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Airborne polycyclic aromatic hydrocarbons (PAHs) and their derivatives are of particular concern for population health due to their abundance and toxicity via inhalation. Lung toxicity testing includes exposing lung epithelial cell lines to PAHs in a culture medium containing inorganic species, lipids, proteins, and other biochemicals where the cell response is influenced among others by the toxic chemical accessibility in the medium. While inhalation bioaccessibility of PAHs and other toxicants was previously studied in surrogate lung fluids, studies measuring bioaccessibility in cell culture media are rare. In this work, a method was developed to characterize PAH bioaccessibility in a culture medium used for mouse lung epithelial (FE1) cells. Further, the optimised method was tested using commercially available standard reference material of urban particulate matter (PM) as well as polyurethane foam passive air samplers (PUF-PAS). The method provided a high precision and recovery of analytes, indicating no losses during sample processing and analysis. PAHs had non-linear concentration-responses, with the culture medium approaching saturation with PM concentration of 500 μg mL -1 . The results showed that phenanthrene, a 3-ring PAH, was significantly more bioaccessible than ≥4-ring congeners in the culture medium (up to ∼2.5 folds; p < 0.05). Finally, using pre-deployed PUF-PAS from a residential and an industrial site, five PAHs were found in the culture medium, including naphthalene, phenanthrene, anthracene, fluoranthene, and pyrene. This work provides a proof of concept to enable future studies to assess the inhalation bioaccessibility of polycyclic aromatic compounds and other airborne pollutants collected using PUF-PAS., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Crown Copyright © 2024. Published by Elsevier Ltd. All rights reserved.)

A mapping study targeting emissions of polycyclic aromatic compounds (PACs) from an oil sands tailings pond was undertaken in the Athabasca Oil sands Region (AOSR). Ten passive air samplers comprising polyurethane foam (PUF) disks were deployed around the perimeter of Suncor Tailings Pond 2/3 for a five-week period to generate time-integrated concentrations in air for PACs, which included ∑unsubstituted polycyclic aromatic hydrocarbons (PAHs), ∑alkylated PAHs (alk-PAHs), and ∑dibenzothiophenes (DBTs) (both unsubstituted and alkylated). Concentrations in air ranged from 13 to 70, 220-970, and 30-210 ng/m 3 , respectively, and were elevated in samplers downwind of the tailings pond. PAC emissions to air from the pond were estimated using only the air-side concentration information by applying a simplified Gaussian dispersion model and found to be 896 μg/m 2 /day. ∑alk-PAHs and ∑DBTs had the highest contribution to the total PAC fluxes (79% and 16%, respectively). This flux estimate for PACs is equivalent to 460 kg on an annual basis and 35 000 kg/year when scaled to represent all tailings ponds in the region. The results generally agree with fluxes estimated from coupled high volume air sampling data and tailings pond water concentrations from the same field study but which are complicated due to uncertainties associated with the use of pure water Henry's Law values for tailings pond water as well as the potential for surface oily films on the tailings ponds to impact water-air exchange of PACs. Overall, these findings support the use of relatively simple and electricity-free PUF disk samplers for mapping and estimating emissions from area sources such as tailings ponds, using only air-side concentration information., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Crown Copyright © 2023. Published by Elsevier Ltd. All rights reserved.)

The study reports on the atmospheric concentrations of per- and polyfluoroalkyl substances (PFAS) and volatile methyl siloxanes (VMS) measured using sorbent-impregnated polyurethane foam disks (SIPs) passive air samplers. New results are reported for samples collected in 2017, which extends temporal trend information to the period 2009-2017, for 21 sites where SIPs have been deployed since 2009. Among neutral PFAS, fluorotelomer alcohols (FTOHs) had higher concentrations than perfluoroalkane sulfonamides (FOSAs) and perfluoroalkane sulfonamido ethanols (FOSEs) with levels of ND‒228, ND‒15.8, ND‒10.4 pg/m 3 , respectively. Among ionizable PFAS, the sum of perfluoroalkyl carboxylic acids (PFCAs) and perfluoroalkyl sulfonic acids (PFSAs) in air were 0.128-781 and 6.85-124 pg/m 3 , respectively. Longer-chain i.e. C 9 -C 14 PFAS, which are relevant to the recent proposal by Canada for a listing of long-chain (C 9 -C 21 ) PFCAs to the Stockholm Convention, were also detected in the environment at all site categories including Arctic sites. Cyclic and linear VMS ranged between 1.34‒452 and 0.01-12.1 ng/m 3 , respectively, showing dominance in urban areas. Despite the wide range of levels observed across different site categories, geometric means of the PFAS and VMS groups were fairly similar when grouped according to the five United Nations regions. Variable temporal trends in air (2009-2017) were observed for both PFAS and VMS. PFOS, which has been listed in the Stockholm Convention since 2009, is still showing increasing tendencies at several sites, indicating constant input from direct and/or indirect sources. These new data inform international chemicals management for PFAS and VMS., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Crown Copyright © 2023. Published by Elsevier Ltd. All rights reserved.)

Pollution from vehicle tires has received world-wide research attention due to its ubiquity and toxicity. In this study, we measured various tire-derived contaminants semi-quantitatively in archived extracts of passive air samplers deployed in 18 major cities that comprise the Global Atmospheric Passive Sampling (GAPS) Network (GAPS-Megacities). Analysis was done on archived samples, which represent one-time weighted passive air samples from each of the 18 monitoring sites. The target analytes included cyclic amines, benzotriazoles, benzothiazoles, and p-phenylenediamine (PPD) derivatives. Of the analyzed tire-derived contaminants, diphenylguanidine was the most frequently detected analyte across the globe, with estimated concentrations ranging from 45.0 pg/m 3 in Beijing, China to 199 pg/m 3 in Kolkata, India. The estimated concentrations of 6PPD-quinone and total benzothiazoles (including benzothiazole, 2-methylthio-benzothiazole, 2-methyl-benzothiazole, 2-hydroxy-benzothiazole) peaked in the Latin American and the Caribbean region at 1 pg/m 3 and 100 pg/m 3 , respectively. In addition, other known tire-derived compounds, such as hexa(methoxymethyl)melamine, phenylguanidine, and various transformation products of 6PPD, were also monitored and characterized semi-quantitatively or qualitatively. This study presents some of the earliest data on airborne concentrations of chemicals associated with tire-wear and shows that passive sampling is a viable techniquefor monitoring airborne tire-wear contamination. Due to the presence of many tire-derived contaminants in urban air across the globe as highlighted by this study, there is a need to determine the associated exposure and toxicity of these chemicals to humans., Competing Interests: Declaration of competing interest The authors declare the following financial interests/personal relationships which may be considered as potential competing interests: Tom Harner reports financial support was provided by Government of Canada., (Copyright © 2022 The Authors. Published by Elsevier Ltd.. All rights reserved.)

