Henry's law constant, octanol-air partition coefficient and supercooled liquid vapor pressure of carbazole as a function of temperature: application to gas/particle partitioning in the atmosphere

The Henry's law constant for carbazole was experimentally determined between 5 and 35 degrees C using a gas-stripping technique. The following equation was obtained for dimensionless Henry's law constant (H') versus temperature (T, K): ln H' = -3982(T,K)(-1) + 1.01. Temperature-dependent octanol-air partition coefficients (KOA) and supercooled liquid vapor pressures (PL,Pa) of carbazole were also determined using the GC retention time method. The temperature dependence of KOA and PL were explained by the following: log KOA = 4076/(T,K) - 5.65, log PL(Pa) = -3948(T,K)(- 1) + 11.48.The gas and particle-phase carbazole concentrations measured previously in Chicago, IL in 1995 was used for gas/particle partitioning modeling. Octanol based absorptive partitioning model consistently underpredicted the gas/particle partition coefficients (Kp) for all sampling periods. However, overall there was a good agreement between the measured Kp and soot-based model predictions.     

Gas- and particle-phase distribution of polycyclic aromatic hydrocarbons in two-stroke, 50-cm3 moped emissions

Gas- and particle-phase polycyclic aromatic hydrocarbons (PAHs) concentrations evaluated in the exhaust of 10 two-stroke, 50-cm³ mopeds belonging to three different levels of emission legislation (EURO-0, EURO-1 and EURO-2) were used to assess the prevalent mechanism driving the gas/particle partitioning of PAHs in moped exhaust. Sampling was performed on a dynamometer bench both during the “cold-start” and the “hot” phases of the ECE-47 driving cycle. Gas and particulate phase PAHs were collected on polyurethane foam (PUF) plugs and 47-mm Pallflex T60A20 filters, respectively, under isokinetic conditions by using sampling probes inserted into the dilution tunnel of a Constant Volume Sampling – Critical Flow Venturi (CVS–CFV) system.The results show that semi-volatile PAHs were predominantly partitioned to the particle phase. The soluble organic fraction (SOF) of the collected particulates ranged between 72 and 98%. Measured total suspended particulate matter normalized partition coefficients (K_p) were predicted within a factor of 3–5 by assuming absorption into the organic fraction according to a model developed by Harner and Bidleman [Harner, T., Bidleman, T.F., 1998. Octanol–air partition coefficient for describing particle/gas partitioning of aromatic compounds in urban air. Environmental Science & Technology 32, 1494–1502.]. This suggests that the gas/particle partitioning in moped exhaust is mainly driven by the high fraction of organic matter of the emitted particles and that absorption could be the main partitioning mechanism of PAHs.     

Daytime resolved analysis of polycyclic aromatic hydrocarbons in urban aerosol samples - impact of sources and meteorological conditions

Urban aerosol was collected in a summer and a winter campaign for 7 and 3 days, respectively. Low volume samples were taken with a time resolution of 160 min using a filter/sorption cartridge system extended by an ozone scrubber. Concentrations of mainly particle associated polycyclic aromatic hydrocarbons (PAH) and oxidised PAH (O-PAH) were determined by gas chromatography/high resolution mass spectrometry. The sampling site was located in the city centre of Augsburg, Germany, near major roads with high traffic volume. The daily concentrations and profiles were mainly governed by local emissions from traffic and domestic heating, as well as by the meteorological conditions. During the winter campaign, concentrations were more than 10 fold higher than during the summer campaign. Highest concentrations were found concurrent with low boundary layer heights and low wind speeds. Significant diurnal variation of the PAH profiles was observed. Enhanced influences of traffic related PAH on the PAH profiles were evident during daytime in summer, whereas emissions from hot water generation and domestic heating were obvious during the night time of both seasons. A general idea about the global meteorological situation was acquired using back trajectory calculations (NOAA ARL HYSPLIT4). Due to high local emissions in combination with low air exchange during the two sampling campaigns, effects of mesoscale transport were not clearly observable.     

