PCB 153, which is associated with non-Aroclor 1268 PCB formulations, correlated significantly to human population indicating contamination from a general urban PCB source. Factors influencing regional differences of other POPs were less clear and warrant further study. This work puts into geographical context POP contamination in dolphins to help prioritize efforts examining health effects from POP exposure in bottlenose dolphins.     

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.     

Further studies on the latitudinal and temporal trends of persistent organic pollutants in Norwegian and U.K. background air

Data are presented for PBDEs, PCBs, and selected organochlorine compounds, measured at background locations by passive air samplers (semipermeable membrane devices, SPMDs) along a latitudinal transect from the south of the U.K. to the north of Norway during 2000-2002. This work is part of an ongoing air sampling campaign in which PCB data were previously obtained in 1994-1996 and 1998-2000. Comparisons of the masses of chemicals sequestered by the SPMDs during these different time intervals are used to investigate spatial and temporal trends. The study yielded examples of compounds that increase, decrease, or remain uniform with latitude, suggestive of differences in the relative importance of deposition versus atmospheric reaction in controlling their long-range atmospheric transport potential. The main constituents of the penta-BDE product were detected at amounts equivalent to 2.0 (range 1.1-2.5) and 1.1 (0.8-1.6) pg m(-3) for the U.K. and Norway background sites, respectively. Fractionation of PBDEs was observed, because the amounts of lighter BDEs decreased with latitude, while the heavier molecular weight congeners were quite uniformly distributed. In contrast, the sequestered amounts of the lighter PCBs were uniformly distributed with latitude, with heavier PCBs decreasing. Sequestered amounts of hexachlorobenzene increased with latitude. Preliminary PCB atmospheric clearance rates were derived using the 1994-1996, 1998-2000, and 2000-2002 data. They averaged ca. 3.5 years for all congeners/locations. No systematic differences in congeners or locations were noted, supporting the hypothesis that the underlying trends in European background air are still controlled by primary, rather than secondary, sources.     

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.     

Factors influencing the soil-air partitioning and the strength of soils as a secondary source of polychlorinated biphenyls to the atmosphere

Soils are a major reservoir of persistent organic pollutants, and soil-air partitioning and exchange are key processes controlling the atmospheric concentrations and regional fate of pollutants. Here, we report and discuss the concentrations of polychlorinated biphenyls (PCBs) in soils, their measured fugacities in soil, the soil-air partition coefficients (K(SA)) and soil-air fugacity gradients in rural background areas of N-NE Spain and N-NW England. Four sampling campaigns were carried out to assess seasonal and daily variability and differences between sampling sites. K(SA) values were significantly dependent on soil temperature and soil organic matter quantity, and to a minor extent organic matter type. All the PCB congeners in the soil are close to equilibrium with the atmosphere at rural Ebro sites, but soil fugacities tend to be higher than ambient air fugacities in early and late summer, consistent with the influence of temperature on soil-air partitioning. Therefore, during warm periods, soils increment their strength as secondary sources to the atmosphere. The mixture of PCBs found in the atmosphere is clearly strongly influenced by the mixture of PCBs which escape from soil, with significant correlations between them (R(2) ranging between 0.35 and 0.74 and p-level <0.001 for the Ebro sampling sites). Conversely, the close-to-equilibrium to net sink status of rural UK sites, suggest a close coupling of air and soil concentrations, but it is not possible to elucidate the importance of these soils as secondary sources yet, and presumably there are still significant primary sources to the regional/global environment.     