Carbonaceous aerosol species, such as elemental carbon (EC), are important Short-Lived Climate Forcers (SLCFs), contributing to climate and health effects of air pollution. The quantification of carbonaceous aerosols has been conventionally carried out using active air sampling followed by various analytical techniques, such as thermal/thermal-optical analysis. Active sampling requires specific equipment and infrastructure with electricity and therefore may not be the best choice for studying carbonaceous aerosols at remote locations. Passive sampling on the other hand provides a simple and cost-effective alternative to study time-weighted temporal and spatial trends. For the first time in this study, we have developed a method to examine the viability of measuring EC using polyurethane foam passive air samplers (PUF-PAS) coupled with a thermal analysis, i.e., EnCan-Total-900 (ECT9). The method was found reproducible with coefficients of variation as low as 3% for EC measured in ambient passive samples. The method had relatively low background with EC levels in blanks being as low as 0.1% of those in deployed samples, allowing quantification within a wide range of concentrations. The results indicate a homogenous distribution of particles within the PUF-PAS substrate. EC concentrations measured with the passive method were not significantly different from those obtained from active samples at the study sites (p > 0.01). This proof of concept of the PUF-PAS method provides an opportunity to cost-effectively expand measurements of elemental carbon at the global scale, and could be further extended to include other carbonaceous aerosol species in the future. This helps address regional data gaps for improving uncertainties of SLCF impacts on global climate forcing and to inform policy decisions., (Crown Copyright © 2022. Published by Elsevier Ltd. All rights reserved.)

Commercial chemicals are used extensively across urban centres worldwide 1 , posing a potential exposure risk to 4.2 billion people 2 . Harmful chemicals are often assessed on the basis of their environmental persistence, accumulation in biological organisms and toxic properties, under international and national initiatives such as the Stockholm Convention 3 . However, existing regulatory frameworks rely largely upon knowledge of the properties of the parent chemicals, with minimal consideration given to the products of their transformation in the atmosphere. This is mainly due to a dearth of experimental data, as identifying transformation products in complex mixtures of airborne chemicals is an immense analytical challenge 4 . Here we develop a new framework-combining laboratory and field experiments, advanced techniques for screening suspect chemicals, and in silico modelling-to assess the risks of airborne chemicals, while accounting for atmospheric chemical reactions. By applying this framework to organophosphate flame retardants, as representative chemicals of emerging concern 5 , we find that their transformation products are globally distributed across 18 megacities, representing a previously unrecognized exposure risk for the world's urban populations. More importantly, individual transformation products can be more toxic and up to an order-of-magnitude more persistent than the parent chemicals, such that the overall risks associated with the mixture of transformation products are also higher than those of the parent flame retardants. Together our results highlight the need to consider atmospheric transformations when assessing the risks of commercial chemicals., (© 2021. Crown.)

Mining-related activities in the Alberta Oil Sands Region (AOSR) are known to emit polycyclic aromatic hydrocarbons (PAHs) and related compounds to ambient air. This is a concern due to the toxicity of PAHs, including their transformation products such as nitrated (NPAHs) and oxygenated (OPAHs) PAHs. This is the first study that provided a more extensive outlook into the sources, occurrence in air, and spatial and seasonal patterns of NPAHs and OPAHs in the AOSR by using passive air sampling. A sampling campaign from 2013 to 2016 revealed concentrations of NPAHs that were much lower than those of OPAHs. The highest concentrations of NPAHs were concentrated in the region associated with extensive mining activities, with ∑NPAH concentrations ranging from 20 to 250 pg/m 3 . Within the oil sands (OS) mineable area, NPAHs associated with primary release appear more commonly, while NPAHs produced via oxidative transformation are predominant outside of this area. The concentrations of ∑OPAH ranged from 400 to 2400 pg/m 3 , with the highest air concentrations in the region located south of the main OS activity zone, with peak concentrations attributed to a 2016 forest fire event. Uptake of PAHs from ambient air and their subsequent conversion to generate OPAHs is believed to play an important role in wildfire emissions of OPAHs. The seasonal trend investigation was inconclusive, with NPAHs slightly higher during the winter, while OPAHs were slightly elevated during summer. A preliminary comparison of ambient concentrations of OPAHs and NPAHs in the AOSR to measurements in the Greater Toronto Area revealed a similar range of concentrations, but also a unique presence of certain NPAHs such as 4-nitrobiphenyl, 2-nitrodibenzothiophene, 2,8-dinitrodibenzothiophene and 6-nitrobenzo-(a)-pyrene. This indicates that AOSR might have its own NPAH profile - creating the need to better understand associated NPAH toxicity and propensity for long range transport., (Copyright © 2021 The Authors. Published by Elsevier Ltd.. All rights reserved.)

This study provides guidance on using polyurethane foam-based passive air samplers (PUF-PASs) for atmospheric nonane chlorinated paraffins (C 9 -CPs) and short-chain CPs (SCCPs) and reports SCCP concentrations in air in the Greater Toronto Area (GTA), Canada. We estimated the partition coefficients between PUF and air ( K PUF-A ) and between octanol and air ( K OA ) for C 9 -CP and SCCP congeners using the COSMO-RS method, so that PUF disk uptake profiles for each formula group could be calculated. We then measured SCCP concentrations in PUF disk samples collected from distinct source sectors in urban air across the GTA. Concentrations in samplers were used to calculate C 9 -CP and SCCP concentrations in air and the PUF disk uptake profiles revealed that time-weighted linear phase sampling was possible for congeners having log K OA values greater than 8.5. The highest SCCP concentrations, with an annual average concentration of 35.3 ng/m 3 , were measured at the industrial site, whereas lower but comparable SCCP concentrations were found in residential and background sites, with annual averages of 7.73 and 10.5 ng/m 3 , respectively. No consistent seasonal variation in SCCP concentrations was found in the six distinct source sectors. Direct measurements of K PUF-A and K OA values as a function of temperature could be used to increase accuracy in future studies.

Summer intensive air measurements of alkylated polycyclic aromatic compounds (Alk-PACs), nitrated polycyclic aromatic hydrocarbons (NPAHs), and oxygenated polycyclic aromatic hydrocarbons (OPAHs) was conducted during the summer of 2013 at an air monitoring site near the community of Fort McKay in the Athabasca oil sands region (AOSR). This study uses the ambient air measurements in conjunction with supplementary meteorological and air quality data from coordinated ground- and aircraft-based sampling over the same period to characterize diurnal variations and changes in the organic air pollutant profiles associated with the plume episodes. Principal component analysis showed a distinct PAC profile during plume episodes, driven mainly by higher fluorenone (FLO) and 9,10-anthraquinone (ANQ) concentrations. During the plume episodes (August 23-24), means of NPAHs and OPAHs concentrations were 120 and 2020 pg/m 3 , respectively, which were 2.7 and 2.5 times higher than those measured on the other days, while Alk-PACs did not reach maxima. The relative constancy of Alk-PACs during the plume episodes and baseline air quality periods likely reflects a continuous and broad emission of Alk-PACs from the oil sands mining activities. Only four OPAHs, including FLO, ANQ, benzo(a)fluorenone, and benzanthrone, exhibited higher average daytime than nighttime concentrations (p-value < 0.05). Categorizing air samples into clean and polluted conditions demonstrated that the polluted condition air samples were characterized by higher percent composition of alkylated fluorenes, FLO, MANQ, and photochemically-derived 1M4NN. A comparison of PAC profiles in air samples and oil sand ore samples suggests that the NPAHs were likely influenced by atmospheric formation while the OPAHs were impacted by a combination of primary sources and atmospheric formation. The strong correlations found between a number of NPAHs and OPAHs, and PM 2.5 and NO x in this study could support the modelling of ambient air burdens of these compounds across the region., (Crown Copyright © 2021. Published by Elsevier Ltd. All rights reserved.)