Gas/particle partitioning of polycyclic aromatic hydrocarbons in coastal atmosphere of the north Yellow Sea, China

Samples of gas- and particle-phase polycyclic aromatic hydrocarbons (PAHs) were collected at three sampling stations (Xiaomai Island, Laohutan, and Zhangzi Island) in the north Yellow Sea, China during November 2008 and September 2009 to study their atmospheric transport potential and the gas/particle distributions. The composition of PAHs was dominated by gaseous compounds. The percentages of the particle-phase PAHs to the total concentrations were found to be higher during the heating period than the non-heating period. The ratios of naphthalene and acenaphthene to phenanthrene, chrysene and dibenzo(a,h)anthracene showed an increasing trend from Xiaomai Island to Zhangzi Island, which can be called as the local atmospheric distillation of PAHs. Gas/particle partitioning coefficients (K _p) and their relationship with the sub-cooled liquid vapor pressures (pº_L) of PAHs were investigated. The regressions of logK _p versus logpº_L gave significant correlations for all samples of the three sites with r ² values in the range 0.56–0.66 (p?<?0.01). Both Junge–Pankow adsorption model and octanol–air partition coefficient absorption model tended to underestimate the sorption for most PAHs, but the absorption model appeared to be more suitable for predicting the particle fraction of PAHs than the Junge–Pankow model.     

Gas/particle partitioning of polychlorinated dibenzo-p-dioxins and dibenzofurans in atmosphere; evaluation of predicting models

The gas/particle partitioning of polychlorinated dibenzo-p-dioxins and furans (PCDD/Fs) was measured at three sites for a year in order to monitor the variation of PCDD/Fs levels and describe their partitioning. The air concentrations of PCDD/Fs ranged from 71 to 1161 fg I-TEQ/m³ and large changes in these levels did not correlate with seasonal changes during this study. Different homolog patterns were observed in the gas/particle phase. High chlorinated dioxin/furans dominated the particle phase while low chlorinated dioxin/furans dominated the gas phase. The high correlation coefficient between log [(PCDD/Fs_vap)(TSP)/(PCDD/Fs_pat)] and 1/T was observed in lower chlorinated dioxin/furans unlike in OCDD/F. The slope of homolog ranged from −0.410 to −1.025 and that of 2,3,7,8-substituted isomers ranged from −0.379 to −0.772 in plots of the log partition coefficient (K_p) versus the log subcooled vapor pressure (P_L°).The octanol/air partition coefficient (K_oa)-based model of PCDD/Fs is more compatible with experimental data than those of the Junge–Pankow model that tends to overestimate results, even though both models include some level of uncertainty. However, both models can underestimate the particle phase of PCDD/Fs, especially when the ambient air temperature is extremely low in winter.     

Theoretical versus Observed Gas-Particle Partitioning of Carbonyl Emissions from Motor Vehicles

Abstract

A state-of-the-science thermodynamic model describing gas-particle absorption processes was used to predict the gas-particle partitioning of mixtures of approximately 60 carbonyl compounds emitted from low-emission gasoline-powered vehicles, three-way catalyst gasoline-powered vehicles, heavy-duty diesel vehicles under the idle-creep condition (HDDV idle), and heavy-duty diesel vehicles under the five-mode test (HDDV 5-mode). Exhaust was diluted by a factor of 120–580 with a residence time of approximately 43 sec. The predicted equilibrium absorption partitioning coefficients differed from the measured partitioning coefficients by several orders of magnitude. Time scales to reach equilibrium in the dilution sampling system were close to the actual residence time during the HDDV 5-mode test and much longer than the actual residence time during the other vehicle tests. It appears that insufficient residence time in the sampling system cannot uniformly explain the failure of the absorption mechanism to explain the measured partitioning. Other gas-particle partitioning mechanisms (e.g., heterogeneous reactions, capillary adsorption) beyond the simple absorption theory are needed to explain the discrepancy between calculated carbonyl partitioning coefficients and observed partitioning. Both of these alternative partitioning mechanisms imply great challenges for the measurement and modeling of semi-volatile primary organic aerosol (POA) species from motor vehicles. Furthermore, as emitted particle concentrations from newer vehicles approach atmospheric background levels, dilution sampling systems must fundamentally change their approach so that they use realistic particle concentrations in the dilution air to approximately represent real-world conditions. Samples collected with particle-free dilution air yielding total particulate matter concentrations below typical ambient concentrations will not provide a realistic picture of partitioning for semi-volatile compounds.     

