Mixture effect assessment applying in vitro bioassays to in-tissue silicone extracts of traditional foods prepared from beluga whale blubber.

We complement an earlier study on the nutrient and environmental contaminant levels in Arctic beluga whale traditional foods by mixture effect assessment using in vitro bioassays. Mixtures were extracted by in-tissue sampling of raw blubber and several traditional food preparations including Muktuk and Uqsuq using silicone (polydimethylsiloxane, PDMS) as sampler. PDMS extracts persistent and degradable neutral organic chemicals of a wide range of hydrophobicity with defined lipid-PDMS partition ratios. The solvent extracts of PDMS were dosed in various reporter gene assays based on human cell lines. Cytotoxicity was consistent across all cell lines and was a good indicator of overall chemical burden. No hormone-like effects on the estrogen receptor, the progesterone receptor and the glucocorticoid receptor were observed but a few samples activated the androgen receptor, albeit with low potency. The peroxisome-proliferator activated receptor (PPARγ) was the most sensitive endpoint followed by activation of oxidative stress response and activation of the arylhydrocarbon (AhR) receptor. The detected pollutants only explained a small fraction of the experimental mixture effects, indicating additional bioactive pollutants. The effect levels of the extracted mixtures were higher than those observed in blubber extracts of dugongs living off the shore of Australia. Roasting over an open fire or food preparation near a smokehouse led to increased PAH levels that were reflected in increased oxidative stress response and activation of the AhR. So far in vitro assays have only been used to quantify persistent dioxin-like chemicals in food and feed but this pilot study demonstrates a much broader potential for food safety evaluations complementing chemical analytical monitoring.

Semivolatile Organic Contaminants in the Hawaiian Atmosphere.

An air sampling campaign on the Island of Hawaii aimed to assess background concentrations of semivolatile organic compounds (SVOCs) over the Central Northern Pacific and to explore their distribution along an altitudinal transect. XAD-resin-based passive air samplers were deployed from May to September 2011 at six sites along a transect from the northeastern coast to the Mauna Loa Observatory and at three other island sites. By crossing the trade wind inversion, the transect comprised the marine boundary layer and free troposphere. At the two ends of the transect, flow-through samplers simultaneously sampled air at monthly resolution. Elevated levels of dieldrin, chlordane- and DDT-related pesticides, polycyclic aromatic hydrocarbons (PAHs), and polybrominated diphenyl ethers (PBDEs) at two urban sites indicated contributions from local sources. The composition of chlordane and DDT-related residues indicated recent emissions. PAHs concentrations that decline more rapidly with increasing elevation than those for PBDEs are consistent with faster atmospheric degradation of PAHs. SVOC levels on Mauna Loa were generally at the lower end of concentration ranges reported for remote sites, including the Arctic. However, in contrast to the Arctic, long-range atmospheric transport is deemed less important than human-induced material flow as the source of SVOCs to the island's atmosphere.

Effects of preparation on nutrient and environmental contaminant levels in Arctic beluga whale (Delphinapterus leucas) traditional foods.