The Global Atmospheric Passive Sampling (GAPS) network, initiated in 2005 across 55 global sites, supports the global monitoring plan (GMP) of the Stockholm Convention on Persistent Organic Pollutants (POPs) by providing information on POP concentrations in air on a global scale. These data inform assessments of the long-range transport potential of POPs and the effectiveness evaluation of chemical regulation efforts, by observing changes in concentrations over time. Currently, measurements spanning 5-10 sampling years are available for 40 sites from the GAPS Network. This study was the first time that POP concentrations in air were reported on a global scale for an extended time period and the first to evaluate worldwide trends with an internally consistent sample set. For consistency between sampling years, site- and sample specific sampling rates were calculated with a new, public online model, which accounts for the effects of wind speed variability. Concentrations for legacy POPs in air between 2005 and 2014 show different trends for different organochlorine pesticides (OCPs) and polychlorinated biphenyls (PCBs). The POPs discussed in this study were chosen due to being the most frequently detected, with detection at the majority of sites. PCB, endosulfan, and hexachlorocyclohexane (HCH) concentrations in air are decreasing at most sites. The global trends reflect global sources and recycling of HCH, ongoing emissions from old stockpiles for PCBs, and recent use restrictions for endosulfan. These chlorinated OCPs continue to present exposure threat to humans and ecosystems worldwide. Concentrations of other OCPs, such as chlordanes, heptachlor and dieldrin, are steady and/or declining slowly at the majority of sites, reflecting a transition from primary to secondary sources (i.e., re-emission from reservoirs where these POPs have accumulated historically) which now control ambient air burdens.

Air pollution is a major environmental health risk and it contributes to respiratory and cardiovascular diseases and excess mortality worldwide. The adverse health effects have been associated with the inhalation of fine particulate matter (PM 2.5 ) and induction of respiratory oxidative stress. In this work, we quantified the oxidative potential (OP) of PM 2.5 from several Canadian cities (Toronto, Hamilton, Montreal, Vancouver) using a recently developed bioanalytical method which measures the oxidation of lung antioxidants, glutathione, cysteine, and ascorbic acid, the formation of glutathione disulfide and cystine, and the related redox potential (RP) in a simulated epithelial lining fluid (SELF). We evaluated the application of empirical SELF RP as a new metric for aerosol OP. We further investigated how PM 2.5 chemical composition and OP are related across various emission source sectors and whether these features are linked to specific properties of aerosol aqueous phase, such as pH and metal-ligand complexation. The OP indicators including SELF RP were strongly correlated among each other, indicating that the empirical RP could be used as a reliable metric in future studies. OP based on ascorbic acid showed dependency on the emission source sectors, most likely due to variation in the solubility of Fe. Traffic emissions resulted in the highest OP, followed by industrial emissions and resuspended crustal matter. OP presented low correlation with PM 2.5 concentrations, low-moderate correlation with the aerosol organic matter, and moderate-strong association with black carbon and transition metals across the sites. We did not find strong association between the concentration of biomass burning tracers and OP. Copper was the only metal that showed high association with OP across all sites, whereas the correlation with other metals, such as iron, manganese, and titanium, showed clear dependency on the source sectors. The aerosol pH correlated negatively with ambient temperature and positively with biomass burning tracers and the levels of nitrate, ammonium, and aerosol liquid water content. The solubility of Fe was associated with sulfate and aerosol pH at most sites, suggesting the involvement of proton-mediated dissolution pathway, while this was not visible at the site influenced by industrial emission, most likely due to the abundance of pyrogenic Fe. The effect of metal-ligand complexation on the solubility of transition metals, in particular Fe, was clearly observed at all sites, whereas a combined effect with aerosol pH, and a subsequent impact on OP, was only seen at the traffic site in Toronto. The enhanced solubility of Fe due to proton- and ligand-mediated dissolution pathways and subsequent formation of reactive oxygen species may in part explain the health effects of PM 2.5 seen in previous epidemiological studies., (Crown Copyright © 2020. Published by Elsevier Ltd. All rights reserved.)

A pilot study was initiated in 2018 under the Global Atmospheric Passive Sampling (GAPS) Network named GAPS-Megacities. This study included 20 megacities/major cities across the globe with the goal of better understanding and comparing ambient air levels of persistent organic pollutants and other chemicals of emerging concern, to which humans residing in large cities are exposed. The first results from the initial period of sampling are reported for 19 cities for several classes of flame retardants (FRs) including organophosphate esters (OPEs), polybrominated diphenyl ethers (PBDEs), and halogenated flame retardants (HFRs) including new flame retardants (NFRs), tetrabromobisphenol A (TBBPA) and hexabromocyclododecane (HBCDD). The two cities, New York (USA) and London (UK) stood out with ∼3.5 to 30 times higher total FR concentrations as compared to other major cities, with total concentrations of OPEs of 15,100 and 14,100 pg/m 3 , respectively. Atmospheric concentrations of OPEs significantly dominated the FR profile at all sites, with total concentrations in air that were 2-5 orders of magnitude higher compared to other targeted chemical classes. A moderately strong and significant correlation (r = 0.625, p < 0.001) was observed for Gross Domestic Product index of the cities with total OPEs levels. Although large differences in FR levels were observed between some cities, when averaged across the five United Nations regions, the FR classes were more evenly distributed and varied by less than a factor of five. Results for Toronto, which is a 'reference city' for this study, agreed well with a more in-depth investigation of the level of FRs over different seasons and across eight sites representing different urban source sectors (e.g. traffic, industrial, residential and background). Future sampling periods under this project will investigate trace metals and other contaminant classes, linkages to toxicology, non-targeted analysis, and eventually temporal trends. The study provides a unique urban platform for evaluating global exposome., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 The Author(s). Published by Elsevier Ltd.. All rights reserved.)

Organophosphate esters (OPEs), novel flame retardants (NFRs) and organochlorine pesticides (OCPs) are volatile to semi-volatile chemicals and therefore susceptible to approach equilibrium during typical deployments of polyurethane foam (PUF) disk passive air samplers. A generator column approach was used to measure the PUF-air partitioning coefficient (K PUF-air ) for these targeted chemicals. K PUF-air values are required for these chemicals to estimate sampled equivalent air volumes, which vary substantially with temperature. Log K PUF-air measurements were made at temperatures ranging from +6 to +35 °C and resulting values ranged from 5.14 to 7.77. Enthalpies of phase change for PUF to air (ΔH PUF-air , kJ/mol) ranged from 51.3 to 98.9. Two relationships of log K PUF-air versus log K octanol-air (K OA ) were derived, grouping OPEs and NFRs separately. The relationship for NFRs was in fair agreement (within about 0.6 log units) to a long-standing relationship by Shoeib and Harner (since 2002) for polychlorinated biphenyls (PCBs). However, the estimated values using Shoeib-Harner relationship substantially underestimates K PUF-air for the OPEs than directly measured values (by about an order of magnitude). These findings highlight the importance of the direct measurements of K PUF-air for emerging classes of chemicals whose concentrations are at risk of equilibrating in PUF disk samplers., (Crown Copyright © 2019. Published by Elsevier Ltd. All rights reserved.)

