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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/m3, 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/m2/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.

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Biomass burning (BB) is an important source of atmospheric persistent organic pollutants (POPs) across the world. However, there are few field-based regional studies regarding the POPs released from BB. Due to the current limitations of emission factors and satellites, the contribution of BB to airborne POPs is still not well understood. In this study, with the simultaneous monitoring of BB biomarkers and POPs based on polyurethane foam-based passive air sampling technique, we mapped the contribution of BB to polychlorinated biphenyls (PCBs) and organochlorine pesticides (OCPs) in the Indo-China Peninsula. Spearman correlations between levoglucosan and 16 PCBs (rs = 0.264-0.767, p < 0.05) and 2 OCPs (rs = 0.250-0.328, p < 0.05) confirmed that BB may facilitate POP emissions. Source apportionment indicated that BB contributed 9.3% to the total PCB and OCP mass. The high contribution of positive matrix factorization-resolved BB to PCBs and OCPs was almost consistent with their concentration distributions in the open BB season but not completely consistent with those in the pre-monsoon and/or monsoon seasons. Their contribution distributions may reflect the use history and geographic distribution in secondary sources of POPs. The field-based contribution dataset of BB to POPs is significant in improving regional BB emission inventories and model prediction.

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Short and medium chain chlorinated paraffins (SCCPs and MCCPs) attract increasing attentions due to their persistence, long-range transport capacity. Their gas/particle partitioning from the production emission source, the effects to the ambient environment and exposure for employees are worth revealing. Polyurethane foam based passive air samplers (PUF-PAS) was deployed to determine the environmental levels of SCCPs (63.4-719.7 ng/m3) and MCCPs (151.6-1009.2 ng/m3) in the gas-phase and particle-phase both in the outdoor air in a CP production plant and the indoor air in the workshops. Extremely high SCCPs were found in the chlorination workshop and outdoor samples nearby, attributing to the release during the production. In the workshops, dramatically higher SCCP concentrations were determined than outdoors. SCCPs and MCCPs predominated in the gas-phase with a proportion >80 %. C10-CPs and C14-CPs were dominated with a proportion higher than 20 % and 50 %, respectively. Significant correlations between log Kp' and log PL0 and log KOA were observed in the outdoor air in a CP production plant and the indoor air in the workshops, respectively. A multivariate mechanism based on adsorption by organic matters and influenced by absorption processes might determine the gas/particle partitioning of CPs in the production source area. Two scenarios of occupational exposure i.e. working in the workshops and working outdoors were considered. Higher occupational exposure via inhalation to MCCPs was found for employees than SCCPs in the workshops, which was estimated to be 137.1 ng/kg/day at a worst case. No obvious adverse effects were observed for occupational employees in this CP production plant.

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Field-based sampling can provide more accurate evaluation than MODIS in regional biomass burning (BB) emissions given the limitations of MODIS on unresolved fires. Polyurethane foam-based passive air samplers (PUF-PASs) are a promising tool for collecting atmospheric monosaccharides. Here, we deployed PUF-PASs to monitor monosaccharides and other BB-related biomarkers and presented a dataset of 31 atmospheric BB-related biomarkers in the Indo-China Peninsula (ICP) and Southwest China. The peak concentrations of monosaccharides in the ICP occurred before monsoon season. The highest concentrations were in the eastern Mekong plain, while the lowest were along the eastern coast. BB-related biomarkers displayed elevated concentrations after April, particularly in the monsoon season; however, fewer active fires were recorded by MODIS. This revealed the importance of MODIS unresolved fires (e.g., indoor biofuel combustion, small-scale BB incidents, and charcoal fires) to the regional atmosphere. The PAS derived levoglucosan concentrations indicated that, with the inclusion of MODIS unresolved fires, the estimated top-down emissions of PM (4194-4974 Gg/yr), OC (1234-1719 Gg/yr) and EC (52-384 Gg/yr) would be higher than previous bottom-up estimations in the ICP. Future studies on these MODIS unresolved fires and regional monitoring data of BB are vital for improving the modeling of regional BB emissions.

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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.