For Canadian Arctic indigenous populations, marine mammal (MM) traditional foods (TFs) represent sources of both important nutrients and hazardous environmental contaminants. Food preparation is known to impact the nutrient and environmental contaminant content of processed items, yet the impacts of preparation on indigenous Arctic MM TFs remain poorly characterized. In order to determine how the various processes involved in preparing beluga blubber TFs affect their levels of nutrients and environmental contaminants, we collected blubber samples from 2 male beluga whales, aged 24 and 37 years, captured during the 2014 summer hunting season in Tuktoyaktuk, Northwest Territories, and processed them according to local TF preparation methods. We measured the levels of select nutrients [selenium (Se), polyunsaturated fatty acids (PUFAs)] and contaminants [organochlorine pesticides, perfluoroalkyl and polyfluoroalkyl substances (PFASs), polybrominated diphenyl ethers, polychlorinated biphenyls, polycyclic aromatic hydrocarbons (PAHs), mercury (Hg)] in raw and prepared (boiled, roasted, aged) beluga blubber TFs. The impacts of beluga blubber TF preparation methods on nutrient and environmental contaminant levels were inconsistent, as the majority of processes either did not appear to influence concentrations or affected the two belugas differently. However, roasting and ageing beluga blubber consistently impacted certain compounds: roasting blubber increased concentrations of hydrophilic substances (Se and certain PFASs) through solvent depletion and deposited PAHs from cookfire smoke. The solid-liquid phase separation involved in ageing blubber depleted hydrophilic elements (Se, Hg) and some ionogenic PFASs from the lipid-rich liquid oil phase, while PUFA levels appeared to increase, and hydrophobic persistent organic pollutants were retained. Ageing blubber adjacent to in-use smokehouses also resulted in considerable PAH deposition to processed samples. Our findings demonstrated that contaminant concentration differences were greater between the two sets of whale samples, based on age differences, than they were within each set of whale samples, due to variable preparation methods. When considering means to minimize human contaminant exposure while maximizing nutrient intake, consumption of aged liquid from younger male whales would be preferred, based on possible PUFA enhancement and selective depletion of hydrophilic environmental contaminants in this food item.

Exploring the role of the sampler housing in limiting uptake of semivolatile organic compounds in passive air samplers.

Passive air samplers (PASs) are simple, versatile devices that are increasingly used to determine the concentrations of semivolatile organic compounds (SVOCs) in the atmosphere. Using PAS and interpreting PAS-derived data with confidence requires a detailed understanding of the factors that control the uptake kinetics. A number of experiments were aimed at clarifying the role that the housing has in limiting the uptake of SVOCs in a PAS. Specifically, we quantified the gradient in the amount of polychlorinated biphenyls (PCBs) accumulated in XAD-filled mesh cylinders with increasing distance from the PAS housing's opening. That gradient was non-existent in an artificially ventilated housing (i.e. different segments of a cylinder contained the same amount of PCBs), minor during outdoor deployments (i.e. the bottom third of the cylinder sampled approximately 20% more PCBs than the top third), and strong during indoor deployments (i.e. the bottom third of the cylinder sampled twice the amount sampled by the top third). This is consistent with the thickness of the air boundary layer surrounding the XAD-resin increasing with increasing distance from the housing's opening and decreasing with increasing air turbulence. An experiment with housings absorbing different amounts of sunlight revealed that heat-induced convection has a minor effect on the gradient within the mesh cylinder and on the total amount of accumulated PCB. Similarly, this gradient and the total amount sorbed was also not influenced by the number of XAD-filled mesh cylinders placed within a housing as long as they were deployed outdoors. However, if four mesh cylinders were placed in one housing in a calm indoor setting, the top third of the mesh cylinders was notably starved of PCBs, suggestive of an air concentration gradient within the sampler housing.

Effect of wind on the chemical uptake kinetics of a passive air sampler.

Passive air samplers (PASs) operate in different types of environment under various wind conditions, which may affect sampling rates and thus introduce uncertainty to PAS-derived air concentrations. To quantify the effect of wind speed and angle on the uptake in cylindrical PASs using XAD-resin as the sampling medium, we measured the uptake kinetics of polychlorinated biphenyls (PCBs) in XAD and of water in silica-gel, both under quasi wind-still condition and with lab-generated wind blowing toward the PASs at various speeds and angles. Passive sampling rates (PSRs) of PCBs under laboratory generated windy conditions were approximately 3-4 times higher than under wind-still indoor conditions. The rate of water uptake by silica-gel increased with wind speed, following a logarithmic function so that PSRs are more strongly influenced at lower wind speed. PSRs of both PCBs and water varied little with wind angle, which is consistent with computational fluid dynamic simulations showing that different angles of wind incidence cause only minor variations of air velocities within the cylindrical sampler housing. Because modifications of the design of the cylindrical PAS were not successful in eliminating the wind speed dependence of PSRs at low wind levels, indoor and outdoor deployments require different sets of PSRs. The effect of wind speed and angle on the PSRs of the cylindrical PAS are much smaller than what has been reported for the double-bowl polyurethane foam PAS. PSRs of the cylindrical XAD-PAS therefore tend to vary much less between sampling sites exposed to different wind conditions.