Temporal trends of polycyclic aromatic hydrocarbons in the U.K. atmosphere: 1991-2005

Internationally there are few long-term air monitoring programs, which are necessary to assess the effectiveness of source abatement measures as required underthe UNECE POPs protocol. In the United Kingdom, the Toxic Organic Micropollutants (TOMPS) program, funded by the Department for Environment, Food, and Rural Affairs (Defra), was started in 1991 and includes regular monitoring of a range of compounds including polycyclic aromatic hydrocarbons (PAHs). In this study, the time series (1991-2005) of atmospheric concentrations of 15 PAHs at six U.K. monitoring sites were investigated. Most show a statistically significant decrease in PAH levels over time, broadly consistent with the reported decline in emissions. Higher levels of heavier PAHs were noted in winter than in summer at most sites. At one coastal site, higher levels of lighter PAHs were noted in summer, possibly due to temperature-driven outgassing of these compounds from seawater. Current annual averages of benzo[a]pyrene are below the recently introduced annual air quality standard of 0.25 ng m(-3) at all sites, although quarterly averages have exceeded 0.25 ng m(-3) in recent years but only at the urban sites in winter. The atmospheric signature of total PAHs closely mirrors the emission signature, which lends strength to the idea that levels of PAHs in air are still mostly influenced by direct/local sources.     

Abundances, depositional fluxes, and homologue patterns of polychlorinated biphenyls in dated sediment cores from the Pearl River Delta, China

Despite the recent efforts to investigate the distribution and fate of persistent organic pollutants in the tropical and subtropical regions of Asia, very little was known about the temporal change of polychlorinated biphenyls (PCBs) in the environmental ecosystem of China. In this study, three dated sediment cores collected from the Pearl River Delta of southern China were analyzed for a large suite of PCB congeners, from which the temporal profiles of PCB abundances, fluxes, and homologue patterns were constructed. The sedimentary inventories of total PCBs at the sampling sites ranged from 480 to 1310 ng/cm2, at the low end of the worldwide figures. Although production and use of PCBs have been banned or highly restricted in China since the early 1980s, the fluxes of total PCBs continued to increase in the Pearl River Delta sediments. There was a concurrent increase of PCB fluxes and gross domestic product per capita in the region from 1980 to 1997, and a decline of agricultural land use was evident at the same time. Apparently, large-scale land transform since the early 1980s as well as emissions from the PCB-containing electrical equipments were responsible for the sharp rise of PCB fluxes in the recent sediments. The difference in the PCB homologue patterns from 1940 to the mid-1970s was probably indicative of the different timelines of PCB usage in Macao/Hong Kong and mainland China and the differenttypes of technical PCBs commercially used. PCBs were detectable in sediments deposited well before the time frame when production of PCBs began (before 1930) and were relatively enriched in the less chlorinated homologue groups (3Cl and 4Cl PCBs), suggesting the downward mobility of lightly chlorinated PCB congeners in the sediment column.     

Are PCBs in the Canadian Arctic atmosphere declining? Evidence from 5 years of monitoring

A long-term database of weekly air concentrations was examined to establish temporal trends of PCBs in the Arctic atmosphere. Several methods were employed to reduce the intra-annual variability allowing the elucidation of longterm trends for a selection of congeners at Alert located in the Canadian Arctic. These methods included temperature normalization (TN), multiple linear regression (MLR), and digital filtration (DF). Estimation of the slope (m) resulting from the linear regression between the natural logarithm of the partial pressure in air versus reciprocal temperature (In P = m/T + b), required for TN and MLR, proved difficult due to the poor correlation with temperature experienced forthe majority of congeners. Values of m were considerably lower than those obtained from temperate studies, implying that regional air-surface exchange plays a minor role in supporting the observed air concentrations in the Arctic. The lighter congeners generally showed very low slopes, and some even showed positive correlation with 1/T. This might be a result of their relatively fast reaction rates with OH radicals following the onset of 24-h sunlight in spring. Use of DF (in combination with TN and MLR) revealed declining trends for several of the lower chlorinated congeners in the high Arctic atmosphere, with estimated first-order half-lives, t1/2, ranging from approximately 3 to 20 yr. Declining trends of the lower congeners probably reflect falling levels in source regions, as a result of long-range transport to this Arctic site. There were no apparent trends for the higher chlorinated congeners (penta-substituted and above), exceptfor PCB 180, in marked contrast to temperate studies, indicating a lag time for decline between the Arctic and source regions.     