The effects of ozone/limonene reactions on indoor secondary organic aerosols

An indoor air quality model was used to predict dynamic particle mass concentrations based on homogeneous chemical mechanisms and partitioning of semi-volatile products to particles. The ozone–limonene reaction mechanism was combined with gas-phase chemistry of common atmospheric organic and inorganic compounds and incorporated into the indoor air quality model. Experiments were conducted in an environmental chamber to investigate secondary particle formation resulting from ozone/limonene reactions. Experimental results indicate that significant fine particle growth occurs due to the interaction of ozone and limonene and subsequent intermediate by-products. Secondary particle mass concentrations were estimated from the measured particle size distribution. Predicted particle mass concentrations were in good agreement with experimental results—generally within ∼25% at steady-state conditions. Both experimental and predicted results suggest that air exchange rate plays a significant role in determining secondary fine particle levels in indoor environments. Secondary particle mass concentrations are predicted to increase substantially with lower air exchange rates, an interesting result given a continuing trend toward more energy efficient buildings. Lower air exchange rates also shifted the particle size distribution toward larger particle diameters. Secondary particle mass concentrations are also predicted to increase with higher outdoor ozone concentrations, higher outdoor particle concentrations, higher indoor limonene emission rates, and lower indoor temperatures.     

Theoretical versus observed gas-particle partitioning of carbonyl emissions from motor vehicles

A state-of-the-science thermodynamic model describing gas-particle absorption processes was used to predict the gas-particle partitioning of mixtures of approximately 60 carbonyl compounds emitted from low-emission gasoline-powered vehicles, three-way catalyst gasoline-powered vehicles, heavy-duty diesel vehicles under the idle-creep condition (HDDV idle), and heavy-duty diesel vehicles under the five-mode test (HDDV 5-mode). Exhaust was diluted by a factor of 120-580 with a residence time of approximately 43 sec. The predicted equilibrium absorption partitioning coefficients differed from the measured partitioning coefficients by several orders of magnitude. Time scales to reach equilibrium in the dilution sampling system were close to the actual residence time during the HDDV 5-mode test and much longer than the actual residence time during the other vehicle tests. It appears that insufficient residence time in the sampling system cannot uniformly explain the failure of the absorption mechanism to explain the measured partitioning. Other gas-particle partitioning mechanisms (e.g., heterogeneous reactions, capillary adsorption) beyond the simple absorption theory are needed to explain the discrepancy between calculated carbonyl partitioning coefficients and observed partitioning. Both of these alternative partitioning mechanisms imply great challenges for the measurement and modeling of semi-volatile primary organic aerosol (POA) species from motor vehicles. Furthermore, as emitted particle concentrations from newer vehicles approach atmospheric background levels, dilution sampling systems must fundamentally change their approach so that they use realistic particle concentrations in the dilution air to approximately represent real-world conditions. Samples collected with particle-free dilution air yielding total particulate matter concentrations below typical ambient concentrations will not provide a realistic picture of partitioning for semi-volatile compounds.     

