Characterization of polymer coated glass as a passive air sampler for persistent organic pollutants

The use of thin-film polymer-coated glass surfaces or POGs as passive air samplers was investigated during an uptake experiment in an indoor environment with high levels of gas-phase polychlorinated biphenyls (PCBs). POGs consisted of a micron thick layer of ethylene vinyl acetate (EVA) coated onto glass cylinders. The uptake was initially linear with time and governed by the air-side mass transfer coefficient and surface area of the sampler. This was followed by a curvilinear region and finally a constant phase when equilibrium was established between air and EVA. The high surface area-to-volume ratio of the POGs allowed rapid equilibrium with gas-phase PCBs; equilibration times were on the order of hours for the low molecular weight congeners. The equilibrium concentration was dependent on the EVA-air partition coefficient, K(EVA-A), which was shown to be very well correlated to the octanol-air partition coefficient, K(OA). When POGs of varying thickness were equilibrated with air, the amount of PCB accumulated increased with increasing thickness of the EVA, indicating that uptake was by absorption into the entire polymer matrix. A wind field of 4 m s(-1) resulted in an increased uptake rate by a factor of approximately six compared to uptake in relatively still air. This wind speed effect was diminished, however, when POGs were housed in deployment chambers consisting of inverted stainless steel bowls. Relationships based on the air-side mass transfer coefficient and K(EVA-A) were developed for PCBs that describe the entire uptake profile and allow air concentrations to be determined from the amount of chemical accumulated in the POG. It is believed that these relationships are also valid when POGs are used to detect other classes of persistent organic pollutants.     

Rapidly equilibrating micrometer film sampler for priority pollutants in air

Modified polymer-coated glass samplers (POGs), termed EVA samplers, consist of micrometer-thin layers of ethylene vinyl acetate (EVA) coated onto a glass fiber filter or aluminum foil substrate. These samplers were designed to equilibrate rapidly with priority pollutants in air, making them ideal for short-term spatial studies in ambient or indoor air. The EVA sampler was calibrated by measuring the uptake of polychlorinated biphenyls (PCBs) over 8 weeks in an indoor environment, and four different film thicknesses were monitored that ranged from 0.1 to 30 μm. The results were used to calculate the average mass transfer coefficient (50.5 m/day) and generate contour maps that provide guidance in choosing an appropriate EVA sampler for a particular study based on film thickness, deployment time, and the log K(OA) of the anlayte. A range of air pollutant classes was also added to the EVA sampler prior to deployment to assess depuration rates. These included polychlorinated biphenyls (PCBs), current-use pesticides (CUPs), perfluorinated compounds (PFCs), and polybrominated diphenyl ethers (PBDEs). On the basis of the depuration profiles, the EVA sampler was a suitable equilibrium sampler for several CUPs and PCBs; however, for the high molecular weight PCBs and PBDEs, the EVA sampler operates as a linear uptake sampler. Samplers were also evaluated for their use as a rapid screening tool for assessing concentrations of siloxanes in indoor air. The EVA sampler was used to estimate air concentrations for D4 and D5 in laboratory air to be 118 and 89 ng/m(3), respectively. Analyses were performed directly using thermal desorption gas chromatography/mass spectrometry (TDS-GC-MS). EVA samplers show promise due to their relatively low cost and ease of deployment and applicability to a wide range of priority chemicals. The ability to alter the film thickness, and hence the sorption capacity and performance of the EVA sampler, allows for a versatile sampler that can be used under varying sampling conditions and deployment times.     