Multivariate data analyses of persistent organic pollutants in maternal adipose tissue in Singapore

Persistent organic pollutants (POPs) were detected in 88 maternal adipose tissue samples collected during year 2004 to 2006, in Singapore. Organochlorine pesticides (OCPs) were the most dominant followed by polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs). Multivariate data analyses (MVA) including principal component analysis (PCA), partial least-squares regression (PLSR), and partial least-squares discriminant analysis (PLS-DA) were applied to elucidate the relationship between concentrations of POPs in adipose tissues and donors' characteristics. Food consumption played the most significant role in accounting for levels of POPs in adipose tissue. Fish and poultry consumption was the route of PCBs and PBDEs in mothers in Singapore, while beta-HCH came mainly from vegetables. An age-dependent accumulation of POPs was found for beta-HCH and PCB congeners, and lactation and gestation functioned as a decontamination processes for PCBs in adipose tissue. Gestational diabetes mellitus (GDM) may change the profile of POPs in adipose tissue, probably due to an alteration in lipid metabolism. POPs investigated here may not be the cause of antenatal complication in pregnant women, and baby gender was not related to the pattern of contaminants in maternal adipose tissue.     

Time trends of atmospheric PBDEs inferred from archived U.K. herbage

Aerial portions of vegetation receive the bulk of their burden of persistent organic pollutants (POPs) from the atmosphere. Vegetation can therefore be a useful indicator of the changing atmospheric burden of POPs. Samples of archived pasture, collected from Rothamsted Experimental Station in the United Kingdom between 1930 and 2004, were analyzed for a range of polybrominated diphenyl ethers (PBDEs). PBDEs could not be routinely detected in the pre-1970 samples. Thereafter, the dominant congeners BDE 28, 47, 49, 99, 100, 153, 154, and 183 were frequently detected. The general trend was (a) a rise through the 1970s; (b) a minipeak in the mid-1980s, strongly influenced by one particularly high sample for 1984; (c) values remaining high through the late 1980s/1990s; (d) an indication of a more recent decline for all congeners (except BDE-28), consistent with recent restrictions on PBDE usage in Europe. These trends were compared to recent modeled estimates of U.K. PBDE emissions. The congener profiles of technical mixtures, U.K. air, soil, and pasture were compared and shown to be broadly similar. The implications for environmental release mechanisms are discussed.     

Congener-specific survey for polychlorinated biphenlys in sediments of industrialized bays in Korea: regional characteristics and pollution sources

Areas of the Korean coastline with heavy industry and major harbors were investigated for polychlorinated biphenyl (PCB) pollution. This investigation paid attention to variations in the PCB congener patterns for a possible source of contamination. Surface sediments from 49 sites were sampled. Although the occurrence of PCBs in coastal marine environment correlates well with shipping and industrial activities, the contribution from shipping activities is considerable because of its enormous economical importance in Korea. The highest concentrations were found in harbors with heavy ship traffic and ship construction. Principal component analysis (PCA) of congener-specific composition of PCBs revealed distinct regional patterns, especially in a harbor and steel manufacturing area. PCB signatures with enhanced higher chlorinated congeners were typical for harbors with shipping activities and correlated well with commercial formulations that were formerly used in ship painting. Lower chlorinated congeners with up to five chlorines were significantly abundant in steel works zones which differed from harbor zones. This distinction was consistent with the congener patterns in the ambient air and the effluent of the steel works as well as in the nearby surface sediments. This study identified steel manufacturing as a recent and ongoing emission source of PCBs in Korea's coastal zone.     

Investigation into the importance of the stomatal pathway in the exchange of PCBs between air and plants

