Airborne Precursors Predict Maternal Serum Perfluoroalkyl Acid Concentrations.

Human exposure to persistent perfluoroalkyl acids (PFAAs), including perfluorooctanoic acid (PFOA), perfluorononanoic acid (PFNA), and perfluorooctanesulfonate (PFOS), can occur directly from contaminated food, water, air, and dust. However, precursors to PFAAs (PreFAAs), such as dipolyfluoroalkyl phosphates (diPAPs), fluorotelomer alcohols (FTOHs), perfluorooctyl sulfonamides (FOSAs), and sulfonamidoethanols (FOSEs), which can be biotransformed to PFAAs, may also be a source of exposure. PFAAs were analyzed in 50 maternal sera samples collected in 2007-2008 from participants in Vancouver, Canada, while PFAAs and PreFAAs were measured in matching samples of residential bedroom air collected by passive sampler and in sieved vacuum dust (<150 µm). Concentrations of PreFAAs were higher than for PFAAs in air and dust. Positive associations were discovered between airborne 10:2 FTOH and serum PFOA and PFNA and between airborne MeFOSE and serum PFOS. On average, serum PFOS concentrations were 2.3 ng/mL (95%CI: 0.40, 4.3) higher in participants with airborne MeFOSE concentrations in the highest tertile relative to the lowest tertile. Among all PFAAs, only PFNA in air and vacuum dust predicted serum PFNA. Results suggest that airborne PFAA precursors were a source of PFOA, PFNA, and PFOS exposure in this population.

Temporal variations of cyclic and linear volatile methylsiloxanes in the atmosphere using passive samplers and high-volume air samplers.

Cyclic and linear volatile methylsiloxanes (cVMSs and lVMSs, respectively) were measured in ambient air over a period of over one year in Toronto, Canada. Air samples were collected using passive air samplers (PAS) consisting of sorbent-impregnated polyurethane foam (SIP) disks in parallel with high volume active air samplers (HV-AAS). The average difference between the SIP-PAS derived concentrations in air for the individual VMSs and those measured using HV-AAS was within a factor of 2. The air concentrations (HV-AAS) ranged 22-351 ng m(-3) and 1.3-15 ng m(-3) for ΣcVMSs (D3, D4, D5, D6) and ΣlVMSs (L3, L4, L5), respectively, with decamethylcyclopentasiloxane (D5) as the dominant compound (∼75% of the ΣVMSs). Air masses arriving from north to northwest (i.e., less populated areas) were significantly less contaminated with VMSs compared to air arriving from the south that are impacted by major urban and industrial areas in Canada and the U.S. (p < 0.05). In addition, air concentrations of ΣcVMSs were lower during major snowfall events (on average, 73 ng m(-3)) in comparison to the other sampling periods (121 ng m(-3)). Ambient temperature had a small influence on the seasonal trend of VMS concentrations in air, except for dodecamethylcyclohexasiloxane (D6), which was positively correlated with the ambient temperature (p < 0.001).

Heterogeneous OH initiated oxidation: a possible explanation for the persistence of organophosphate flame retardants in air.

Heterogeneous reactions between OH radicals and emerging flame retardant compounds coated on inert particles have been investigated. Organophosphate esters (OPEs) including triphenyl phosphate (TPhP), tris-2-ethylhexyl phosphate (TEHP), and tris-1,3-dichloro-2-propyl phosphate (TDCPP) were coated on (NH4)2SO4 particles and exposed to OH radicals in a photochemical flow tube at 298 K and (38.0 ± 2.0) % RH. The degradation of these particle-bound OPEs was observed as a result of OH exposure, as measured using a Time-of-Flight Aerosol Mass Spectrometer. The derived second-order rate constants for the heterogeneous loss of TPhP, TEHP, and TDCPP were (2.1 ± 0.19) × 10(-12), (2.7 ± 0.63) × 10(-12), and (9.2 ± 0.92) × 10(-13) cm(3) molecule(-1) s(-1), respectively, from which approximate atmospheric lifetimes are estimated to be 5.6 (5.2-6.0), 4.3 (3.5-5.6), and 13 (11-14) days. Additional coating of the OPE coated particles with an OH radical active species further increased the lifetimes of these OPEs. These results represent the first reported estimates of heterogeneous reaction rate constants for these species. The results demonstrate that particle bound OPEs are highly persistent in the atmosphere with regard to OH radical oxidation, consistent with the assumption that OPEs can undergo medium or long-range transport, as previously proposed on the basis of field measurements. Finally, these results indicate that future risk assessment and transport modeling of emerging priority chemicals with semi- to low-volatility must consider particle phase heterogeneous loss processes when evaluating environmental persistence.