Characterization and comparison of three passive air samplers for persistent organic pollutants

The accumulation of persistent organic pollutants by three passive sampling media--semipermeable membrane devices (SPMDs), polyurethane foam (PUF) disks, and an organic-rich soil--was investigated. The media were exposed to contaminated indoor air over a period of 450 days, and concentrations in the air and in the media were monitored for individual polychlorinated biphenyl (PCB) congeners and polychlorinated naphthalene homologue groups. Uptake was initially linear and governed by the surface area of the sampler and the boundary layer airside mass transfer coefficient (MTC). Mean values of the MTC were 0.13, 0.11, and 0.26 cm s-1 for SPMD, PUF, and soil, respectively. As the study progressed, equilibrium was established between ambient air and the passive sampling media for the lower molecular weight PCB congeners. This information was used to calculate passive sampler-air partition coefficients, KPSM-A. These were correlated to the octanol-air partition coefficient, and the resulting regressions were used to predict KPSM-A for the full suite of PCBs. Information on MTC, KPSM-A, surface area, and effective thickness of each sampler was used to estimate times to equilibrium for each medium. These ranged from tens of days for the lower molecular weight congeners to tens of years for the higher molecular weight PCBs. Expressions were also developed to relate the amount of chemical accumulated by the passive sampling media to average ambient air concentrations over the integration period of the sample.     

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.     

Field testing passive air samplers for current use pesticides in a tropical environment

Air was sampled for one year in the central valley of Costa Rica using an active high-volume sampler as well as passive samplers (PAS) based on polyurethane foam (PUF) disks and XAD-resin filled mesh cylinders. Extracts were analyzed for pesticides that are either banned or currently used in Costa Rican agriculture. Sampling rates for PUF-based passive air samplers, determined from the loss of depuration compounds spiked on the disks prior to deployment averaged 5.9 +/- 0.9 m3 x d(-1) and were higher during the windier dry season than during the rainy season. Sampling rates for the XAD-based passive sampler were determined from the slopes of linear relationships that were observed between the amount of pesticide sequestered in the resin and the length of deployment, which varied from 4 months to 1 year. Those sampling rates increased with decreasing molecular size of a pesticide, and their average of 2.1 +/- 1.5 m3 x d(-1) is higher than rates previously reported for temperate and polar sampling sites. Even though the trends of the sampling rate with molecular size and temperature are consistent with the hypothesis that molecular diffusion controls uptake in passive samplers, the trends are much more pronounced than a direct proportionality between sampling rate and molecular diffusivity would suggest. Air concentrations derived by the three sampling methods are within a factor of 2 of each other, suggesting that properly calibrated PAS can be effective tools for monitoring levels of pesticides in the tropical atmosphere. In particular, HiVol samplers, PUF-disk samplers, and XAD-based passive samplers are suitable for obtaining information on air concentration variability on the time scale of days, seasons and years, respectively. This study represents the first calibration study for the uptake of current use pesticides by passive air samplers.     

Passive air sampling using semipermeable membrane devices at different wind-speeds in situ calibrated by performance reference compounds

Semipermeable membrane devices (SPMDs) are passive samplers used to measure the vapor phase of organic pollutants in air. This study tested whether extremely high wind-speeds during a 21-day sampling increased the sampling rates of polycyclic aromatic hydrocarbons (PAHs) and polychlorinated biphenyls (PCBs), and whether the release of performance reference compounds (PRCs) was related to the uptakes at different wind-speeds. Five samplers were deployed in an indoor, unheated, and dark wind tunnel with different wind-speeds at each site (6-50 m s(-1)). In addition, one sampler was deployed outside the wind tunnel and one outside the building. To test whether a sampler, designed to reduce the wind-speeds, decreased the uptake and release rates, each sampler in the wind tunnel included two SPMDs positioned inside a protective device and one unprotected SPMD outside the device. The highest amounts of PAHs and PCBs were found in the SPMDs exposed to the assumed highest wind-speeds. Thus, the SPMD sampling rates increased with increasing wind-speeds, indicating that the uptake was largely controlled by the boundary layer at the membrane-air interface. The coefficient of variance (introduced by the 21-day sampling and the chemical analysis) for the air concentrations of three PAHs and three PCBs, calculated using the PRC data, was 28-46%. Thus, the PRCs had a high ability to predict site effects of wind and assess the actual sampling situation. Comparison between protected and unprotected SPMDs showed that the sampler design reduced the wind-speed inside the devices and thereby the uptake and release rates.     