Passive air sampling was conducted in Toronto and the Greater Toronto Area from 2016 to 2017 for 6 periods, in order to investigate ambient levels of polycyclic aromatic compounds (PACs) associated with different source types. The selected sampling sites (n = 8) cover geographical areas with varying source emissions including background, traffic, urban, industrial and residential sites. Passive air samples were analyzed for PACs which include PAHs, alkylated PAHs (alk-PAHs), dibenzothiophene and alkylated dibenzothiophenes (DBTs) and results for PAHs were used to calculate inhalation cancer risks using different approaches. The samples were also characterized for PAH derivatives including nitrated PAHs (NPAHs) and oxygenated PAHs (OPAHs). Concentrations of Σalk-PAHs and DBTs, which are known to be enriched in fossil fuels, as well as ΣNPAHs, were highest at a traffic site (MECP) located adjacent to the 18-lane Highway 401 that runs across Toronto. Except for an industrial site (HH/BU), PAC compositions were similar across the sampling sites with Σalk-PAHs being the most abundant class of PACs suggesting traffic emission was a major contributor to PACs in the atmosphere of Toronto. The industrial site exhibited a distinct chemical composition with ΣPAHs dominating over Σalk-PAHs and with elevated levels of fluoranthene, 9-nitroanthracene, and 9,10-anthraquinone, which likely reflects emissions from nearby industrial sources. MECP and HH/BU exhibited higher lifetime excess inhalation cancer risks indicating an association with traffic and industrial sources. The importance of the traffic sector as a source of PACs to ambient air is further supported by strong correlations of the ΣPAHs, Σalk-PAHs, DBTs, and ΣOPAHs with NO x . This study highlights the importance of traffic as an emission source of PACs to urban air and the relevance of PAC classes other than just unsubstituted PAHs that are important but currently not included in air quality guidelines or for assessing inhalation cancer risks., (Crown Copyright © 2019. Published by Elsevier Ltd. All rights reserved.)

Based on distinct land-use categories, a sampling campaign was carried out at eight locations across Toronto and the Greater Toronto Area in 2016-2017. Source sectors' dependent patterns of atmospheric concentrations of 9 organophosphate esters (OPEs), 9 polybrominated diphenyl ethers (PBDEs) and 5 novel flame retardants (NFRs) showed dominance of OPEs and PBDEs at highly commercialised urban and traffic sites, while NFRs, were dominant at residential sites. Overall, average concentrations of Σ 9 OPEs (1790 pg/m 3 ) were two orders of magnitude higher than Σ 9 PBDEs (9.17 pg/m 3 ) and Σ 5 NFRs (8.14 pg/m 3 ). The atmospheric concentrations of given chemical classes also showed a general trend of lower levels in winter as compared to summer months. Statistically significant negative correlations between the natural logarithm of concentrations and inverse of temperature for some OPEs and PBDEs highlighted the role of volatilization from local sources at given sites as primarily influencing their atmospheric concentrations. Overall, this study adds to the current knowledge of urban settings as a major emitter of the chemicals of emerging concern and their replacements, as well as the ongoing problem of phased out PBDEs due to their presence in existing inventories of commercial/recycled products. It is recommended that long-term monitoring programs targeting flame retardants (FRs) include urban sites, which provide an early indicator of effectiveness of control measures of targeted FRs, while at the same time providing information on emission sources and trends of replacement FR chemicals., (Crown Copyright © 2019. Published by Elsevier Ltd. All rights reserved.)

A special initiative in the Global Atmospheric Passive Sampling (GAPS) Network was implemented to provide information on new and emerging persistent organic pollutants (POPs) in the Group of Latin America and Caribbean (GRULAC) region. Regional-scale atmospheric concentrations of the new and emerging POPs hexachlorobutadiene (HCBD), pentachloroanisole (PCA) and dicofol indicators (breakdown products) are reported for the first time. HCBD was detected in similar concentrations at all location types (<20-120 pg/m 3 ). PCA had elevated concentrations at the urban site Concepción (Chile) of 49-222 pg/m 3 , with concentrations ranging <1-8.5 pg/m 3 at the other sites in this study. Dicofol indicators were detected at the agricultural site of Sonora (Mexico) at concentrations ranging 30-117 pg/m 3 . Legacy POPs, including a range of organochlorine (OC) pesticides and polychlorinated biphenyls (PCBs), were also monitored to compare regional atmospheric concentrations over a decade of monitoring under the GAPS Network. γ-hexachlorocyclohexane (HCH) and the endosulfans significantly decreased (p < 0.05) from 2005 to 2015, suggesting regional levels are decreasing. However, there were no significant changes for the other legacy POPs monitored, likely a reflection of the persistency and slow decline of environmental levels of these POPs. For the more volatile OCs, atmospheric concentrations derived from polyurethane foam (PUF) (acting as an equilibrium sampler) and sorbent impregnated PUF (SIP) (acting as a linear phase sampler), were compared. The complimentary methods show a good agreement of within a factor of 2-3, and areas for future studies to improve this agreement are further discussed., (Crown Copyright © 2018. Published by Elsevier Ltd. All rights reserved.)

Poly- and per-fluoroalkyl substances (PFAS) and volatile methyl siloxanes (VMS) were monitored at 21 sites in the Global Atmospheric Passive Sampling (GAPS) Network. Atmospheric concentrations previously reported from 2009 were compared to concentrations measured at these sites in 2013 and 2015, to assess trends over 7 years of monitoring. Concentrations of the fluorotelomer alcohols (FTOHs) and fluorinated sulfonamides and sulfonamidoethanols (FOSAs and FOSEs) were stable at these sites from 2009 to 2015 with no significant difference (p > 0.05) in concentrations. Elevated concentrations of all the neutral PFAS were detected at the urban sites as compared to the polar/background sites. The perfluorosulfonic acids (PFSAs), meanwhile, saw a significant increase (p < 0.001) in concentrations from 2009 to 2015. The perfluorocarboxylic acids (PFCAs) had elevated concentrations in 2015, however, the difference was not statistically significant (p > 0.05). Concentrations of the PFSAs and the PFCAs were similar at all location types, showing the global reach of these persistent compounds. Concentrations of the cyclic VMS (cVMS) were at least an order of magnitude higher than the linear VMS (lVMS) and the PFAS. Octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5) and dodecamethylcyclohexasiloxane (D6) saw a weak significant increase in concentrations from 2009 to 2013 (p < 0.05), however, hexamethylcyclotrisiloxane (D3) had a strong significant decrease in concentrations from 2009 to 2015 (p < 0.01)., (Copyright © 2018 The Authors. Published by Elsevier Ltd.. All rights reserved.)

Passive air samplers equipped with polyurethane foam (PUF-PAS) are frequently used to measure persistent organic pollutants (POPs) in ambient air. Here we present and evaluate a method to determine sampling rates (R S ), and the effective sampling volume (V eff ), for gas-phase chemical compounds captured by a PUF-PAS sampler deployed anywhere in the world. The method uses a mathematical model that requires only publicly available hourly meteorological data, physical-chemical properties of the target compound, and the deployment dates. The predicted R S is calibrated from sampling rates determined from 5 depuration compounds ( 13 C PCB-9, 13 C PCB-15, 13 C PCB-32, PCB-30, and d 6 -γ-HCH) injected in 82 samples from 24 sites deployed by the Global Atmospheric Passive Sampling (GAPS) network around the world. The dimensionless fitting parameter, gamma, was found to be constant at 0.267 when implementing the Integrated Surface Database (ISD) weather observations and 0.315 using the Modern Era Retrospective-Analysis for Research and Applications (MERRA) weather dataset. The model provided acceptable agreement between modelled and depuration determined sampling rates, with 13 C PCB-9, 13 C PCB-32, and d 6 -γ-HCH having mean percent bias near zero (±6%) for both weather datasets (ISD and MERRA). The model provides inexpensive and reliable PUF-PAS gas-phase R S and V eff when depuration compounds produce unusual or suspect results and for sites where the use of depuration compounds is impractical, such as sites experiencing low average wind speeds, very cold temperatures, or remote locations.