Characterization of two passive air samplers for per- and polyfluoroalkyl substances.

Two passive air sampler (PAS) media were characterized under field conditions for the measurement of per- and polyfluoroalkyl substances (PFASs) in the atmosphere. The PASs, consisting of polyurethane foam (PUF) and sorbent-impregnated PUF (SIP) disks, were deployed for over one year in parallel with high volume active air samplers (HV-AAS) and low volume active air samplers (LV-AAS). Samples were analyzed for perfluoroalkyl carboxylic acids (PFCAs), perfluoroalkane sulfonic acids (PFSAs), fluorotelomer alcohols (FTOHs), fluorotelomer methacrylates (FTMACs), fluorotelomer acrylates (FTACs), perfluorooctane sulfonamides (FOSAs), and perfluorooctane sulfonamidoethanols (FOSEs). Sampling rates and the passive sampler medium (PSM)-air partition coefficient (KPSM-A) were calculated for individual PFASs. Sampling rates were similar for PFASs present in the gas phase and particle phase, and the linear sampling rate of 4 m(-3) d(-1) is recommended for calculating effective air sample volumes in the SIP-PAS and PUF-PAS for PFASs except for the FOSAs and FOSEs in the PUF-PAS. SIP disks showed very good performance for all tested PFASs while PUF disks were suitable only for the PFSAs and their precursors. Experiments evaluating the suitability of different isotopically labeled fluorinated depuration compounds (DCs) revealed that (13)C8-perfluorooctanoic acid (PFOA) was suitable for the calculation of site-specific sampling rates. Ambient temperature was the dominant factor influencing the seasonal trend of PFASs.

Phosphorus-containing fluorinated organics: polyfluoroalkyl phosphoric acid diesters (diPAPs), perfluorophosphonates (PFPAs), and perfluorophosphinates (PFPIAs) in residential indoor dust.

Indoor dust is thought to be a source of human exposure to perfluorocarboxylates (PFCAs) and perfluorosulfonates (PFSAs), but exposures to emerging organofluorine compounds, including precursors to PFCAs and PFSAs via indoor dust, remain unknown. We report an analytical method for measuring several groups of emerging phosphorus-containing fluorinated compounds, including polyfluoroalkyl phosphoric acid diesters (diPAP), perfluorophosphonates (PFPA), and perfluorophosphinates (PFPIA), as well as perfluoroethylcyclohexane sulfonate (PFECHS) in indoor dust. This method was used to analyze diPAP, PFPA, and PFPIA levels in 102 residential dust samples collected in 2007-2008 from Vancouver, Canada. The results indicated a predominant and ubiquitous presence of diPAPs (frequency of detection 100%, mean and median ΣdiPAPs 7637 and 2215 ng/g). Previously measured median concentrations of perfluorooctane sulfonate (PFOS), perfluorooctanoate (PFOA), and fluorotelomer alcohols (FTOHs) in the same samples were 14-74 times lower than ΣdiPAP levels, i.e. 71 ng/g PFOS, 30 ng/g PFOA, and 152 ng/g ΣFTOHs. PFPAs and PFPIAs were detected in 62% and 85% of samples, respectively, at concentrations nearly 3 orders of magnitude lower than diPAPs (median 2.3 ng/g ΣPFPAs and 2.3 ng/g ΣPFPIAs). PFECHS was detected in only 8% of dust samples. To the best of our knowledge, this is the first report of these compounds in indoor dust. In this study, diPAP concentrations represented 98% ± 7% of the total measured analytes in the dust samples. Detection of diPAPs at such high concentrations in indoor dust may represent an important and as-yet unrecognized indirect source of PFCA exposure in humans, given the identified biotransformation pathways. Identifying the sources of diPAPs to the indoor environment is a priority for future research to improve air quality in households.

Improved characterization of gas-particle partitioning for per- and polyfluoroalkyl substances in the atmosphere using annular diffusion denuder samplers.