Calibration of a passive sampler for both gaseous and particulate phase polycyclic aromatic hydrocarbons

A novel passive air sampler was designed and tested that individually collects the gaseous and particulate phase polycyclic aromatic hydrocarbons (PAHs) in air. The sampler was calibrated against a conventional active sampler in an indoor environment. A PUF (polyurethane foam) disk and a piece of GFF (glass fiber filter) were installed in a sampling shelter for collecting gaseous and particulate phase PAHs, respectively. The passive samplers were deployed in seven indoor locations for 86 days. Six times during this period, 24-h conventional active sampling was conducted for calibration at an average interval of 17-days. Principle component analysis showed that the measured congener profile compositions were totally different between the gaseous and particulate phase PAHs, but similar between the passive and the active samples. This suggested that gaseous and particulate phase PAHs were primarily trapped by the PUF disk and GFF, respectively. Linear relationships between the passively and the actively measured and log-transformed concentrations were derived for calibration of both gaseous and particulate phase PAHs. The uptake rates of the sampler were 0.10 +/- 0.014 m3/d and 0.007 +/- 0.001 m3/d for gaseous and particulate phase PAHs, respectively. The rates were significantly lower than those reported in the literature using similar PUF samplers, mainly because of the special design with limited air circulation.     

Field validation of polyethylene passive air samplers for parent and alkylated PAHs in Alexandria, Egypt

Polyethylene samplers (PEs) were deployed at 11 locations in Alexandria, Egypt during summer and winter to test and characterize them as passive samplers for concentrations, sources, and seasonal variations of atmospheric concentrations of polycyclic aromatic hydrocarbons (PAHs). PE-air equilibrium was attained faster for a wider range of PAHs during the winter season possibly due to increased wind speeds. Calculated PE-air partitioning constants, K(PE-A), in our study [Log K(PE-A) = 0.9426 × Log K(OA) - 0.022 (n = 12, R(2) = 0.99, Std error = 0.053)] agreed with literature values within <46%. For parent (except naphthalene), mono- and dialkylated PAHs, active sampling based concentrations of PAHs were within an average factor of 1.4 (1.0-5.6) compared to the PE based values. For C(3-4) alkylated PAHs, K(PE-A) values were lower than predicted, on average by ~0.8 log units per carbon in the alkylation. Enthalpies of vaporization (ΔH(vap)) accurately corrected K(PE-A)s for temperature differences between winter and summer sampling. PAH profiles were dominated by naphthalene, phenanthrene, and alkylated phenanthrenes. Calculated diagnostic ratios indicated that PAHs originated mainly from vehicle emissions.     

Use of passive samplers to mimic uptake of polycyclic aromatic hydrocarbons by benthic polychaetes

Experiments were conducted to test whether passive samplers made of low-density polyethylene (polyethylene devices, or PEDs) can estimate the extent of uptake of polycyclic aromatic hydrocarbons (PAHs) by benthic polychaetes (Nereis virens) in contaminated marine sediments. For a variety of PAHs, PEDs reached 90% equilibrium with sediment PAHs in 60 days or less. Using 60-day sediment bioaccumulation tests, we have demonstrated a significant relationship between PAH concentrations in the polychaetes and the PEDs (R2 = 0.67, p = 0.002), with the PEDs taking up less PAHs than the polychaetes. Because of this relationship, PEDs can potentially be used in a regulatory context to simulate uptake of bioavailable PAHs in contaminated marine sediments. The PED PAH concentrations were also used to calculate porewater PAH concentrations that allowed for the estimation of a linear free-energy relationship between the lipid-water distribution coefficient (Klip) and the octanol-water distribution coefficient (KOW) for PAH uptake in marine polychaetes (R2 = 0.94, p < 0.0001).     

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.     