Passive air samplers were used to evaluate long-term trends and spatial distribution of trace organic compounds in Antarctica. Duplicate PUF disk samplers were deployed at six automatic weather stations in the coastal area of the Ross sea (East Antarctica), between December 2010 and January 2011, during the XXVI Italian Scientific Research Expedition. Among the investigated persistent organic compounds, Hexachlorobenzene was the most abundant, with air concentrations ranging from 0.8 to 50 pg m -3 . In general, the following decreasing concentration order was found for the air samples analyzed: HCB > PeCB > PCBs > DDTs > HCHs. While HCB concentrations were in the same range as those reported in the atmosphere of other Antarctic sampling areas and did not show a decline, HCHs and DDTs levels were lower or similar to those determined one or two decades ago. In general, the very low concentrations reflected the pristine state of the East Antarctica air. Backward trajectories indicated the prevalence of air masses coming from the Antarctic continent. Local contamination and volatilization from ice were suggested as potential sources for the presence of persistent organic pollutants in the atmosphere., (Copyright © 2017 Elsevier Ltd. All rights reserved.)

Polyurethane foam - air partition coefficients (K PUF-air ) for 9 polycyclic aromatic hydrocarbons (PAHs), 10 alkyl-substituted PAHs, 4 organochlorine pesticides (OCPs) and dibenzothiophene were measured as a function of temperature over the range 5 °C-35 °C, using a generator column approach. Enthalpies of PUF-to-air transfer (ΔH PUF-air , kJ/mol) were determined from the slopes of log K PUF-air versus 1000/T (K), and have an average value of 81.2 ± 7.03 kJ/mol. The log K PUF-air values at 22 °C ranged from 4.99 to 7.25. A relationship for log K PUF-air versus log K OA was shown to agree with a previous relationship based on only polychlorinated biphenyls (PCBs) and derived from long-term indoor uptake study experiments. The results also confirm that the existing K OA -based model for predicting log K PUF-air values is accurate. This new information is important in the derivation of uptake profiles and effective air sampling volumes for PUF disk samplers so that results can be reported in units of concentration in air., (Crown Copyright © 2017. Published by Elsevier Ltd. All rights reserved.)

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/m 3 for the HV-AAS. Sampling rates and the passive sampler medium (PSM)-air partition coefficient (K PSM-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 m 3 /day for the PUF and SIP disks, respectively, and within the range of the recommended default value of 4 ± 2 m 3 /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 K PUF-Air for the OPEs. The estimated values of log K PUF-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)., (Crown Copyright © 2016. Published by Elsevier Ltd. All rights reserved.)

Much effort has been made to standardise sampling procedures, laboratory analysis, data analysis, etc. for semi volatile organic contaminants (SVOCs). Yet there are some unresolved issues in regards to comparing measurements from one of the most commonly used passive samplers (PAS), the polyurethane foam (PUF) disk PAS (PUF-PAS), between monitoring networks or different studies. One such issue is that there is no universal means to derive a sampling rate (R s ) or to calculate air concentrations (C air ) from PUF-PAS measurements for SVOCs. C air was calculated from PUF-PAS measurements from a long-term monitoring program at a site in central Europe applying current understanding of passive sampling theory coupled with a consideration for the sampling of particle associated compounds. C air were assessed against concurrent active air sampler (AAS) measurements. Use of "site-based/sampler-specific" variables: R s , calculated using a site calibration, provided similar results for most gas-phase SVOCs to air concentrations derived using "default" values (commonly accepted R s ). Individual monthly PUF-PAS-derived air concentrations for the majority of the target compounds were significantly different (Wilcoxon signed-rank (WSR) test; p < 0.05) to AAS regardless of the input values (site/sampler based or default) used to calculate them. However, annual average PUF-PAS-derived air concentrations were within the same order of magnitude as AAS measurements except for the particle-phase polycyclic aromatic hydrocarbons (PAHs). Underestimation of PUF-derived air concentrations for particle-phase PAHs was attributed to a potential overestimation of the particle infiltration into the PUF-PAS chamber and underestimation of the particle bound fraction of PAHs., (Crown Copyright © 2016. Published by Elsevier Ltd. All rights reserved.)

A discussion is presented on the limitations for air monitoring studies around the Group of Latin American and Caribbean Countries (GRULAC), highlighting key issues requiring further attention, and reports on how a special initiative is addressing these limitations. Preliminary results are presented for the first reported data on organophosphorus flame retardant (OPFR) concentrations in outdoor air from the GRULAC region. At the majority of sites the concentrations and the profile of the OPFRs detected were similar with tris (chloroisopropyl) phosphate (TCPP) dominating (3 ). However, the urban location at Concepción, Chile presented higher concentrations and a different profile with tris (2-butoxyethyl) phosphate (TBEP) dominating (mean 800pg/m 3 vs 80pg/m 3 at the other locations) -indicating different sources at this location. OPFRs, used extensively as flame retardants and plasticizers, are found ubiquitously in indoor environments yet only few studies report outdoor air levels. This preliminary study of only 7 sites highlights how extensive regional passive sampling networks (such as GAPS) can provide important new information to support risk assessment of these and similar chemicals. Finally, the various challenges with implementing a regional monitoring program are discussed, including harmonizing data from various monitoring programs for reporting to the GMP., (Copyright © 2016 Elsevier B.V. All rights reserved.)

The occurrence of persistent organic pollutants (POPs) in the atmosphere of the near-coast South Atlantic Ocean was studied. Air samples were collected using a high-volume air sampler (filter and polyurethane foam) on board the Argentinean research cruise R/V Puerto Deseado (CONICET). Samples were analyzed for 50 polychlorinated biphenyl (PCBs), 22 organochlorine pesticides (OCPs) and 14 polybrominated diphenyl ethers (PBDEs). These POPs classes showed a trend of decreasing levels from near-shore to open ocean sites. OCPs and PCBs were in the same order of magnitude (2.71-87.1pg/m(3) and 9.56-130pg/m(3), respectively) while PBDEs levels were significantly lower (0.69-2.58pg/m(3)). Dichlorodiphenyltrichloroethanes (DDTs), endosulfans, chlordanes, hexachlorocyclohexanes (HCHs) and heptachlors were between 0.20 and 17.8pg/m(3), while drines and hexachlorobenzene (HCB) were at lower levels (0.28-3.71pg/m(3)). The most frequently detected PCBs were congeners 32, 28, 44, 52, 95, representing >50% of the total. The PBDEs congener pattern was dominated by congener 209 (70%), followed by 47 and 99 (16% and 7%, respectively). Air parcel back trajectories for the study period provided few insights as trajectories mainly stemmed from the open ocean with limited inputs from continental sources. These results indicate that the concentration of POPs (namely PCBs, OCPs, and PBDEs) in air remain elevated in the near-shore environment and then drop-off substantially beyond a distance of about 400km. This has implications for the loading of POPs and delivery to the marine environment in the near coastal zone., (Copyright © 2016 Elsevier B.V. All rights reserved.)

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)., (Copyright © 2016. Published by Elsevier Ltd.)

A retrospective analysis was conducted on air samples that were collected in 2005 under the Global Atmospheric Passive Sampling (GAPS) Network around the time period when the Stockholm Convention on Persistent Organic Pollutants came into force. Results are presented for several new flame retardants, including hexabromocyclododecane (HBCD), which was recently listed under the Convention (2013). These results represent the first global-scale distributions in air for these compounds. The targeted compounds are shown to have unique global distributions in air, which highlights the challenges in understanding the sources and environmental fate of each chemical, and ultimately in their assessments as persistent organic pollutants. The study also demonstrates the feasibility of using the PUF disk passive air sampler to study these new flame retardants in air, many of which exist entirely in the particle-phase as demonstrated in this study using a KOA-based partitioning model., (Crown Copyright © 2016. Published by Elsevier Ltd. All rights reserved.)