Long range transport and gas/particle distribution of polycyclic aromatic hydrocarbons at a remote site in the Mediterranean Sea

Polycyclic aromatic hydrocarbon (PAH) concentrations have been determined for 14 successive days in a remote site of the Mediterranean Sea situated in Corsica, France. Both particulate and gas phases were collected and analyzed. For any receptor site the concentration of adsorbed PAH on particles is determined by three parameters, in order of decreasing importance: the source area, nearby sources and precipitation along the trajectory followed by the particles. For two air masses originating from the same source area, PAH concentrations can be reduced by 60% by particle scavenging during precipitation events. The identification of the source area is in complete agreement with the classification based on the mineral elements. The gas phase concentrations are determined by the source area only; they remain high compared to the concentrations in the industrial zone, thus proving that the gaseous PAH are not strongly degraded by chemical aggressors during transport. Factor analysis clearly shows the different effects involved during transport. The gas/particle ratio is determined essentially by the temperature and molecular weight of the PAH and not by the origin of the emissions. However precipitation influences this ratio to a non-negligible extent through scavenging of the aerosols. For example, the gas/particle ratio, for pyrene, varies from 2 to 4 between two ‘dry’ episodes with a temperature difference of 2.2° C, and from 6 to 13 because of the particle scavenging by rain. These results can be used as a data base and are expected to guide the conception of transport models including the parameters considered in this study.     

Polycyclic aromatic hydrocarbons in Costa Rican air and soil: A tropical/temperate comparison

Surface soil and passive air samples from a network of 23 sampling sites across Costa Rica were analyzed for polycyclic aromatic hydrocarbons (PAHs), allowing for an evaluation of absolute levels, spatial distribution patterns, air/soil concentration (A/S) ratios and relative composition. Annual mean concentrations of four-ring PAHs in air were low (median of approximately 40 pg m⁻³), except in Costa Rica's densely populated central valley (approximately 650 pg m⁻³). PAH concentrations in soil were also low (median of 5 ng g⁻¹ dry weight) and comparable to those reported for other tropical regions. These low soil concentrations result in A/S ratios of four-ring PAHs in Costa Rica that are higher than the equilibrium air–soil partitioning coefficients and also higher than A/S ratios reported for temperate locations. A series of model calculations of increasing complexity were used to seek an explanation for variable A/S ratios of PAHs under tropical and temperate conditions. Temperature-driven changes in air–soil partitioning and differences in PAH degradability under temperate and tropical conditions are insufficient to explain the higher soil concentrations and lower A/S ratios in temperate regions. However, these can be explained by atmospheric deposition of PAHs during historical periods of much higher emissions and air concentrations and by persistence of PAHs in soils on the order of decades. Low PAH concentrations in tropical soils were found to be consistent with constant or increasing emissions, and in particular, do not require that degradation rates in soil are much faster than in temperate areas. In comparison to temperate soils, soils from Costa Rica and other tropical regions have a higher relative abundance of the lighter PAHs. This likely reflects a higher source contribution from biomass burning in the tropics, as well as the preferential loss of lighter PAHs from temperate soils that experienced high PAH deposition in the past.     