Calibration and application of a passive air sampler (XAD-PAS) for volatile methyl siloxanes.

Because the atmosphere is key to understanding the environmental behavior of volatile methyl siloxanes (VMS), a variety of reliable air sampling methods are needed. The purpose of this study was to calibrate and evaluate an existing, polystyrene-divinylbenzene copolymeric resin-based passive air sampler (XAD-PAS) for VMS. Sixteen XAD-PAS were deployed for 7-98 days at a suburban site in Toronto, Canada, while the VMS concentration in air was monitored by an active sampling method. This calibration and a subsequent field test further allowed for investigation of the temporal and spatial variability of VMS in the region. Uptake in the XAD-PAS of octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and three linear VMS was linear throughout the whole deployment period. Sampling rates were between 0.4 and 0.5 m(3)/day. The XAD-PAS measured ∑VMS concentrations ranged from nondetects in rural areas (n = 3), to 169 ± 49 ng/m(3) in the urban region (n = 21), to levels above 600 ng/m(3) at sewage treatment plants (n = 2). Levels and composition of VMS within the urban area were remarkably uniform in space. Levels, but not composition, were highly variable in time and weakly correlated with temperature, wind speed, and wind direction.

Influence of sampler configuration on the uptake kinetics of a passive air sampler.

Passive air samplers (PAS) are simple and cost-effective tools to monitor semivolatile organic compounds in air. Chemical uptake occurs by molecular diffusion from ambient air to a passive sampling medium (PSM). Previous calibration studies indicate that even for the same type of PAS, passive air sampling rates (R, m(3)(air)/d) can be highly variable due to the influence of a number of factors. Earlier studies mainly focused on factors (e.g., wind speed and temperature) influencing R via the kinetic resistance posed by the air boundary layer surrounding the PSM because that layer was deemed to be the main factor determining the uptake kinetics. Whereas recent calibration studies suggest that the PAS configuration can influence R, so far few studies have specifically focused on this factor. In this study, with the objective to understand the effect of PAS configurations on R, we applied a gravimetrical approach to study the kinetics of water vapor uptake from indoor air by silica gel placed inside cylindrical PAS of various configurations. We also conducted an indoor calibration for polychlorinated biphenyls on the same type of PAS using XAD-resin as the PSM. R was found to be proportional to the interfacial transfer area of the PSM but not the amount of the PSM because chemicals mainly accumulated in the outer layer of the PSM during the deployment time of the PAS. The sampler housing and the PSM can introduce kinetic resistance to chemical uptake as indicated by changes in R caused by positioning the PSM at different distances from the opening of the sampler housing and by using PSM of different diameters. Information gained from this study is useful for optimizing the PAS design with the objective to reduce the material and shipping costs without sacrificing sampling efficiency.

Sampling medium side resistance to uptake of semivolatile organic compounds in passive air samplers.