Gas-phase perfluoroalkyl carboxylic acids (PFCAs) sorb strongly on filter material (i.e., GFF, QFF) used in conventional high volume air samplers, which results in an overestimation of the particle-phase concentration. In this study, we investigated an improved technique for measuring the gas-particle partitioning of per- and polyfluoroalkyl substances (PFASs) using an annular diffusion denuder sampler. Samples were analyzed for 7 PFAS classes [i.e., PFCAs, perfluoroalkane sulfonic acids (PFSAs), fluorotelomer alcohols (FTOHs), fluorotelomer methacrylates (FTMACs), fluorotelomer acrylates (FTACs), perfluorooctane sulfonamides (FOSAs), and perfluorooctane sulfonamidoethanols (FOSEs)]. The measured particulate associated fraction (Φ') using the diffusion denuder sampler generally followed the trend FTACs (0%) < FTOHs (~8%) < FOSAs (~21%) < PFSAs (~29%) < FOSEs (~66%), whereas the Φ' of the C(8)-C(18) PFCAs increased with carbon chain length, and ranged from 6% to 100%. The ionizability of some PFASs, when associated with particles, is an important consideration when calculating the gas-particle partitioning coefficient as both ionic and neutral forms can be present in the particles. Here we differentiate between a gas-particle partitioning coefficient for neutral species, K(p), and one that accounts for both ionic and neutral species of a compound, K(p)'. The measured K(p)' for PFSAs and PFCAs was 4-5 log units higher compared to the interpolated K(p) for the neutral form only. The measured K(p)' can be corrected (to apply to the neutral form only) with knowledge of the pK(a) of the chemical and the pH of the condensed medium ("wet" particle or aqueous aerosol). The denuder-based sampling of PFASs has yielded a robust data set that demonstrates the importance of atmospheric pH and chemical pK(a) values in determining gas-particle partitioning of PFASs.

Polyfluorinated compounds in serum linked to indoor air in office environments.

We aimed to investigate the role of indoor office air on exposure to polyfluorinated compounds (PFCs) among office workers. Week-long, active air sampling was conducted during the winter of 2009 in 31 offices in Boston, MA. Air samples were analyzed for fluorotelomer alcohols (FTOHs), sulfonamides (FOSAs), and sulfonamidoethanols (FOSEs). Serum was collected from each participant (n = 31) and analyzed for 12 PFCs including PFOA and PFOS. In air, FTOHs were present in the highest concentrations, particularly 8:2-FTOH (GM = 9920 pg/m(3)). FTOHs varied significantly by building with the highest levels observed in a newly constructed building. PFOA in serum was significantly correlated with air levels of 6:2-FTOH (r = 0.43), 8:2-FTOH (r = 0.60), and 10:2-FTOH (r = 0.62). Collectively, FTOHs in air significantly predicted PFOA in serum (p < 0.001) and explained approximately 36% of the variation in serum PFOA concentrations. PFOS in serum was not associated with air levels of FOSAs/FOSEs. In conclusion, FTOH concentrations in office air significantly predict serum PFOA concentrations in office workers. Variation in PFC air concentrations by building is likely due to differences in the number, type, and age of potential sources such as carpeting, furniture, and/or paint.

Comparison of annular diffusion denuder and high volume air samplers for measuring per- and polyfluoroalkyl substances in the atmosphere.

Overestimation of the particle phase concentration collected on glass-fiber filters (GFFs) has been reported for perfluoroalkyl carboxylic acids (PFCAs) using conventional high volume air samplers. In this study, per- and polyfluoroalkyl substances (PFASs) were determined in the gas and particulate phases using colocated annular diffusion denuder and high volume air samplers at a semiurban site in Toronto, Canada, in winter 2010. Samples were analyzed for 7 PFAS classes (i.e., PFCAs, perfluoro-alkane sulfonic acids (PFSAs), fluorotelomer alcohols (FTOHs), fluorotelomer methacrylates (FTMACs), fluorotelomer acrylates (FTACs), perfluorooctane sulfonamides (FOSAs), and perfluorooctane sulfonamidoethanols (FOSEs)). The gas diffusion coefficients for individual PFASs were calculated and the denuder performance was evaluated. Modeled subcooled liquid vapor pressures (p(L)) correlated well with the vapor phase breakthrough for the denuder and high volume air systems. Total air concentrations for PFASs measured using annular diffusion denuders and high volume samplers were in agreement within a factor of 4; however, much greater differences were observed for measurements of gas-particle partitioning. Vapor phase PFSAs and PFCAs can adsorb to the GFF using high volume air samplers, resulting in much higher particle-associated fractions for these chemicals compared to the annular diffusion denuder sampler. This effect was not observed for the FTOHs, FTMACs, FTACs, FOSAs, and FOSEs. Thus, for investigations of gas-particle partitioning of PFSAs and PFCAs, the diffusion denuder sampler is the preferred method. The results of this study improve our understanding of the gas-particle partitioning of PFASs, which is important for modeling their long-range transport in air.