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Some derivatives of polycyclic aromatic hydrocarbons (PAHs) such as chlorinated and brominated PAHs (Cl/BrPAHs), nitrated and oxygenated PAHs (N/OPAHs) have attracted significant concern due to their high toxicity. Knowledge of the profiles, formation mechanisms, and potential sources of these toxic chemicals near the industrial complexes is essential for their pollution control and management. In this study, we monitored Cl/BrPAHs, N/OPAHs, and PAHs at 24 sampling sites near a heavily industrialized area (steel, chemical, and rubber plants) using passive air samplers during the heating period (7 December 2019 to 15 April 2020) and the non-heating period (2 June 2020 to 4 October 2020). The total average concentrations of 16 BrPAHs, 8 ClPAHs, 17 NPAHs, 6 OPAHs, and 18 PAHs during both sampling periods were 471 pg/m3, 229 pg/m3, 312 pg/m3, 2120 pg/m3, and 63.1 ng/m3, respectively. Except for NPAHs, BrPAHs, ClPAHs, OPAHs, and PAHs all showed higher levels during the heating period. The spatial distributions of Cl/BrPAHs, N/OPAHs, and PAHs exhibited a similar pattern, with the highest concentrations detected in the vicinity of the steel industry. Congener profiles of PAH derivatives indicated that mono-substituted low molecular weight compounds (2-3 rings) were dominant. The major formation mechanisms of halogenated PAHs were discussed by correlation analysis and relative Gibbs free energies, and direct bromination of parent PAHs could be the major formation mechanism of BrPAHs in this study. Diagnostic ratios showed that NPAHs were mainly derived from primary emissions, but the contribution of secondary formation was increased at heavily contaminated sites. The positive matrix factorization model extracted four Cl/BrPAHs, three N/OPAHs, and four PAHs factors, and the result showed that PAHs and their derivatives mainly derived from industrial and combustion sources, photochemical reactions, vehicle emissions, and crude oil volatilization, etc.

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Because most relevant studies have used small sample sizes, to date, representative atmospheric monitoring of persistent organic pollutants (POPs) on a regional scale has been very limited, which makes it difficult to precisely identify "hotspots" and possible pollution sources. In this study, an ultrahigh resolution monitoring technique was used to measure the atmospheric spatial variations in POP concentrations on a regional scale, throughout Campania, Italy. The occurrence of specific POPs-including polychlorinated biphenyls (PCBs), organochlorine pesticides (OCPs), polycyclic aromatic hydrocarbons (PAHs), polybrominated diphenyl ethers (PBDEs) and phthalate esters (PAEs)-were investigated using polyurethane foam-based passive air samplers (PUF-PAS), which were deployed at 129 sites across the Campania Territory between April and July 2016. The results show that the highest POP levels occurred in the Naples metropolitan area (NMA), although there were other problematic spots throughout the Territory. More specifically, hotspot areas in the NMA that depict serious POP pollution were found in the Bagnoli brownfield site, Sarno River Basin, and parts of the northeastern NMA sector. The atmospheric POP contamination in Campania is jointly controlled by the contributions of local emissions and long-range atmospheric transport. Diffusion model was employed to identify the potential sources of various POPs. The simulation showed that all the POP sources are located in the NMA and are closely related to industrial sites. This study demonstrates the advantage of using large sample sizes to identify POP source locations and achieve geospatial visualization of POP concentration and risk assessment levels.

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Recent studies from India reported polychlorinated biphenyls (PCBs) associated with incomplete combustion processes. In this study we have monitored atmospheric PCBs in Agra, a non-metropolitan city of northern India. During first month of summer and winter of 2017, polyurethane foam based passive air sampler (PUF-PAS) was deployed at each of 14 locations across urban, suburban and rural transects and one background site. Range of Σ25PCBs varied between 25 and 1433 pg/m3 (Avg ± Stdev: 460 ± 461) in summer and 26-205 pg/m3 (Avg ± Stdev: 106 ± 59) in winter. Mean Σ25PCBs concentration, showed an urban > suburban > rural trend in summer while, in winter a rural > urban > suburban trend was observed. PCB-52 was the dominant congener and after excluding this congener no significant difference was observed between summer and winter PCB concentrations. Using a combination of K-means cluster and principal component analysis (PCA) four major source types were identified. Open burning source accorded 80% of atmospheric PCBs, majorly indicator PCBs while the remaining 20% was contributed by atmospheric transport, petrogenic combustion and biomass burning. From the ten days back trajectory of the air mass it can be suggested that atmospheric transport from the hotspots resulted in a minor percentage of dioxin like PCBs in Agra. Maximum TEQs was accorded by PCB-77 (30%) and it is consistent with previous observations from Agra. Levels observed in the current study are well within the public health guideline based on inhalation unit risk (10 ng/m3) and United States Environmental Protection Agency's regional screening level high risk tier (4.9 ng/m3) for ambient air.