Current theory of the uptake of semivolatile organic compounds in passive air samplers (PAS) assumes uniform chemical distribution and no kinetic resistance within the passive sampling media (PSM) such as polystyrene-divinylbenzene resin (XAD) and polyurethane foam (PUF). However, these assumptions have not been tested experimentally and are challenged by some recently reported observations. To test the assumptions, we performed kinetic uptake experiments indoors using cylindrical PSM that had been concentrically segmented into three layers. Both XAD and PUF were positioned in the same type of sampler housing to eliminate the variation caused by the different housing designs, which enabled us to quantify differences in uptake caused by the properties of the PSM. Duplicated XAD (PUF) samples were retrieved after being deployed for 0, 1 (0.5), 2 (1), 4 (2), 8 (4), 12 (8), and 24 (12) weeks. Upon retrieval, the PSM layers were separated and analyzed individually for PCBs. Passive sampling rates (R) were lower for heavier PCB homologues. Within a homologue group, R for XAD was higher than that for PUF, from which we infer that the design of the "cylindrical can" housing typically used for XAD PAS lowers the R compared to the "double bowl" shelter commonly used for PUF-disk PAS. Outer layers of the PSM sequestered much higher levels of PCBs than inner layers, indicative of a kinetic resistance to chemical transfer within the PSM. The effective diffusivities for chemical transfer within PSM were derived and were found negatively correlated with the partition coefficients between the PSM and air. Based on the results, we conclude that the PSM-side kinetic resistance should be considered when investigating factors influencing R and when deriving R based on the loss of depuration compounds.

Current-use pesticide transport to Costa Rica's high-altitude tropical cloud forest.

To gain insight into the atmospheric transport and deposition of organic contaminants in high-altitude forests in the humid tropics, pesticides were analyzed in air, water, and soil samples from Costa Rica. Passive samplers deployed across the country revealed annually averaged air concentrations of chlorothalonil, endosulfan, and pendimethalin that were higher in areas with intensive agricultural activities than in more remote areas. Atmospheric concentrations were particularly high in the intensively cultivated central valley. Only endosulfan and its degradation products were found in soils sampled along an altitudinal transect on the northern side of Volcano Turrialba, which is facing heavily cultivated coastal plains. Consistent with calculations of cold trapping in tropical mountains, concentrations of endosulfan sulfate increased with altitude. Pesticide levels in lake, creek, fog, and arboreal water samples from high-elevation cloud forests were generally below 10 ng · L(-1). Endosulfan sulfate was the most abundant pesticide in water, with concentrations ranging from 0.4 to 9.4 ng · L(-1). Its levels were highest in water sampled from bromeliads. Levels of total endosulfan in water are much lower than the reported median lethal concentration (LC50) value for acute toxicity of α-endosulfan to tadpoles. Although this suggests that the presence of pesticide might not have a direct impact on amphibian populations, the possibility of effects of chronic exposure to a mixture of substances cannot be excluded. Fog was relatively enriched in some of the analyzed pesticides, such as dacthal and chlorothalonil, and may constitute an important deposition pathway to high-altitude tropical cloud forest.

Fate of pesticides in the arid subtropics, Botswana, Southern Africa.

Despite a history of pesticide usage, few data exist on their concentrations in air and soil of Southern Africa. To add to the understanding of the processes controlling the fate of organic contaminants in arid regions, the levels, spatial trends, and seasonal variability of pesticides were studied in air and soil from Botswana. XAD resin-based passive air samplers (PAS) were deployed at 15 sites across the country from May 2006 to May 2007. Soil samples were collected from the vicinity of nine of the PAS sampling sites. In addition, 27 24-h high-volume air samples were collected in Maun, at the southeastern edge of the Okavango Delta, every two weeks for one year. Levels of pesticides in PAS were low, with α-endosulfan and lindane being most abundant. Concentrations in soils were extremely low and only soils with high organic carbon contained notable amounts of dieldrin and traces of other pesticides. In particular, air and soil from the Okavango Delta had very low levels even though the area had repeatedly been sprayed with DDT and endosulfan in the past. Air samples from Eastern Botswana, where the majority of the population lives, contained higher levels. Higher air concentrations of α-endosulfan occurred during summer and higher HCB levels occurred in winter. This seasonality was related with neither minor seasonal changes in temperature nor hydrological seasonal events such as the rainy season or the flooding of the Okavango Delta. Thus, the observed spatial and seasonal patterns are more likely related to pesticide usage pattern than to environmental factors or historical use. High temperature and low organic matter content limit the uptake capacity of most subtropical soils for pesticides. No evidence was found that sorption to dry mineral matter plays a major role. Arid soils in subtropical regions are therefore neither a major reservoir of organic contaminants nor do they constitute a significant long-term source of pesticides to the atmosphere.