Indoor sources of poly- and perfluorinated compounds (PFCS) in Vancouver, Canada: implications for human exposure.

Perfluorooctane sulfonate (PFOS) and perfluorooctanoate (PFOA) are widely detected in human blood and serum and are of concern due to their potential toxicity. This study investigated the indoor sources of these compounds and their neutral precursors through a survey of 152 homes in Vancouver, Canada. Samples were collected of indoor air, outdoor air, indoor dust, and clothes dryer lint and analyzed for neutral [i.e., fluorotelomer alcohols (FTOHs), perfluorooctane sulfonamide (FOSA), and perfluorooctane sulfonamidoethanol (FOSE)] and ionic [i.e., PFOS and perfluoroalkyl carboxylates (PFCAs)] poly- and perfluorinated compounds (PFCs). Indoor air was dominated by 8:2 FTOH with a geometric mean concentration (pg/m(3)) of 2900. Among the FOSAs and FOSEs, MeFOSE exhibited the highest air concentration with a geometric mean of 380 pg/m(3). PFOA was the major ionic PFC and was detected in all indoor air samples with a geometric mean of 28 pg/m(3), whereas PFOS was below the detection limit. The results for the ionic PFCs in indoor air are the first for North America. The pattern of the neutral PFCs in house dust was also dominated by 8:2 FTOH, with a geometric mean of 88 ng/g. Dusts were enriched (relative to air) with sulfonamidoethanol (FOSE) which comprised ∼22% of the total neutral PFC content compared to only ∼3% in air. PFOS and PFOA were the most prominent compounds detected in dust samples. Levels of neutral PFCs in clothes dryer lint were an order of magnitude lower compared to house dust. Human exposure estimates to PFCs for adults and children showed that inhalation was the main exposure route for neutral and ionic PFCs in adults. For toddlers, ingestion of PFCs via dust was more relevant and was on the order of a few mg/day. Results from this study contribute to our understanding of exposure pathways of PFCs to humans. This will facilitate investigations of related health effects and human monitoring data.

Wastewater treatment plant and landfills as sources of polyfluoroalkyl compounds to the atmosphere.

Polyfluoroalkyl compounds (PFCs) were determined in air around a wastewater treatment plant (WWTP) and two landfill sites using sorbent-impregnated polyurethane foam (SIP) disk passive air samplers in summer 2009. The samples were analyzed for five PFC classes (i.e., fluorotelomer alcohols (FTOHs), perfluorooctane sulfonamides (FOSAs), sulfonamidoethanols (FOSEs), perfluoroalkyl sulfonic acids (PFSAs), and perfluoroalkyl carboxylic acids (PFCAs)) to investigate their concentration in air, composition and emissions to the atmosphere. ∑PFC concentrations in air were 3-15 times higher within the WWTP (2280-24 040 pg/m(3)) and 5-30 times higher at the landfill sites (2780-26 430 pg/m(3)) compared to the reference sites (597-1600 pg/m3). Variations in the PFC pattern were observed between the WWTP and landfill sites and even within the WWTP site. For example, FTOHs were the predominant PFC class in air for all WWTP and landfill sites, with 6:2 FTOH as the dominant compound at the WWTP (895-12 290 pg/m(3)) and 8:2 FTOH dominating at the landfill sites (1290-17 380 pg/m(3)). Furthermore, perfluorooctane sulfonic acid (PFOS) was dominant within the WWTP (43-171 pg/m(3)), followed by perfluorobutanoic acid (PFBA) (55-116 pg/m(3)), while PFBA was dominant at the landfill sites (101-102 pg/m(3)). It is also noteworthy that the PFCA concentrations decreased with increasing chain length and that the emissions for the even chain length PFCAs outweighed emissions for the odd chain length compounds. Furthermore, highly elevated PFC concentrations were found near the aeration tanks compared to the other tanks (i.e., primary and secondary clarifier) and likely associated with increased volatilization during aeration that may be further enhanced through aqueous aerosol-mediated transport. ∑PFC yearly emissions estimated using a simplified dispersion model were 2560 g/year for the WWTP, 99 g/year for landfill site 1, and 1000 g/year for landfill site 2. These results highlight the important role of WWTPs and landfills as emission sources of PFCs to the atmosphere.