Wood smoke as a source of particle-phase organic compounds in residential areas

The objective of this study was to investigate the organic composition of wood smoke emissions and ambient air samples in order to determine the wood smoke contribution to the ambient air pollution in the residential areas. From November 2005 to March 2006 particle-phase PM₁₀ samples were collected in the residential town Dettenhausen surrounded by forests near Stuttgart in southern Germany. Samples collected on pre-baked glass fibre filters were extracted using toluene with ultrasonic bath and analysed by gas chromatography mass spectrometry (GC-MS). 21 polycyclic aromatic hydrocarbons (PAH) including 16 USEPA priority pollutants, different organic wood smoke tracers, primarily 21 species of syringol and guaiacol derivatives, levoglucosan and its isomers mannosan, galactosan and dehydroabietic acid were detected and quantified in this study. The concentrations of these compounds were compared with the fingerprints of emissions from hardwood and softwood combustion carried out in test facilities at Universitaet Stuttgart and field investigations at a wood stove during real operation in Dettenhausen. It was observed that the combustion derived PAH was detected in higher concentrations than other PAH in the ambient air PM₁₀ samples. Syringol and its derivatives were found in large amounts in hardwood burning but were not detected in softwood burning emissions. On the other hand, guaiacol and its derivatives were found in both softwood and hardwood burning emissions, but the concentrations were higher in the softwood smoke compared to hardwood smoke. So, these compounds can be used as typical tracer compounds for the different types of wood burning emissions. In ambient air samples both syringol and guaiacol derivatives were found which indicates the wood combustion contribution to the PM load in such residential areas. Levoglucosan was detected in high concentrations in all ambient PM₁₀ samples. A source apportionment modelling, Positive Matrix Factorization (PMF) was implemented to quantify the wood smoke contribution to the ambient PM₁₀ bound organic compounds in the residential area.     

Vapor-phase and fine particulate matter concentrations of polycyclic aromatic hydrocarbons measured during the winter months in a northern Rocky Mountain urban airshed

A fine particulate matter (PM2.5) sampling program was conducted in Missoula, MT, to investigate both the particle and vapor phases of PM2.5-associated polycyclic aromatic hydrocarbons (PAHs) found in a northern Rocky Mountain urban airshed. Twenty-four-hour samples were collected during the cold winter months of January through April 2002, when many of the more volatile organic components of PM2.5 were expected to be found in the condensed particle form. To meet analytical detection limits, each of the 12 individual sample days were aggregated into four total filter and polyurethane foam (PUF) samples, respectively, with each aggregate containing 3 sample days. Quartz filter (particle-phase PAHs) and PUF (vapor-phase PAHs) aggregates were analyzed separately for 18 individual PAHs and phenolics by gas chromatography/mass spectrometry. Results showed that 87% of the PM2.5-associated phenolics and PAHs measured in this study were found in the vapor phase. PM2.5-associated gas/particle partition coefficients (Kp,2.5) ranged from 0 for the lighter phenolics and PAHs to approximately 0.1 for some of the heavier PAHs, such as fluoranthene and pyrene. Calculating Kp,2.5 for the heaviest measured PAHs was not feasible because of low or undetectable concentrations in the vapor phases of these compounds. Phenolics and two-ringed and three-ringed PAHs were found almost exclusively in the vapor phase. Four-ringed PAHs were distributed between the particle and vapor phases, with more mass measured in the vapor phase. Very little five-ringed and higher PAHs were measured from either the filter or PUF sampling medium. These results provide information on both the concentrations and different phases of PM2.5-associated PAHs measured during the winter months in a northern Rocky Mountain urban airshed, when concentrations of PM2.5 are generally at their highest compared with the rest of the year.     

Uptake of PAHs into polyoxymethylene and application to oil-soot (lampblack)-impacted soil samples

Polyoxymethylene (POM) is a polymeric material used increasingly in passive sampling of hydrophobic organic contaminants such as PAHs and PCBs in soils and sediments. In this study, we examined the sorption behavior of 12 PAH compounds to POM and observed linear isotherms spanning two orders of magnitude of aqueous concentrations. Uptake kinetic studies performed in batch systems for up to 54 d with two different volume ratios of POM-to-aqueous phase were evaluated with coupled diffusion and mass transfer models to simulate the movement of PAHs during the uptake process and to assess the physicochemical properties and experimental conditions that control uptake rates. Diffusion coefficients of PAHs in POM were estimated to be well correlated with diffusants' molecular weights as D(POM) proportional, variant(MW)(-3), descending from 2.3 x 10(-10) cm(2) s(-1) for naphthalene to 7.0 x 10(-11) cm(2) s(-1) for pyrene. The uptake rates for PAHs with log K(ow)<5.8 were controlled by the POM phase and the hydrophobicity of PAH compounds. For more hydrophobic PAH compounds, the aqueous boundary layer played an increasingly important role in determining the overall mass transfer rate. The POM partitioning technique was demonstrated to agree well with two other procedures for measuring PAH soil-water distribution coefficients in oil-soot (lampblack) containing soil samples.     