Levels of polycyclic aromatic hydrocarbons in Canadian mountain air and soil are controlled by proximity to roads.

Concentrations of polycyclic aromatic hydrocarbons (PAHs) were measured in soil and XAD-based passive air samples taken from a total of 22 sites along three transects (Revelstoke, Yoho, and Observation, 6-8 sites for each transect) in the mountains of Western Canada in 2003-2004. Median concentrations in air (4-ring PAHs: 33 pg/m(3)) were very low and comparable to those in global background regions such as the Arctic. Low median soil concentrations (16 EPA PAHs: 16 ng/g dry weight) and compositional profiles dominated by naphthalene and phenanthrene are similar to those of tropical soils, indicative of remote regions influenced mostly by PAHs from traffic and small settlements. Comparing levels and composition of PAHs in soils between and along transects indeed suggests a clear relationship with proximity to local sources. Sampling sites that are closer to major traffic arteries and local settlements have higher soil concentrations and a higher relative abundance of heavier PAHs than truly remote sites at higher elevations. This remains the case when the variability in soil organic carbon content between sites is taken into account. Both air/soil concentration ratios and fugacity fractions suggest atmospheric net deposition of four-ring PAHs to soils.

Field testing a flow-through sampler for semivolatile organic compounds in air.

Even without access to the electrical grid, a flow-through sampler (FTS) can collect gaseous and particle-bound semivolatile organic compounds (SOCs) from large volumes of air by turning into the wind and having the wind blow through a porous sampling medium. To test its performance under field conditions, a FTS and a traditional pumped high volume air sampler, both using polyurethane foam (PUF) as sampling medium, were codeployed at the campus of the University of Toronto Scarborough from August 2006 to June 2007. Quantitative relationships between the wind speed outside the sampler and after passage through the PUF were established and allow the accurate estimation of sampling volumes under conditions of low and high wind speed. Polychlorinated biphenyls (PCBs) and polycyclic aromatic hydrocarbons (PAHs) were quantified in the samples taken by both air samplers. Separate analysis of seven PUF disks arranged sequentially within the FTS, confirm that even relatively volatile SOCs do not experience serious break-through. Theoretical plate number analysis of the break-through curves yields an understanding of the effect of temperature and wind speed on FTS sampling efficiency, and reveals different behavior of gaseous and particle-bound-compounds on the PUF. Air concentrations of PCBs and PAHs obtained with the FTS compare favorably with those obtained by averaging the concentrations of several 24 h active high volume samples taken during the same time period.

Pesticides in western Canadian mountain air and soil.

The distribution of organochlorine pesticides (OCP; in past and current use) in the mountains of western Canada was determined by sampling air, soil, and lichen along three elevational transects in 2003-2004. Two transects west of the Continental Divide were located in Mount Revelstoke and Yoho National Park, while the Observation Peak transect in Banff National Park is east of the divide. XAD-based passive air samplers, yielding annually averaged air concentrations, were deployed, and soils were collected at all 22 sampling sites, whereas lichen were only sampled in Revelstoke. Back trajectory analysis showed limited air mass transport from the Prairies to the east, but a high frequency of air arriving from the southwest, which includes agricultural regions in British Columbia and Washington State. Endosulfan, dieldrin, and a-hexachlorocyclohexane were the most prevalent OCPs in air and soil; hexachlorobenzene was only abundant in air; chlorothalonil, dacthal, and pentachloronitrobenzene were also consistently present. OCP air concentrations were similar across the three transects, suggesting efficient atmospheric mixing on a local and regional scale. Soil concentrations and soil/air concentration ratios of many OCPs were significantly higher west of the Continental Divide. The soil and lichen concentrations of most OCPs increased with altitude in Revelstoke, and displayed maxima at intermediate elevations at Yoho and Observation Peak. These distribution patterns can be understood as being determined by the balance between atmospheric deposition to, and retention within, the soils. Higher deposition, due to more precipitation falling at lower temperatures, likely occurs west of the divide and at higher elevations. Higher retention, due to higher soil organic matter content, is believed to occur in soils below the tree line. Highest pesticide concentrations are thus found intemperate mountain soils that are rich in organic matter and receive large amounts of cold precipitation.