Global distribution of linear and cyclic volatile methyl siloxanes in air.

The global distribution of linear and cyclic volatile methyl silxoanes (VMS) was investigated at 20 sites worldwide, including 5 locations in the Arctic, using sorbent-impregnated polyurethane foam (SIP) disk passive air samplers. Cyclic VMS are currently being considered for regulation because they are high production volume chemicals that are potentially persistent, bioaccumulative, and toxic. Linear and cyclic VMS (including L3, L4, L5, D3, D4, D5, and D6) were analyzed for in air at all urban, background, and Arctic sites. Concentrations of D3 and D4 are significantly correlated, as are D5 and D6, which suggests different sources for these two pairs of compounds. Elevated concentrations of D3 and D4 on the West coast of North America and at high elevation sites suggest these sites are influenced by trans-Pacific transport, while D5 and D6 have elevated concentrations in urban areas, which is most likely due to personal care product use. Measured concentrations of D5 were compared to modeled concentrations generated using both the Danish Eulerian Hemispheric Model (DEHM) and the Berkeley-Trent Global Contaminant Fate Model (BETR Global). The correlation coefficients (r) between the measured and modeled results were 0.73 and 0.58 for the DEHM and BETR models, respectively. Agreement between measurements and models indicate that the sources, transport pathways, and sinks of D5 in the global atmosphere are fairly well understood.

Urban sources of synthetic musk compounds to the environment.

The occurrence and potential sources of synthetic musk compounds (SMCs) in the urban and surrounding environment were investigated. We analyzed air, soils and surface waters from a wide array of land-use types and urban densities including air from wastewater treatment plants (WWTPs), indoor, urban, rural, and remote Arctic sites; surface waters from urban and rural tributaries; and effluents of three WWTPs. In air, the median sum concentration of six selected polycyclic musks (Σ6PCMs) (i.e., galaxolide, tonalide, cashmeran, celestolide, phantolide, traseolide) were the highest from WWTP on-site > indoor > urban > WWTP off-site > rural. SMCs were not found in remote Arctic air indicating low potential for long-range atmospheric transport. SMCs were not found in soils, likely because of their high volatility and fast biodegradation rate. Galaxolide (HHCB) and tonalide (AHTN) were the two most abundant SMCs in air, tributaries and WWTP effluents. Σ6PCM concentrations in air taken along urban-rural transects and in tributary water were positively correlated with population density. In WWTP on-site air, trace levels of the toxic nitro-musks, namely musk xylene and musk ketone were detected and macrocyclic musks accounted for ∼10% of the total SMCs measured. In WWTP effluents, the concentrations of Σ6PCMs were proportional to the population served. We conclude that sources of SMCs to the outdoor urban environment and hence the surrounding region, originate from releases from indoor air, and temperature-dependent volatilization from WWTPs during treatment.

Characterization of polyurethane foam (PUF) and sorbent impregnated PUF (SIP) disk passive air samplers for measuring organophosphate flame retardants.