Isomers of alkyl-substituted polycyclic aromatic hydrocarbons (PAHs) and dibenzothiophenes are modelled with COSMO-RS theory to determine the effectiveness and accuracy of this approach for estimation of isomer-specific partition coefficients between air and polyurethane foam (PUF), i.e., KPUF-AIR. Isomer-specific equilibrium partitioning coefficients for a series of 23 unsubstituted and isomeric alkyl-substituted PAHs and dibenzothiophenes were measured at 22 °C. This data was used to determine the accuracy of estimated values using COSMO-RS, which is isomer specific, and the Global Atmospheric Passive Sampling (GAPS) template approach, which treats all alkyl-substitutions as a single species of a given side-chain carbon number. A recently developed oligomer-based model for PUF was employed, which consisted of a 1:1 condensed pair of 2,4-toluene-diisocyanide and glycerol. The COSMO-RS approach resulted in a significant reduction in the RMS error associated with simple PAHs and dibenzothiophene compared with the GAPS template approach. When used with alkylated PAHs and dibenzothiophenes grouped into carbon-number categories, the GAPS template approach gave lower RMS error (0.72) compared to the COSMO-RS result (0.87) when the latter estimates were averaged within the carbon-number-based categories. When the isomer-specific experimental results were used, the COSMO-RS approach resulted in a 21% reduction in RMS error with respect to the GAPS template approach, with a 0.57 RMS error for all alkylated PAHs and dibenzothiophenes studied. The results demonstrate that COSMO-RS theory is effective in generating isomer-specific PUF-air partition coefficients, supporting the application of PUF-based passive samplers for monitoring and research studies of polycyclic aromatic compounds (PACs) in air., (Copyright © 2015 Elsevier Ltd. All rights reserved.)

PFASs concentrations in dust samples collected from three microenvironments in Cairo ranged from 1.3 to 69 ng g(-1) with FTOHs being dominant. The 8:2 FTOH was detected in all samples. Among the FOSAs and FOSEs the MeFOSE was dominant while among ionic PFASs, PFOS and PFOA were most prominent. The concentrations of PFASs were among the lowest worldwide. Correlations between worldwide concentrations of PFOS + PFOA and country development indexes highlight higher usage and human exposure in more developed countries. Food packaging was analyzed for PFSAs, PFCAs and PAPs. The 6:2 and 8:2 monoPAPs were found to be above the MDL in 18% of the samples. PFOA was detected in 79% of the samples with median concentration of 2.40 ng g(-1). PFOS was detected in 58% of the samples with median concentration of 0.29 ng g(-1) while PFHxS and PFDS were below detection limit. Different human exposure scenarios were estimated., (Copyright © 2015 Elsevier Ltd. All rights reserved.)

This study addresses human health concerns in the city of Temuco that are attributed to wood smoke and related pollutants associated with wood burning activities that are prevalent in Temuco. Polycyclic Aromatic Hydrocarbons (PAHs) were measured in air across urban and rural sites over three seasons in Temuco using polyurethane foam (PUF) disk passive air samplers (PUF-PAS). Concentrations of ΣPAHs (15 congeners) in air ranged from BDL to ∼70 ng m(-3) and were highest during the winter season, which is attributed to emissions from residential heating by wood combustion. The results for all three seasons showed that the PAH plume was widespread across all sites including rural sites on the outskirts of Temuco. Some interesting variations were observed between seasons in the composition of PAHs, which were attributed to differences in seasonal point sources. A comparison of the PAH composition in the passive samples with active samples (gas+particle phase) from the same site revealed similar congener profiles. Overall, the study demonstrated that the PUF disk passive air sampler provides a simple approach for measuring PAHs in air and for tracking effectiveness of pollution control measures in urban areas in order to improve public health., (Copyright © 2015 Elsevier Ltd. All rights reserved.)

Polycyclic aromatic hydrocarbon (PAH) measurements were conducted by Wood Buffalo Environmental Association (WBEA) at four community ambient Air quality Monitoring Stations (AMS) in the Athabasca Oil Sands Region (AOSR) in Northeastern Alberta, Canada. The 2012 and 2013 mean concentrations of a subset of the 22 PAH species were 9.5, 8.4, 8.8, and 32 ng m(-3) at AMS 1 (Fort McKay), AMS 6 (residential Fort McMurray), AMS 7 (downtown Fort McMurray), and AMS 14 (Anzac), respectively. The average PAH concentrations in Fort McKay and Fort McMurray were in the range of rural and semirural areas, but peak values reflect an industrial emission influence. At these stations, PAHs were generally associated with NO, NO2, PM2.5, and SO2, indicating the emissions were from the combustion sources such as industrial stacks, vehicles, residential heating, and forest fires, whereas the PAH concentrations at AMS 14 (∼35 km south of Fort McMurray) were more characteristic of urban areas with a unique pattern: eight of the lower molecular weight PAHs exhibited strong seasonality with higher levels during the warmer months. Enthalpies calculated from Clausius-Clapeyron plots for these eight PAHs suggest that atmospheric emissions were dominated by temperature-dependent processes such as volatilization at warm temperatures. These findings point to the potential importance of localized water-air and/or surface-air transfer on observed PAH concentrations in air.

A passive air sampling network has been established to investigate polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) at Global Atmospheric Passive Sampling (GAPS) sites and six additional sites in the Group of Latin American and Caribbean Countries (GRULAC) region. The air sampling network covers background, agricultural, rural, and urban sites. Samples have been collected over four consecutive periods of 6 months, which started in January 2011 [period 1 (January to June 2011), period 2 (July to December 2011), period 3 (January to June 2012), and period 4 (July 2012 to January 2013)]. Results show that (i) the GAPS passive samplers (PUF disk type) and analytical methodology are adequate for measuring PCDD/F burdens in air and (ii) PCDD/F concentrations in air across the GRULAC region are widely variable by almost 2 orders of magnitude. The highest concentrations in air of Σ4-8PCDD/Fs were found at the urban site São Luis (Brazil, UR) (i.e., 2560 fg/m3) followed by the sites in São Paulo (Brazil, UR), Mendoza (Argentina, RU), and Sonora (Mexico, AG) with values of 1690, 1660, and 1610 fg/m3, respectively. Very low concentrations of PCDD/Fs in air were observed at the background site Tapanti (Costa Rica, BA), 10.8 fg/m3. This variability is attributed to differences in site characteristics and potential local/regional sources as well as meteorological influences. The measurements of PCDD/Fs in air agree well with model-predicted concentrations performed using the Global EMEP Multimedia Modeling System (GLEMOS) and emission scenario constructed on the basis of the UNEP Stockholm Convention inventory of dioxin and furan emissions.