Accumulation of current-use pesticides in neotropical montane forests.

In Central America, chemical-intensive tropical agriculture takes place in close proximity to highly valued and biologically diverse ecosystems, yet the potential for atmospheric transport of pesticides from plantations to national parks and other reserves is poorly characterized. The specific meteorological conditions of mountain ranges can lead to contaminant convergence at high altitudes, raising particular concern for montane forest ecosystems downwind from pesticide use areas. Here we show, based on a wide-ranging air and soil sampling campaign across Costa Rica, that soils in some neotropical montane forests indeed display much higher concentrations of currently used pesticides than soils elsewhere in the country. Specifically, elevated concentrations of the fungicide chlorothalonil, the herbicide dacthal, and the insecticide metabolite endosulfan sulfate on volcanoes Barva and Poas, lying directly downwind of the extensive banana plantations of the Caribbean lowland, indicate the occurrence of atmospheric transport and wet deposition of pesticides at high altitudes. Calculations with a contaminant fate model, designed for mountain regions and parametrized to the Costa Rican environment, show that chemicals with a log K(AW) between -3 and -5 have a greater potential for accumulation at high altitudes. This enrichment behavior is quantified by the Mountain Contamination Potential and is sensitive to contaminant degradability. The modeling work supports the hypothesis suggested by the field results that it is enhanced precipitation scavenging at high elevations (caused by lower temperatures and governed by K(AW)) that causes pesticides to accumulate in tropical montane areas. By providing for the first time evidence of significant transfer of currently used pesticides to Central American montane cloud forests, this study highlights the need to evaluate the risk that tropical agricultural practices place on the region's ecological reserves.

Organochlorine pesticides in the soils and atmosphere of Costa Rica.

A survey of the contamination of the physical environment of Costa Rica with banned organochlorine pesticides (OCPs) relied on sampling air and soil at 23 stations acrossthe country in 2004. Average annual air concentrations, determined with XAD-based passive samplers, and surface soil concentrations were generally low when compared to values reported for North and Central America, which is consistent with relatively low historical domestic use and little atmospheric inflow from neighboring countries. Statistical analysis and concentration maps reveal three types of spatial distribution: alpha-hexachlorocyclohexane and p,p'-DDD had a relatively uniform distribution across the country; other DDT-related species were greatly elevated over the national average at Manuel Antonio, a National Park on the Pacific coast; and dieldrin, lindane, and chlordane-related species had higher concentrations in Costa Rica's populated Central Valley. An altitudinal transect of stations in the Central Valley shows declining air-soil concentration ratios with elevation for lindane, likely driven by atmospheric inversions and soil organic carbon content. Enantiomeric composition of chiral OCPs in air and soil was close to racemic, with slight depletion of (-)-alpha-HCH, (-)-cis-chlordane, and (+)-trans-chlordane. Estimated air-soil fugacity fractions are highly uncertain but indicate equilibrium conditions for most OCPs, net volatilization of lindane at some sites, and net deposition for p,p'-DDE. The study demonstrates an approach for quickly evaluating the spatial distribution of OCPs in an understudied area, identifying regionally important contaminants and areas of elevated concentrations.

A flow-through sampler for semivolatile organic compounds in air.