This study aimed to characterize the uptake of organophosphate esters (OPEs) by polyurethane foam (PUF) and sorbent-impregnated polyurethane foam (SIP) disk passive air samplers (PAS). Atmospheric OPE concentrations were monitored with high-volume active air samplers (HV-AAS) that were co-deployed with passive air samplers. Samples were analyzed for tris(2-chloroisopropyl) phosphate (TCIPP), tri(phenyl) phosphate (TPhP), tris(2-chloroethyl) phosphate (TCEP), and tris(2,3-dichloropropyl) phosphate (TDCIPP). The mean concentration of ∑OPEs in air was 2650 pg/m3 for the HV-AAS. Sampling rates and the passive sampler medium (PSM)-air partition coefficient (KPSM-Air) were calculated for individual OPEs. The average calculated sampling rates (R) for the four OPEs were 3.6 ± 1.2 and 4.2 ± 2.0 m3/day for the PUF and SIP disks, respectively, and within the range of the recommended default value of 4 ± 2 m3/day. Since most of the OPEs remained in the linear uptake phase during the study, COSMO-RS solvation theory and an oligomer-based model were used to estimate KPUF-Air for the OPEs. The estimated values of log KPUF-Air were 7.45 (TCIPP), 9.35 (TPhP), 8.44 (TCEP), and 9.67 (TDCIPP). Finally, four configurations of the PUF and SIP disks were tested by adjusting the distance of the gap opening between the upper and lower domes of the sampler housing: i.e. 2 cm, 1 cm, no gap and 1 cm overlap. The sampling rate did not differ significantly between these four configurations (p < 0.05).

Perfluoroalkyl acids and their precursors in indoor air sampled in children's bedrooms.

The contamination levels and patterns of perfluoroalkyl acids (PFAAs) and their precursors in indoor air of children's bedrooms in Finland, Northern Europe, were investigated. Our study is among the most comprehensive indoor air monitoring studies (n = 57) and to our knowledge the first one to analyse air in children's bedrooms for PFASs (17 PFAAs and 9 precursors, including two acrylates, 6:2 FTAC and 6:2 FTMAC). The most frequently detected compound was 8:2 fluorotelomer alcohol (8:2 FTOH) with the highest median concentration (3570 pg/m3). FTOH concentrations were generally similar to previous studies, indicating that in 2014/2015 the impact of the industrial transition had been minor on FTOH levels in indoor air. However, in contrast to earlier studies (with one exception), median concentrations of 6:2 FTOH were higher than 10:2 FTOH. The C8 PFAAs are still the most abundant acids, even though they have now been phased out by major manufacturers. The mean concentrations of FOSE/As, especially MeFOSE (89.9 pg/m3), were at least an order of magnitude lower compared to previous studies. Collectively the comparison of FTOHs, PFAAs and FOSE/FOSAs with previous studies indicates that indoor air levels of PFASs display a time lag to changes in production of several years. This is the first indoor air study investigating 6:2 FTMAC, which was frequently detected (58%) and displayed some of the highest maximum concentrations (13 000 pg/m3). There were several statistically significant correlations between particular house and room characteristics and PFAS concentrations, most interestingly higher EtFOSE air concentrations in rooms with plastic floors compared to wood or laminate.

Passive sampler derived air concentrations of PBDEs along an urban-rural transect: spatial and temporal trends.

Passive air samplers consisting of polyurethane foam (PUF) disks housed in chambers were deployed at several sites along a approximately 75 km urban-rural gradient in Toronto and analyzed for polybrominated diphenyl ethers (PBDEs). Samplers were allowed to integrate gas-phase PBDEs over three consecutive seasons starting in the summer of 2000. PBDEs were fairly uniform along the transect with air concentrations in Toronto (10-30 pgm(-3)) about a factor of two greater than at rural sites. Lowest concentrations were observed during the winter and probably associated with reduced inputs from indoor sources of PBDEs and to a preference for PBDEs to partition to the particle-phase at colder temperatures. The composition of PBDEs in the air samples did not differ across the transect or for the different seasons.

Human exposure to per- and polyfluoroalkyl substances (PFASs) via house dust in Korea: Implication to exposure pathway.