The transfer of persistent organic pollutants (POPs) from air to vegetation is an important air-surface exchange process that affects global cycling and can result in human and wildlife exposure via the terrestrial food chain. To improve understanding of this process, the role of stomata in uptake of gas-phase polychlorinated biphenyls (PCBs) was investigated using Hemerocallis x hybrida "Black Eyed Stella", a plant with a high stomatal density. Uptake of PCBs was monitored over a 72-h period in the presence and absence of light. Uptake rates were significantly greater in illuminated (stomata open) plants than unilluminated (stomata closed) plants for 18 of the 28 measured PCB congeners (p < 0.05). Depuration of PCBs was monitored in a subsequent experiment over a period of 3 weeks. Levels after 3 weeks of depuration time were still much higher than the concentration prior to contamination. Tri- and tetrachlorinated PCBs showed the greatest depuration, with less than 20% and 50% of accumulated PCBs respectively remaining, while approximately 70% of higher chlorinated PCB congeners remained in the plants at the end of the experiment. Treatments with/without light (to control stomatal opening during uptake) and with/without abscisic acid (ABA) application (to control stomatal opening during depuration) were compared. After contamination indoors for 3 days, there was a significantly higher concentration of PCBs (p < 0.05) in the light contaminated plants than the dark-contaminated plants for 13 of the 28 measured PCB congeners. The ABA treatment affected depuration of PCB-18 only. "Light/ABA-treated" plants had a significantly slower depuration rate for PCB-18 than "light/untreated", "dark/ABA-treated", and "dark/untreated" plants (p < 0.05). The results of the study indicate that there is a stomatal effect on the rate of exchange of PCBs between Hemerocallis leaves and air.     

Has the burden and distribution of PCBs and PBDEs changed in European background soils between 1998 and 2008? Implications for sources and processes

Background soils were collected from 70 locations on a latitudinal transect in the United Kingdom and Norway in 2008, ten years after they had first been sampled in 1998. The soils were analyzed for polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers (PBDEs), and organochlorine pesticides (OCs), to see whether there had been any change in the loadings or distributions of these persistent organic pollutants (POPs). The same transect has also been used to sample air between the mid-1990s and the present, so the air and soil spatial and temporal trends provide information on air-soil transfers, source-receptor relationships, long-range atmospheric transport (LRAT), and recycling phenomena. Comparisons of the 2008 and 1998 data sets show a general decline for PBDEs in surface soil, and a smaller averaged net decline of PCBs. Changes between the years were observed for total POP concentrations in soil and also for correlations with site and sample characteristics assumed to affect those concentrations. POP concentrations were correlated to distance and strength of possible sources, a relationship that became weaker in the 2008 data. Fractionation, a commonly discussed process for the global cycling of POPs was also lost in the 2008 data. As in 1998, soil organic matter content continues to have a strong influence on the loadings of POPs in surface soils, but changes in the PCB loads were noted. These factors indicate an approach to air-surface soil equilibrium and a lessening of the influence of primary sources on POP concentrations in soil between 1998 and 2008.     

Long-term fate of polychlorinated biphenyls and polycyclic aromatic hydrocarbons in an agricultural soil

Laboratory studies are useful for understanding the behavior of persistent organic pollutants (POPs) in soil, although such investigations do not always relate directly to field conditions. Outdoor lysimeter studies may be used to overcome this problem. This work aimed to investigate the behavior of two polycyclic aromatic hydrocarbons (PAHs) (fluoranthene and benzo[a]pyrene) and two polychlorinated biphenyls (PCBs; congeners 28 and 52) in soil, using lysimeters established in 1990 atthe Agrosphere Institute (Forschungszentrum Julich GmbH, Germany). The two PAHs were in one lysimeter, and the PCBs were in a second lysimeter. Afurther aim of the study was to determine soil half-lives for each of the contaminants. The overall decline in PAH concentrations was considerably greater than forthe PCBs over the 152 month study. The PCBs exhibited greater chemical extractability than the PAHs and were demonstrated to have migrated through the soil column to a greater extent than the PAHs. Loss of PCBs from surface soil was not considered to have been congener specific for the two PCB congeners in this study. The two PAHs varied in their extents of total loss and movement through the soil column. Soil half-lives were determined as 10.9 y for [12C]PCB 28, 11.2 yr for [12C]PCB 52, 2.7 yr for benzoqpyrene, and 32 d (phase 1) to 38 yr (phase 2) for fluoranthene. These are shown to disagree with some previous estimates of POP half-lives in soil, suggesting that previous studies underestimated persistence by 10-fold or more.