Results are reported from an ongoing passive air monitoring study for polycyclic aromatic compounds (PACs) in the Athabasca oil sands region in Alberta, Canada. Polyurethane foam (PUF) disk passive air samplers were deployed for consecutive 2-month periods from November 2010 to June 2012 at 17 sites. Samples were analyzed for polycyclic aromatic hydrocarbons (PAHs), alkylated PAHs, dibenzothiophene and its alkylated derivatives (DBTs). Relative to parent PAHs, alkylated PAHs and DBTs are enriched in bitumen and therefore considered to be petrogenic markers. Concentrations in air were in the range 0.03-210 ng/m(3), 0.15-230 ng/m(3) and 0.01-61 ng/m(3) for ∑PAHs, ∑alkylated PAHs and ΣDBTs, respectively. An exponential decline of the PAC concentrations in air with distance from mining areas and related petrogenic sources was observed. The most significant exponential declines were for the alkylated PAHs and DBTs and attributed to their association with mining-related emissions and near-source deposition, due to their lower volatility and greater association with depositing particles. Seasonal trends in concentrations in air for PACs were not observed for any of the compound classes. However, a forest fire episode during April to July 2011 resulted in greatly elevated PAH levels at all passive sampling locations. Alkylated PAHs and DBTs were not elevated during the forest fire period, supporting their association with petrogenic sources. Based on the results of this study, an "Athabasca PAC profile" is proposed as a potential source marker for the oil sands region. The profile is characterized by ∑PAHs/∑Alkylated PAHs = ∼0.2 and ∑PAHs/∑DBTs = ∼5.

Changes in environmental and wildlife health from contaminants in tailings water on the Canadian oil sands have been well-studied; however, effects of air contaminants on wildlife health have not. A field study was conducted to assess biological costs of natural exposure to oil sands-related air emissions on birds. Nest boxes for tree swallows (Tachycineta bicolor) were erected at two sites; within 5 km of active oil sands mining and extraction, and ≥ 60 km south, at one reference site. Passive air monitors were deployed at the nest boxes to measure nitrogen dioxide, sulfur dioxide, ozone, volatile organic compounds, and polycyclic aromatic hydrocarbons (PAHs). Nestlings were examined at day 9 post hatching to assess T cell function and morphometry. At day 14 post hatching, a subset of nestlings was euthanized to measure detoxification enzymes, endocrine changes, and histological alterations of immune organs. Except for ozone, all air contaminants were higher at the two oil sands sites than the reference site (up to 5-fold). Adult birds had similar reproductive performance among sites (p>0.05). Nestlings from industrial sites showed higher hepatic ethoxyresorufin O-dealkylase (EROD) induction (p<0.0001) with lower relative hepatic mass (p=0.0001), a smaller T cell response to the phytohemagglutinin skin test (p=0.007), and smaller bursae of Fabricius (p<0.02); a low sample size for one site indicating lower body condition scores (p=0.01) at day 14 warrants cautious interpretation. There were no differences among nestlings for feather corticosterone (p>0.6), and no histological alterations in the spleen or bursa of Fabricius (p>0.05). This is the first report examining toxicological responses in wild birds exposed to air contaminants from industrial activity in the oil sands. It is also the first time that small, individual air contaminant monitors have been used to determine local contaminant levels in ambient air around nest boxes of wild birds., (Copyright © 2014 Elsevier B.V. All rights reserved.)

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 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.

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.

In 1974, Junge postulated a relationship between variability of concentrations of gases in air at remote locations and their atmospheric residence time, and this Junge relationship has subsequently been observed empirically for a range of trace gases. Here, we analyze two previously-published datasets of concentrations of cyclic volatile methyl siloxanes (cVMS) in air and find Junge relationships in both. The first dataset is a time series of concentrations of decamethylcyclopentasiloxane (D5) measured between January and June, 2009 at a rural site in southern Sweden that shows a Junge relationship in the temporal variability of the measurements. The second dataset consists of measurements of hexamethylcyclotrisiloxane (D3), octamethylcyclotetrasiloxane (D4) and D5 made simultaneously at 12 sites in the Global Atmospheric Passive Sampling (GAPS) network that shows a Junge relationship in the spatial variability of the three cVMS congeners. We use the Junge relationship for the GAPS dataset to estimate atmospheric lifetimes of dodecamethylcyclohexasiloxane (D6), 8:2-fluorotelomer alcohol and trichlorinated biphenyls that are within a factor of 3 of estimates based on degradation rate constants for reaction with hydroxyl radical determined in laboratory studies., (Copyright © 2012 Elsevier Ltd. All rights reserved.)

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., (Copyright © 2013 Elsevier Ltd. All rights reserved.)

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.

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.

Two field studies were conducted for one year using sorbent-impregnated polyurethane foam (SIP) disks for PCB and PBDE air sampling. SIP disks were introduced by Shoeib et al. (2008) as an alternative passive air sampling medium to the polyurethane foam (PUF) disk and have the advantage of a higher holding capacity for organic chemicals. The first study on SIP disks confirmed their application for measuring volatile perfluorinated compounds (PFCs) and their ability to maintain time-integrated (linear) air sampling. In this study, the suitability of the SIP disks for long-term sampling of polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers (PBDEs) and hexachlorobenzene (HCB) was assessed. SIP disks were deployed at a rural site in the UK and harvested after periods ranging from 35-350 days. Atmospheric POP concentrations were monitored with a high-volume air sampler during the deployment period. Linear uptake was observed for all monitored PCBs and PBDEs over the full exposure time. Air-sampler equilibrium was observed for HCB after 6 months. In a second field study, SIP disks were deployed for one year at 10 sites on a latitudinal transect in the UK and Norway, at which air sampling has been undertaken previously with different passive air sampling media since 1994. The estimated concentrations and spatial distributions derived from the SIP disks were largely in agreement with previously reported data.

Volatile methyl siloxanes (VMSs) are a class of chemicals with an increasing range of applications and widespread distribution in the environment. Passive air samplers (PAS) comprising sorbent-impregnated polyurethane-foam (SIP) disks were first calibrated and then deployed around two wastewater treatment plants (WWTPs) and at two landfill sites to investigate inputs of VMSs to air. SIP-derived air concentrations for ΣVMSs (ng/m(3)) at background sites on the perimeter of the WWTP were 479 ± 82.3 and comparable to results for the upwind samples at the landfills (333 ± 194). Order of magnitude higher concentrations of ΣVMSs (ng/m(3)) were found for on-site samples at the WWTPs (3980 ± 2620) and landfills (4670 ± 3360). Yearly emissions (kg/yr) to air were estimated and ranged from 60-2100 and 80-250, respectively, for the cyclic VMSs. These findings demonstrate and quantify for the first time, waste sector emissions of VMSs to the atmosphere., (Crown Copyright © 2011. Published by Elsevier Ltd. All rights reserved.)

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.

The first survey of persistent organic pollutant (POP) concentrations in air across several Indian agricultural regions was conducted in 2006-2007. Passive samplers comprising polyurethane foam (PUF) disks were deployed on a quarterly basis at seven stations in agricultural regions, one urban site and one background site. The project was conducted as a sub-project of the Global Atmospheric Passive Sampling (GAPS) Network. In addition to revealing new information on air concentrations of several organochlorine pesticides (OCPs) and polychlorinated biphenyls (PCBs), the study has demonstrated the feasibility of conducting regional-scale monitoring for POPs in India using PUF disk samplers. The following analytes were detected with relatively high concentrations in air (mean for 2006 and 2007, pg/m(3)): α- and γ-hexachlorocyclohexane (HCH) (292 and 812, respectively); endosulfan I and II (2770 and 902, respectively); p,p'-DDE and p,p'-DDT (247 and 931, respectively); and for the sum of 48 PCBs, 12,100 (including a site with extremely high air concentrations in 2007) and 972 (when excluding data for this site)., (Crown Copyright © 2010. Published by Elsevier Ltd. All rights reserved.)