A wide range of per- and polyfluoroalkyl substances (PFASs), including fluorotelomer alcohols (FTOHs), perfluorooctane sulfonamidoethanols (FOSEs), perfluoroalkyl carboxylic acids (PFCAs), and perfluoroalkane sulfonic acids (PFSAs), were measured in fifteen house dust and two nonresidential indoor dust of Korea. Total concentrations of PFASs in house dust ranged from 29.9 to 97.6 ng g(-1), with a dominance of perfluorooctane sulfonic acid (PFOS), followed by 8:2 FTOH, N-Ethyl perfluorooctane sulfonamidoethanol (EtFOSE), perfluoroctanoic acid (PFOA). In a typical exposure scenario, the estimated daily intakes (EDIs) of total PFASs via house dust ingestion were 2.83 ng d(-1) for toddlers and 1.13 ng d(-1) for adults, which were within the range of the mean EDIs reported from several countries. For PFOA and PFOS exposure via house dust ingestion, indirect exposure (via precursors) was a minor contributor, accounting for 5% and 12%, respectively. An aggregated exposure (hereafter, overall-EDIs) of PFOA and PFOS occurring via all pathways, estimated using data compiled from the literature, were 53.6 and 14.8 ng d(-1) for toddlers, and 20.5 and 40.6 ng d(-1) for adults, respectively, in a typical scenario. These overall-EDIs corresponded to 82% (PFOA) and 92% (PFOS) of a pharmacokinetic model-based EDIs estimated from adults' serum data. Direct dietary exposure was a major contributor (>89% of overall-EDI) to PFOS in both toddlers and adults, and PFOA in toddlers. As for PFOA exposure of adults, however direct exposure via tap water drinking (37%) and indirect exposure via inhalation (22%) were as important as direct dietary exposure (41%). House dust-ingested exposure (direct+indirect) was responsible for 5% (PFOS in toddlers) and <1% (PFOS in adults, and PFOA in both toddlers and adults) of the overall-EDIs. In conclusion, house-dust ingestion was a minor contributor in this study, but should not be ignored for toddlers' PFOS exposure due to its significance in the worst-case scenario.

Emission of poly and perfluoroalkyl substances, UV-filters and siloxanes to air from wastewater treatment plants.

The potential of wastewater treatment plants (WWTPs) to act as sources of poly and perfluoroalkyl substances (PFASs), volatile methyl siloxanes (VMSs) and organic UV-filters to the atmosphere was investigated. Target compounds included: PFASs (fluorotelomer alcohols (FTOHs), perfluorooctane sulfonamides/sulfonamidoethanols (FOSAs/FOSEs), perfluroalkyl sulfonic acids (PFSAs) and perfluroalkyl carboxylic acids (PFCAs)), cyclic VMSs (D3 to D6), linear VMSs (L3 to L5) and eight UV-filters. Emissions to air were assessed at eight WWTPs using paired sorbent-impregnated polyurethane foam passive air samplers, deployed during summer 2013 and winter 2014. Samplers were deployed on-site above the active tank and off-site as a reference. Several types of WWTPs were investigated: secondary activated sludge in urban areas (UR-AS), secondary extended aeration in towns (TW-EA) and facultative lagoons in rural areas (RU-LG). The concentrations of target compounds in air were ∼1.7-35 times higher on-site compared to the corresponding off-site location. Highest concentrations in air were observed at UR-AS sites while the lowest were at RU-LG. Higher air concentrations (∼2-9 times) were observed on-site during summer compared to winter, possibly reflecting enhanced volatilization due to higher wastewater temperatures or differences in influent wastewater concentrations. A significant positive correlation was obtained between concentrations in air and WWTP characteristics (influent flow rate and population in the catchment of the WWTP); whereas a weak negative correlation was obtained with hydraulic retention time. Emissions to air were estimated using a simplified dispersion model. Highest emissions to air were seen at the UR-AS locations. Emissions to air (g/year/tank) were highest for VMSs (5000-112,000) followed by UV-filters (16-2000) then ΣPFASs (10-110).

Using measured octanol-air partition coefficients to explain environmental partitioning of organochlorine pesticides.