A study of gas/particle partitioning of SVOCs in the tropical atmosphere of Southeast Asia

Gas- and particle-phase polycyclic aromatic hydrocarbons (PAHs) and polychlorinated biphenyls (PCBs) were collected at a tropical site in Southeast Asia over 12-h periods during November and December 2006 to determine their gas/particle distributions by analyzing integrated quartz filter and polyurethane foam samples. Gas/particle partitioning coefficients, K_p, were calculated, and their relationship with the subcooled liquid vapor pressure p_L^o for both PAHs and PCBs was investigated. The regressions of log K_p vs. log p_L^o for most of samples gave high correlations for both PAHs and PCBs and the slopes were statistically shallower than ?1, but they were relatively steeper than those obtained in temperate zones of the Northern Hemisphere. By comparison, the particle-bound fraction of low molecular weight (LMW) PAHs was underestimated by both Junge-Pankow adsorption and K_OA (octanol–air partition coefficient) absorption models, while the predicted values agree relatively better with those observed ones for high molecular weight (HMW) PAHs. In addition, the adsorption onto the soot phase (elemental carbon) predicted accurately the gas/particle partitioning of PAHs, especially for LMW compounds. On the other hand, the K_OA absorption model using the measured organic matter fraction (f_OM) value fitted the PCB data much better than the adsorption model did, indicating the sorption of nonpolar compounds to aerosols might be dominated by absorption into organic matters in this area.     

The effect of temperature on the gas–particle partitioning of reactive mercury in atmospheric aerosols

Measurements of gas–particle-partitioning coefficients for reactive mercury in dry urban and laboratory aerosol were found to strongly depend on ambient temperature. Samples of atmospheric and laboratory aerosols (defined as both the gas and particle phases) were collected using filter and absorbent methods and analyzed for reactive mercury using thermal desorption combined with cold vapor atomic fluorescence spectroscopy. Synthetic ambient aerosols were generated in the laboratory from ammonium sulfate and adipic acid mixed with mercuric chloride in a purpose-built aerosol reactor. The aerosol reactor was operated in a temperature-controlled laboratory. Linear relationships between the logarithm of inverse gas–particle partitioning and inverse temperature were observed and parameterized for use in the atmospheric modeling of reactive mercury. Reactive mercury was observed to partition from the particle to the gas phase as ambient temperature increased. Good agreement between measurements made using urban and laboratory aerosols was seen after gas–particle-partitioning coefficients were normalized for surface area instead of mass. Thermodynamic analyses of the urban and laboratory gas–particle-partitioning measurements revealed that the strength of interaction between reactive mercury and particle surfaces was suggestive of chemisorption. Gas–particle-partitioning coefficients made with the Tekran ambient mercury analyzer (AMA) also showed a dependence on temperature. However, the Tekran AMA partitioning coefficients did not agree well with partitioning coefficients measured using the filter-based methods. The disagreement is consistent with the 50 °C operational temperature of the Tekran AMA.     

Polycyclic aromatic hydrocarbon exhaust emissions from different reformulated diesel fuels and engine operating conditions