PAHs in air and seawater along a North-South Atlantic transect: trends, processes and possible sources

Polycyclic aromatic hydrocarbons (PAHs) were simultaneously measured in air and surface seawater between 49 degrees N and 25 degrees S in the open Atlantic Ocean. Elevated concentrations of PAHs (sigma10 PAHs approximately 1.4-2.5 ng m(-3) air, and 0.7-1 ng L(-1) seawater) occurred in the Biscay Bay and off the northwest coast of Africa. The unexpectedly high concentrations off NW Africa were discussed assessing the possible contribution of the emerging oil industry along the African shore, the role of biomass burning and natural sources of PAHs. In the southern Atlantic, concentrations of PAHs were close to detection limits (sigma10 PAHs approximately 0.02-0.5 ng m(-3) air, and 0.06-0.5 ng L(-1) seawater) and showed decreasing trends with increasing latitudes. Correlations of PAHs' partial pressures versus inverse temperature were not significant in contrast to results for polychlorinated biphenyls from the same transect. This could have been due to the importance of ongoing primary sources and the shorter atmospheric life-times of PAHs. Air-water fugacity ratios (fa/fw) were calculated for selected compounds. They were close to 1 for fluoranthene and pyrene in remote open ocean areas suggesting air-water partitioning near equilibrium. Ratios for anthracene and phenanthrene were < 0.3 in the remote tropical Atlantic, suggesting net volatilization.     

Controlled exposure chamber study of uptake and clearance of airborne polycyclic aromatic hydrocarbons by wheat grain

Polycyclic aromatic hydrocarbons (PAHs) can partition from the atmosphere into agricultural crops, contributing to exposure through the dietary pathway. In this study, controlled environmental chamber experiments were conducted to investigate the transfer of PAHs from air into wheat grain, which is a major food staple. A series of PAHs ranging in size from naphthalene to pyrene were maintained at elevated gas-phase concentrations in the chamber housing mature and dry wheat grain both on the plant and with the husk removed. The PAHs did not achieve equilibrium between the air and grain over the 6.5 month monitoring period used in this study. Therefore, PAH uptake under field conditions is expected to be kinetically limited. A clearance study conducted for the grain showed the half-life of clearance was approximately 20 days for all compounds studied. The results suggest that atmospheric contaminants that partition into grain may remain in the grain long enough to contribute to dietary exposure for humans. Mass transfer across the air/grain interface appeared to be limited by grain-side resistance. The grain may act as a multicompartment system with rapid exchange at the surface followed by slower transfer into the grain. A grain/air concentration relationship was derived for the uptake time that is relevant to field conditions.     

Development of a passive sampler to measure personal exposure to gaseous PAHs in community settings

A sensitive, simple, and cost-effective passive sampling methodology was developed to quantify personal exposure to gaseous polycyclic aromatic hydrocarbons (PAHs). A Fan-Lioy passive PAH sampler (FL-PPS) is constructed from 320 sections of 1-cm long SPB-5 GC columns (0.75-mm i.d. and 7-microm film thickness), similar to a mini-honeycomb denuder. Given the unique feature of the GC column stationary phase, gaseous PAHs are collected on the inner surfaces of the columns by molecular diffusion and thermally desorbed to GC/MS for analysis. The sampling rates of FL-PPS were determined in the laboratory using a controlled test atmosphere containing eight PAHs for a range of face velocity, temperature, relative humidity, PAH concentration, and sampling duration. The sampling rate (mean, %RSD, cm3/min) was 26.7 (21%) for acenaphthylene, 37.6 (25%) for acenaphthene, 56.2 (13%) for fluorene, 49.1 (25%) for phenanthrene, 62.7 (22%) for anthracene, 65.4 (24%) for fluoranthene, and 64.4 (18%) for pyrene over a sampling duration of 8-48 h. The sampling rate for naphthalene was approximately 14.1 (12%) cm3/min over a sampling period of 8 h but decreased along with an increase of sampling time. The effects of temperature, humidity, face velocity, and PAH concentration on the sampling rate were not significant for all the compounds tested. A reasonable agreement (<30%) was obtained for most compounds measured by FL-PPS and a conventional active PAH sampling method colocated side-by-side in the field, but a sampling time of 24 h or longer was required for detection of less abundant PAHs in community settings.     