Octanol-air partition coefficients (Koa) were measured directly for 19 organochlorine (OC) pesticides over the temperature range of 5 to 35 degrees C. Values of log Koa at 25 degrees C ranged over three orders of magnitude, from 7.4 for hexachlorobenzene to 10.1 for 1,1-dichloro-2,2-bis(p-chlorophenyl) ethane. Measured values were compared to values calculated as KowRT/H (where R is the ideal gas constant [8.314 J mol(-1) K(-1)], T is absolute temperature, and H is Henry's law constant) were, in general, larger. Discrepancies of up to three orders of magnitude were observed, highlighting the need for direct measurements of Koa. Plots of Koa versus inverse absolute temperature exhibited a log-linear correlation. Enthalpies of phase transition between octanol and air (deltaHoa) were determined from the temperature slopes and were in the range of 56 to 105 kJ mol(-1) K(-1). Activity coefficients in octanol (gamma(o)) were determined from Koa and reported supercooled liquid vapor pressures (pL(o)), and these were in the range of 0.3 to 12, indicating near-ideal solution behavior. Differences in Koa values for structural isomers of hexachlorocyclohexane were also explored. A Koa-based model was described for predicting the partitioning of OC pesticides to aerosols and used to calculate particulate fractions at 25 and -10 degrees C. The model also agreed well with experimental results for several OC pesticides that were equilibrated with urban aerosols in the laboratory. A log-log regression of the particle-gas partition coefficient versus Koa had a slope near unity, indicating that octanol is a good surrogate for the aerosol organic matter.

Contribution of diffuse inputs to the aqueous mass load of perfluoroalkyl acids in river and stream catchments in Korea.

Recent studies disagree regarding the contributions of point versus non-point sources to the aqueous mass loads of perfluoroalkyl acids (PFAAs). This study investigated the longitudinal change in PFAA mass load from upstream to downstream stations along rivers and/or streams to assess the relative contributions of point versus nonpoint inputs. With concentrations 10 to 100 times higher than running water, point sources such as wastewater treatment plants (WWTPs) effluent and airport ditch-outlet (ADO) water were separated from neighboring upstream and downstream running waters using principal component analysis. Source waters were characterized by certain predominant components [e.g., perfluorobutylsulfonate (PFBS) and perfluorooctanoic acid (PFOA) in WWTP effluent and perfluorohexylsulfonate (PFHxS) and perfluorooctylsulfonate (PFOS) in ADO water], which were minor components of running water. From a mass balance assessment of PFAA mass load, certain compounds such as PFOA and PFBS dominated the contribution of point sources to the mass load in the running water at downstream stations or in small catchment basins with high levels of industrial activity. Most of the mass load in the investigated catchments was attributable to upstream running water with a minor influence from industrial, commercial, and domestic human activities. Furthermore, the negative relationship of per capita emission factors (hereafter, EFs) with population density and a lower contribution of PFAA from WWTPs (~30% on average) compared to the running water-derived mass load at the national level indicated that diffuse inputs were more important contributors to aqueous PFAA contamination in each catchment basin as well as the entire watershed of the country (Korea). Volatile precursor compounds, which are readily dispersed to neighboring basins and transformed to PFAAs in the ambient environment, can be an important source of these diffuse inputs and will become more significant over time.

In situ air-water and particle-water partitioning of perfluorocarboxylic acids, perfluorosulfonic acids and perfluorooctyl sulfonamide at a wastewater treatment plant.

In situ measurements of air and water phases at a wastewater treatment plant (WWTP) were used to investigate the partitioning behavior of perfluorocarboxylic acids (PFCAs), perfluorosulfonic acids (PFSAs) and perfluorooctyl sulfonamide (HFOSA) and their conjugate bases (PFC(-)s, PFS(-)s, and FOSA(-), respectively). Particle-dissolved (Rd) and air-water (QAW) concentration ratios were determined at different tanks of a WWTP. Sum of concentrations of C4-12,14 PFC(A)s, C4,6,8,10 PFS(A)s and (H)FOSA were as high as 50 pg m(-3) (atmospheric gas phase), 2300 ng L(-1) (aqueous dissolved phase) and 2500 ng L(-1) (aqueous particle phase). Particle-dissolved concentration ratios of total species, log Rd, ranged from -2.9 to 1.3 for PFS(A)s, from -1.9 to 1.1 for PFC(A)s and was 0.71 for (H)FOSA. These field-based values agree well with equilibrium partitioning data reported in the literature, suggesting that any in situ generation from precursors, if they are present in this system, occurs at a slower rate than the rate of approach to equilibrium. Acid QAW were also estimated. Good agreement between the QAW and the air-water equilibrium partition coefficient for C8PFCA suggests that the air above the WWTP tanks is at or near equilibrium with the water. Uncertainties in these QAW values are attributed mainly to variability in pKa values reported in the literature. The WWTP provides a unique environment for investigating environmental fate processes of the PFCAs and PFSAs under 'real' conditions in order to better understand and predict their fate in the environment.