The study of light-duty diesel engine exhaust emissions is important due to their impact on atmospheric chemistry and air pollution. In this study, both the gas and the particulate phase of fuel exhaust were analyzed to investigate the effects of diesel reformulation and engine operating parameters. The research was focused on polycyclic aromatic hydrocarbon (PAH) compounds on particulate phase due to their high toxicity. These were analyzed using a gas chromatography–mass spectrometry (GC–MS) methodology.Although PAH profiles changed for diesel fuels with low-sulfur content and different percentages of aromatic hydrocarbons (5–25%), no significant differences for total PAH concentrations were detected. However, rape oil methyl ester biodiesel showed a greater number of PAH compounds, but in lower concentrations (close to 50%) than the reformulated diesel fuels. In addition, four engine operating conditions were evaluated, and the results showed that, during cold start, higher concentrations were observed for high molecular weight PAHs than during idling cycle and that the acceleration cycles provided higher concentrations than the steady-state conditions. Correlations between particulate PAHs and gas phase products were also observed.The emission of PAH compounds from the incomplete combustion of diesel fuel depended greatly on the source of the fuel and the driving patterns.     

The distribution of particle-phase organic compounds in the atmosphere and their use for source apportionment during the Southern California Children''s Health Study

Atmospheric particulate matter (PM) samples from 12 sites in southern California, collected as part of the Southern California Children's Health Study (SCCHS), were analyzed using gas chromatography/mass spectrometry (GC/MS) techniques. Ninety-four organic compounds were quantified in these samples, including n-alkanes, fatty acids, polycyclic aromatic hydrocarbons (PAH), hopanes, steranes, aromatic diacids, aliphatic diacids, resin acids, methoxyphenols, and levoglucosan. Annual average concentrations of all detected compounds, as well as average concentrations for three seasonal periods, were determined at all 12 sites for the calendar year of 1995. These measurements provide important information about the seasonal and spatial distribution of particle-phase organic compounds in southern California. Also, co-located samples from one site were analyzed to assess precision of measurement. Excellent agreement was observed between annual average concentrations for the broad range of organic compounds measured in this study. Measured concentrations from the 12 sampling sites were used in a previously developed molecular-marker source apportionment model to quantify the primary source contributions to the PM10 organic carbon and mass concentrations at these 12 sites. Source contributions to atmospheric PM from six important air pollution sources were quantified: gasoline-powered motor vehicle exhaust, diesel vehicle exhaust, wood smoke, vegetative detritus, tire wear, and natural gas combustion. Important trends in the seasonal and spatial patterns of the impact of these six sources were observed. In addition, contributions from meat smoke were detected in selected samples.     

Atmospheric concentrations and phase partitioning of polybrominated diphenyl ethers (PBDEs) in Izmir, Turkey

Atmospheric concentrations of 7 PBDE congeners (BDE-28, -47, -99, -100, -153, -154 and -209) were determined at four sites (i.e. Suburban, Urban 1, Urban 2, Industrial) in Izmir, Turkey and their gas/particle partitioning was investigated. Total PBDE ( summation operator(7)PBDE) concentrations ranged between 11 (Urban 1) and 149pgm(-3) (Industrial) in summer, while in winter, they ranged from 6 (Suburban) to 81pgm(-3) (Industrial). BDE-209 was the dominant congener at all sites, followed by BDE-99 and -47. Investigation of source profiles indicated that the air samples were dominated by congeners of the penta and deca-technical BDE mixtures. The measured PBDE particle fractions were compared to the predictions of the K(OA) (octanol-air partition coefficient)-based equilibrium partitioning model and to the dynamic uptake model developed by others for passive samplers, which was adapted to model gas-particle partitioning in this study. For BDE-28, good agreement was observed between the experimental particle fractions and those predicted by the equilibrium partitioning model. However, this model overestimated the particle fractions of other congeners. The predictions of the dynamic uptake model supported the hypothesis that the unexpectedly high partitioning of BDEs (except BDE-28) to the gas-phase is due to their departure from equilibrium partitioning. When congeners with very large octanol-air partition coefficients (i.e. BDE-100, -99, -154, -153, and -209) are emitted from their sources in the gas-phase, they may remain in that phase for several months before reaching equilibrium with atmospheric particles. This may also have important implications for the transport of atmospheric PBDEs. For example, in addition to particle-bound transport, the gas-phase transport of highly brominated congeners (i.e. BDE-209) may also be important.