As part of the Global Atmospheric Passive Sampling (GAPS) study, XAD-resin based passive samplers are being deployed for consecutive one-year periods at numerous sites on all seven continents to determine annually averaged concentrations of persistent organic pollutants. Concentrations of banned organochlorine pesticides as well as a number of current-use pesticides in samples from the first four years, roughly coinciding with 2005, 2006, 2007 and 2008, show distinct spatial and temporal patterns. Whereas organochlorine pesticides such as alpha- and gamma-hexachlorocyclohexane, endosulfans, DDT and its metabolites, and chlordane-related compounds tend to be more prevalent in developing countries, especially in Asia, concentrations of current use pesticides such as trifluralin and chlorothalonil are often higher in Europe and North America. Based on 15 stations with four years of data, levels of hexachlorobenzene, hexachlorocyclohexanes and chlordanes decline in most world regions, which may reflect decreased usage in response to global restrictions. Levels of organochlorine pesticides in India, however, remain exceptionally high. Concentrations of alpha-endosulfan, chlorothalonil and trifluralin decrease in the European atmosphere during the sampling periods, indicating reduced usage. Consistently high alpha/gamma-HCH ratios in air samples from high Northern latitudes confirm that re-volatilization from the Arctic Ocean is a significant source of alpha-HCH. The highest levels of alpha-HCH, however, occur in conjunction with high gamma-HCH levels, suggesting that lindane use is now the major source of alpha-HCH to the global atmosphere. Although a wide variety of sampling site types aids in characterizing the entire global concentration variability of a pesticide, it also increases greatly the number of sites required for a robust regional differentiation.

Sorbent-impregnated polyurethane foam (SIP) disk passive air samplers were deployed alongside polyurethane foam (PUF) disk samplers at 20 sites during the 2009 spring sampling period of the Global Atmospheric Passive Sampling (GAPS) Network. The SIP disk samplers consisted of PUF disks impregnated with finely ground XAD-4 resin. The addition of XAD-4 greatly improves the sorptive capacity of the PUF disk samplers for more volatile and polar chemicals, and allows for linear-phase sampling over several weeks for these compounds. The SIP and PUF disks were analyzed for polychlorinated biphenyls (PCBs), neutral polyfluoroalkyl compounds (PFCs), and ionic PFCs. Correlations between sampler-derived air concentrations for PCBs in the PUF and SIP disks samplers were significant (p < 0.05). The SIP disks effectively captured 4-50% more of the low molecular weight PCBs than the PUF disks samplers, and the PUF disks also had limitations for time-weighted passive sampling of neutral PFCs in air. Theoretical uptake curves for PUF disks showed rapid equilibration occurring in just hours for 8:2 FTOH and in a few days for MeFOSE, while theoretical curves for SIP disks showed superior sampling profiles for the neutral PFCs. PFCs were measured on SIP disks at all sites with 8:2 FTOH being the dominant compound detected and urban centers (n = 3) having the highest total neutral PFC concentrations ranging from 51.7 to 248 pg/m(3). A positive correlation was found between the FTOHs and FOSAs/FOSEs (p < 0.001, Pearson correlation) indicating similar contamination sources. The SIP disk appears to be a promising passive air sampler for measuring both emerging and legacy POPs on a global scale. They can also be used as a complement to the PUF disk sampler for capturing broader classes of compounds, or as a replacement for PUF disks entirely, especially when longer than quarterly deployment periods are desired.

Polychlorinated biphenyl (PCB) concentrations in air and soil, measured by various research groups from around the world, were compiled and analyzed. Data for air were available from most regions, particularly in Europe and Asia. The average air concentrations (pg/m(3)) for SigmaPCB at background sites were 70 (5.1-170) for Europe, 79 (49-120) for North America, 66 (18-110) for South America, 270 (9-670) for Central America, 59 (17-150) for Asia, and 15 (13-17) for Australia. Data for soils exhibited better global coverage compared to air and were available from most regions. The average soil concentrations (pg/g dry weight) for SigmaPCB at background sites were 7500 (47-97 000) for Europe, 4300 (110-25 000) for North America, 1400 (61-9 500) for South America, 580 (120-2 900) for Asia, 390 (94-620) for Africa, and 280 (140-540) for Australia. Based on available studies where coupled measurements of PCBs in air and soil were made, the equilibrium status of PCBs in the air-soil system was investigated for China, West Midlands of the UK, central and southern Europe, and along a latitudinal transect from the south of the UK to the north of Norway. Differences were observed in plots of the soil-air equilibrium status (expressed as the soil-air fugacity fraction, ff) for different PCB homologues. This was explained by varying contributions from primary and secondary emissions-spatially and temporally. The net effect after several decades of PCB emissions to air, preferential transport of lower molecular weight PCBs through primary and secondary emission, and reductions in emissions to air in recent decades is that the lower molecular weight PCBs have achieved (and in some cases exceeded) soil-air equilibrium in many parts of the world. The exception is remote and background sites that are still dominated by primary sources.

A field study was performed to derive uptake rates of airborne polybrominated diphenyl ethers (PBDEs) to polyurethane foam (PUF) disk passive air samplers (PAS) and to investigate the influence of deployment location and device design. Data are presented on the gas-particle partitioning of PBDEs, since atmospheric phase distribution was considered to be a variable which could affect sampler performance. Uptake rates for these compounds were similar to those derived previously for other classes of persistent organic pollutants (POPs) (approximately 2-6 m(3)/day), with rates higher for the higher brominated species. Whilst other compound classes (e.g. polychlorinated biphenyls) are predominantly present in the air in the gas phase, heavier PBDEs have an association with particulates in the atmosphere at ambient temperatures. In this study, the PUF disk PAS therefore sampled PBDEs present in the gas phase and on fine aerosols with a similar sampling efficiency to those which are predominantly gas phase compounds. Compounds which are exclusively on particles are sampled less efficiently. A comparison of the three most commonly used PUF deployment configurations, used by different research groups, indicated little difference in uptake rates. The ranges of derived air concentrations for BDE-47, -99, and -183 between three sampler designs were 7.5-9.8, 7.4-12.4, and 4.7-6.6 pg/m(3), respectively. This suggests the robustness of this sampler in comparisons between regional and global campaigns where these three designs are employed.

Depuration compounds (DCs) are added to passive air samplers (PAS) prior to deployment to account for the wind-dependency of the sampling rate for gas-phase compounds. This correction is particularly useful for providing comparable data for samplers that are deployed in different environments and subject to different meteorological conditions such as wind speeds. Two types of PAS--the polyurethane foam (PUF) disk sampler and semipermeable membrane devices (SPMDs)--were deployed at eight heights on a 100 m tower to test whether the DC approach could yield air concentrations profiles for PCBs and organochlorine pesticides and account for the wind speed gradient with height. Average wind speeds ranged from 0.3 to 4.5 m s(-1) over the 40 day deployment, increasing with height Two low volume active air samples (AAS), one collected at 25 m and one at 73 m over the 40 day deployment showed no significant concentration differences for target compounds. As expected, the target compounds taken up by PAS reflected the wind profile with height This wind-dependency of the PAS was also reflected in the results of the DCs. A correction based on the DC approach successfully accounted for the effect of wind on PAS sampling rates, yielding a profile consistent with the AAS. Interestingly, in terms of absolute air concentrations, there were differences between the AAS and PAS-derived values for some target compounds. These were attributed to different sampling characteristics of the two approaches that may have resulted in slightly different air masses being sampled. Based on the results of this study, guidelines are presented for the use of DCs and for the calibration of PAS using AAS.