A widely acknowledged limitation of current passive air sampling designs for semivolatile organic chemicals is their relatively low sampling rate, severely constraining the temporal resolution that can be achieved. Addressing the need for an improved sampling design which achieves significantly faster uptake while maintaining the capability of providing quantitative information, a new sampler has been developed that provides greatly increased sampling rates by forcing the wind to blow through the sampling medium. The sampler consists of a horizontally oriented, aerodynamically shaped, stainless steel flow tube mounted on a post with ball bearings, which turns into the wind with the help of vanes. A series of polyurethane foam (PUF) discs with relatively large porosity mounted inside the flow tube serve as the sampling medium. The sampled air volume is calculated from wind speed, which is measured outside the sampler and after passage through the sampling medium using precalibrated vortex rotor and turbine anemometers mounted on top of the sampler and at the exit of the flow tube, respectively. Small battery-operated data loggers are used for data storage. Under typical wind speed conditions, the sampler can collect 100 m(3)/ day, which is approaching the sampling rates of conventional high volume samplers. Controlled experiments in the laboratory and frontal chromatography theory yield the theoretical plate number and breakthrough volumes for polychlorinated biphenyls and polycyclic aromatic hydrocarbons in the PUF plugs and allow for the estimation of breakthrough levels for relatively volatile organic chemicals. After correction for breakthrough, the air concentration obtained with the new flow-through sampler are independent of sampling length and volume and compare favorably with those obtained from conventional pumped high volume samples.

Deposition of polybrominated diphenyl ethers, polychlorinated biphenyls, and polycyclic aromatic hydrocarbons to a boreal deciduous forest.

The atmospheric deposition of several groups of semi-volatile organic compounds to a deciduous forest in Canada was determined using an indirect technique based on ratios of measured canopy interception and air concentrations. Air (gas and particle phase) and bulk deposition were sampled for 14 months from October 2001 to December 2002 at both a forest and a nearby clearing, and extracts were quantified for polybrominated diphenyl ethers (PBDEs), polychlorinated biphenyls (PCBs), and polycyclic aromatic hydrocarbons (PAHs). Long-term average dry deposition velocities for vapors and particle-bound species were then derived for the canopy growing period. The mean dry gaseous deposition velocity for PBDEs and PCBs to the Canadian deciduous forest was 2.7 +/- 0.52 cm x s(-1), which is similar to the only other measured value for a deciduous canopy. Particle-bound deposition velocities to the canopy due to diffusion and impaction were 0.8 cm x s(-1) for the PBDEs and 0.11 cm x s(-1) for the PAHs. Differences in the particle-bound deposition velocities between PBDEs and PAHs and between deciduous canopies in Canada and Germany are explainable by differences in particle size distribution. The interception/concentration ratios for several PAHs were too low to be interpretable as dry gaseous deposition velocities. This is likely because the measured deposition flux under the canopy was less than the deposition flux to the canopy, possibly as a result of photodegradation in the canopy. From the ratio of canopy interception and average gas-phase concentration of less chlorinated PCBs, a predictive relationship between the canopy/air partition coefficient KPA and the octanol/air partition coefficient KOA was derived (KPA = 110 KOA0.67). Despite differences in local climate and canopy composition and structure, the deposition velocities and the canopy uptake capacity measured in Canada were remarkably similar to those reported in Germany, lending credibility to the suggestion that high gaseous deposition velocities are common throughout boreal and temperate deciduous forests. These extraordinarily high deposition velocities of semi-volatile organic compounds to deciduous forest canopies are at the core of the hypothesis of a significant filter effect of forests on a regional and global scale.

Comparative evaluation of three high-performance liquid chromatography-based Kow estimation methods for highly hydrophobic organic compounds: polybrominated diphenyl ethers and hexabromocyclododecane.