Competitive sorption of pyrene, phenanthrene, and naphthalene on multiwalled carbon nanotubes

Knowledge of toxic chemical sorption by carbon nanotubes (CNTs) is critical for environmental application of CNTs as superior sorbents and for environmental risk assessment of both CNTs and toxic chemicals. Single-solute sorption results were reported in the literature, however, they cannot be used for predicting pollutant sorption by CNTs in wastewater and natural water systems where multiple organic contaminants are present. In this study, competitive sorption of pyrene, phenanthrene, and naphthalene on a multiwalled CNT material was investigated. All isotherms in single-, bi-, and tri-solute systems were fitted well by the Dubinin-Ashtakhov (DA) model. The isotherm of a given primary solute changed from being significantly nonlinear to nearly linear when competitors were added. The observed competitive sorption depended on the relative equilibrium concentrations of both primary and cosolutes. Significant competition was observed at relatively low concentrations of primary solute and high concentrations of competitors, while competition was much weaker in the case of relatively high concentrations of primary solute and low competitor concentrations. When the relative concentration of primary solute (Ce/Cs) approached 1, competition by other solutes seemed to disappear. Sorption and competition of three polycyclic aromatic hydrocarbons (PAHs) on CNTs could not be explained with either pore-filling or partition-adsorption mechanisms. A Polanyi-based surface adsorption mechanism was proposed to interpret the observed sorption and competition.     

Estimation of the uptake rate constants for polycyclic aromatic hydrocarbons accumulated by semipermeable membrane devices and triolein-embedded cellulose acetate membranes

In this paper we report an extension of our previous work on the triolein-embedded cellulose acetate membrane (TECAM) as a passive sampling device (PSD) and describe the results from simultaneous exposure of TECAMs and triolein-containing semipermeable membrane devices (SPMDs) to PAHs in lake water for 16 days. The data obtained provided a comparison of the uptake rates of specific PAHs by the two PSDs. Using 16-day accumulation tests, similar PAH distribution patterns in TECAMs and in SPMDs (R2 = 0.89, p < 0.0001) were observed. However, it was noted that TECAMs could take up greater amounts of PAHs than SPMDs (735 ng/g of TECAM vs 630 ng/g of SPMD). Uptake rate constants of TECAMs and SPMDs for 16 priority pollutant (PP) PAHs, corrected for dissolved organic carbon, ranged from 0.28 to 2.94 L d(-1) and from 0.16 to 0.91 L d(-1), respectively. The elimination rate constants of TECAMs were 1.4-6.7 times greater than those observed for SPMDs, thereby indicating that PAHs required shorter times to achieve equilibrium in TECAMs than in SPMDs. Thus, the results of the present study suggest that TECAMs have significant potential as a good monitor to assess the pollution of hydrophobic pollutants in aquatic environments.     

Comparison of lichen, conifer needles, passive air sampling devices, and snowpack as passive sampling media to measure semi-volatile organic compounds in remote atmospheres

A wide range of semivolatile organic compounds (SOCs), including pesticides and polycyclic aromatic hydrocarbons (PAHs), were measured in lichen, conifer needles, snowpack and XAD-based passive air sampling devices (PASDs) collected from 19 different U.S. national parks in order to compare the magnitude and mechanism of SOC accumulation in the different passive sampling media. Lichen accumulated the highest SOC concentrations, in part because of its long (and unknown) exposure period, whereas PASDs accumulated the lowest concentrations. However, only the PASD SOC concentrations can be used to calculate an average atmospheric gas-phase SOC concentration because the sampling rates are known and the media is uniform. Only the lichen and snowpack SOC accumulation profiles were statistically significantly correlated (r = 0.552, p-value <0.0001) because they both accumulate SOCs present in the atmospheric particle-phase. This suggests that needles and PASDs represent a different composition of the atmosphere than lichen and snowpack and that the interpretation of atmospheric SOC composition is dependent on the type of passive sampling media used. All four passive sampling media preferentially accumulated SOCs with relatively low air-water partition coefficients, while snowpack accumulated SOCs with higher log K(OA) values compared to the other media. Lichen accumulated more SOCs with log K(OA) > 10 relative to needles and showed a greater accumulation of particle-phase PAHs.     