Three methods for estimating the octanol-water partition coefficient (Kow) based on its relationship with capacity factors on reversed-phase (RP) high-performance liquid chromatography (HPLC) columns were compared in terms of their applicability to highly hydrophobic compounds (HHCs). Methods based on simple isocratic elutions were found to be unsuitable, because the very high organic modifier fractions that are required to elute HHCs from RP columns challenge the basic assumption of the similarity between the octanol-water and RP-eluent systems. Compound planarity was found to exert a considerable influence on the retention of HHCs in RP columns, leading to different linear calibration curves for chlorobenzenes and chlorobiphenyls. Only an empirical exponential regression succeeded in describing the behavior of both groups of compounds during gradient elutions. In a method based on isocratic retention times at multiple temperatures, satisfactory calibration was achieved with a multivariate linear regression that included a numerical indicator of compound planarity. Considering experimental simplicity, speed, precision, and accuracy, with the latter judged by comparison with Kow values for polybrominated diphenyl ethers and polychlorinated naphthalenes as reported in the literature, a gradient elution combined with an exponential calibration curve is recommended for estimating the Kow of HHCs. To our knowledge, the first isomer-specific Kow values for hexabromocyclododecane are reported. Bearing in mind that the influence of structural characteristics on retention is likely to increase with hydrophobicity, it is not justified to judge a HPLC-based Kow estimation method as being suitable for HHCs because it is shown to work well for less hydrophobic substances. Whereas univariate linear regressions often may prove to be sufficient when dealing with substances having a log Kow, of less than five, methods for HHCs need to account for the influence of structure on retention.

Polychlorinated biphenyls and polybrominated diphenyl ethers in the North American atmosphere.

To assess the spatial concentration variability of polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs) in the atmosphere on a large continental scale, their annually integrated air concentrations were determined in 2000/2001 using XAD-based passive air samplers (PAS). The network included 40 stations in Canada, the United States, Mexico, Belize and Costa Rica, and covered 72 degrees of latitude and longitude. Total concentrations of PCB and PBDE congeners ranged from below the detection limit to 130 ng PAS-1 and 24 ng PAS-1, respectively. PCBs displayed a large variation between urban, rural and remote sites, whereas PBDEs did not follow such a pattern. Open burning of "Penta"-containing waste may have contributed to the PBDEs detected in the air samples from rural and remote areas. Air from the Canadian Arctic had a relatively higher percentage of lighter PCB congeners than air sampled in the tropical region, which is interpreted as evidence for global fractionation.

Atmospheric distribution and long-range transport behavior of organochlorine pesticides in North America.

Annually averaged concentrations and enantiomeric compositions of organochlorine pesticides (OCPs) in air were determined in 2000/2001 at 40 stations across North America using XAD-based passive samplers. Absolute concentration differences acrossthe continent, the skewness and kurtosis of the concentration distribution, the relative abundance of parent compound and metabolites, and the chiral signatures can identify regional sources of OCP to the atmosphere. Specifically, air samples collected in the southeastern United States had elevated concentrations of chlordane-related compounds, higher ratios of trans- to cis-chlordane and heptachlor to heptachlor epoxide, as well as higher enantiomeric fractions of trans-chlordane as compared to other regions, suggesting continued release of microbially unprocessed chlordane to the regional atmosphere. Similarly, greatly elevated concentrations of p,p'-DDT, low relative abundance of the metabolite DDE, and a racemic composition of o,p'-DDT in samples from southern Mexico and Belize indicate recent use of DDT in these regions. Belize is also a potential source region for dieldrin. Reflecting its continued use in North America, endosulfan is now one of the most abundant and ubiquitous OCPs in the continental atmosphere. In contrast to these OCPs, air concentrations of penta- and hexachlorobenzene vary only by factors of 2-4 across the continent, reflecting a long atmospheric residence time and few primary sources. Atmospheric levels of the chlorobenzenes, alpha-endosulfan, and p,p'-DDE increase with elevation in the Canadian Rocky Mountains. Empirical travel distances for the OCPs derived from latitudinal concentration profiles are in good agreementwith model-derived indicators of long-range transport potential and, in particular, lead to a similar categorization of the OCPs. Large-scale passive air sampling networks are suitable for monitoring compliance with, and effectiveness of, regulatory control measures and for establishing experimentally the atmospheric long-range transport behavior of organic air pollutants.