Field trial and modeling of uptake rates of in situ lipid-free polyethylene membrane passive sampler

Lipid-free polyethylene membrane tubing (LFT) has been further developed in response to a growing need for an inexpensive and simple time-integrative sampling device for dissolved hydrophobic contaminants in water. The LFT sampler is based on the diffusion of dissolved hydrophobic target compounds through the aqueous boundary layer and into the polyethylene membrane, mimicking uptake by organisms. We demonstrate through laboratory and field validation studies that LFT provided the same benefits as many other passive sampling devices, withoutthe potential of analytical interference from lipid impurities. A total of 370 LFTs and semipermeable membrane devices were deployed for 21 days in paired studies at highly urbanized, undeveloped, and two Superfund sites, representing several river conditions. A simple internal surrogate spiking method served as an in situ calibration indicator of the effects of environmental conditions on the uptake rates. A modified extraction method for the LFT increased recoveries while decreasing solvent use and labor compared to other organic extraction procedures. LFT sampling rates were estimated using ratios, in situ calibration and modeling for over 45 target analytes, including PAHs, PCBs, and pesticides.     

Detecting air-water and surface-deep water gradients of PCBs using polyethylene passive samplers

Polyethylene passive samplers (PEs) were deployed in a vertical array (bottom water, surface water, near-surface air) to study the cycling of active polychlorinated biphenyls (PCBs) between reservoirs in an urban estuary (Narragansett Bay, RI), from May to November 2006. Performance reference compounds were used to account for nonequilibrium of PCBs in PEs. Activity gradients were established from direct comparisons of temperature, salt, and nonequilibrium corrected PE concentrations. The uncertainty of determining air-water gradients was < 70%, and < 50% within the water column. Except during the height of summer, PCB activities were up to 30 times higher in the air than in the surface water, but closer to equilibrium in the water column. Surface waters became depleted in PCBs during periods of highest temperature and stratification, leading to the uptake of gaseous PCBs. Our results demonstrate that passive samplers are powerful tools to determine the flux directions of organic contaminants in the environment.     

Assessing the influence of meteorological parameters on the performance of polyurethane foam-based passive air samplers

Polyurethane foam (PUF) disk passive air samplers were evaluated under field conditionsto assessthe effect of temperature and wind speed on the sampling rate for polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs), and organochlorine pesticides (OCPs). Passive samples integrated over 28-day periods were compared to high-volume air samples collected for 24 h, every 7 days. This provided a large data set of 42 passive sampling events and 168 high-volume samples over a 3-year period, starting in October 2003. Average PUF disk sampling rates for gas-phase chemicals was approximately 7 m3 d(-1) and comparable to previous reports. The high molecular weight PAHs, which are mainly particle-bound, experienced much lower sampling rates of approximately 0.7 m3 d(-1). This small rate was attributed to the ability of the sampling chamber to filter out coarse particles with only the fine/ultrafine fraction capable of penetration and collection on the PUF disk. Passive sampler-derived data were converted to equivalent air volumes (V(EQ), m3) using the high-volume air measurement results. Correlations of V(EQ) against meteorological data collected on-site yielded different behavior for gas- and particle-associated compounds. For gas-phase chemicals, sampling rates varied by about a factor of 2 with temperature and wind speed. The higher sampling rates at colder temperatures were explained bythe wind effecton sampling rates. Temperature and wind were strongly correlated with the greatest winds at coldertemperatures. Mainly particle-phase compounds (namely, the high molecular weight PAHs) had more variable sampling rates. Sampling rates increased greatly atwarmertemperatures as the high molecular weight PAH burden was shifted toward the gas phase and subject to higher gas-phase sampling rates. At colder temperatures, sampling rates were reduced as the partitioning of the high molecular weight PAHs was shifted toward the particle phase. The observed wind effect on sampling for the particle-phase compounds is believed to be tied to this strong temperature dependence on phase partitioning and hence sampling rate. For purposes of comparing passive sampler derived data for persistent organic pollutants, the factor of 2 variability observed for mainly gas-phase compounds is deemed to be acceptable in many instances for semiquantitative analysis. Depuration compounds may be used to improve accuracy and provide site-specific sampling rates, although this adds a level of complexity to the analysis. More research is needed to develop and test passive air samplers for particle-associated chemicals.     

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.