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Polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers (PBDEs), hexabromobiphenyl (BB-153), novel brominated flame retardants (NBFRs), and unsubstituted/methylated polycyclic aromatic hydrocarbons (PAHs/Me-PAHs) were simultaneously monitored in the air samples collected from Vietnamese urban and vehicular waste processing areas by using polyurethane foam-based passive air sampling (PUF-PAS) method. Concentrations (pg m-3) of organic pollutants decreased in the order: PAHs (median 29,000; range 5100-100,000) > Me-PAHs (6000; 1000-33,000) > PCBs (480; 170-1100) > PBDEs (11; 5.3-86) > NBFRs (0.20; n. d. - 51) > BB-153 (n.d.). The difference in total PCB and PBDE concentrations between the urban and waste processing air samples was not statistically significant. Meanwhile, levels of PAHs, Me-PAHs, benzo [a]pyrene equivalents (BaP-EQs), and toxic equivalents of dioxin-like PCBs (WHO-TEQs) were much higher in the waste processing sites. This is the first report on the abundance of mono- and di-CBs (notably CB-11) in the air from a developing country, suggesting their roles as emerging and ubiquitous air pollutants. Our results have indicated potential sources of specific organic pollutants such as dioxin-like PCBs, PAHs, and Me-PAHs from improper treatment of end-of-life vehicles and other vehicle related materials (e.g., waste oils and rubber tires), as well as current emission of PCBs and PBDEs in the urban area in Vietnam. Further atmospheric monitoring studies should be conducted in this developing country that cover both legacy and emerging contaminants with a focus on areas affected by rapid urbanization and informal waste processing activities.

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Some halogenated polycyclic aromatic hydrocarbons (Halo-PAHs) are known to be more toxic than their corresponding parent PAHs, but studies on Halo-PAHs have been somewhat limited. In this study, passive air samplers were used to monitor Halo-PAH and PAH contamination at 20 sampling sites in Ulsan, one of the largest industrial cities in South Korea. The mean concentrations of Σ24 ClPAHs, Σ11 BrPAHs, and Σ13 PAHs were 207 pg/m3, 84 pg/m3, and 26 ng/m3, respectively. Industrial areas displayed higher concentrations of both Halo-PAHs and PAHs than urban and rural areas. Strong correlations between energetically unfavorable Halo-PAHs and their corresponding parent PAHs suggest that the main formation mechanism of Halo-PAHs is not direct halogenation of PAHs. Low molecular weight Halo-PAHs with one halogen atom and their parent PAHs were dominant. The profiles of ClPAHs and BrPAHs in petrochemical, automobile, shipbuilding, and non-ferrous industrial complexes were distinguished. The toxicity equivalency quantities (TEQs) of ClPAHs, BrPAHs, and PAHs at the industrial sites also showed the highest values of 4.2, 0.5, and 18.3 pg-TEQ/m3, respectively, reflecting the high toxicity of Halo-PAHs. To the best of our knowledge, this is the first study reporting atmospheric levels of both ClPAHs and BrPAHs using passive air samplers.

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Polyurethane foam (PUF) disks in passive air samplers (PAS) and passive dry deposition (Pas-DD) collectors were used to assess the presence of persistent organic pollutants (POPs) and current-use pesticides (CUPs) in a rural area of central Chile (Peumo, VI Region). The samplers were exposed from September 2015 (spring) to March 2016 (summer), with the PUFs collected at intervals of 30, 60, and 90 days. Both samplers (PUF-PAS and Pas-DD) captured more than one pesticide per sampling period. Chlorpyrifos-ethyl and pyrimethanil presented the highest air concentration with PUF-PAS (3470.2 ng m-3 for chlorpyrifos-ethyl and 52.8 ng m-3 for pyrimethanil). The deposited amount of chlorpyrifos-ethyl, pyrimethanil, penconazole, diazinon and malathion in some Pas-DD, was superior to amount of pesticides captured by PUF-PAS. Differences between the amount deposited and captured by each sampler should be studied in greater detail, because wind speed, atmospheric particulate matter size and sampler design are some fundamental variables in this process. These results provide preliminary information on the presence of current-use pesticides in the atmosphere of Peumo, VI Region, serving as a foundation for future environmental monitoring programs.

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Of 942 organic micro-pollutants screened, 167 compounds were detected at least once in the atmosphere in some primitive waste processing sites and an urban area in northern Vietnam by using a polyurethane foam-based passive air sampling (PUF-PAS) method and an Automated Identification and Quantification System with a Database (AIQS-DB) for GC-MS. Total concentrations of organic pollutants were higher in samples collected from an urban area of Hanoi city (2300-2600 ng m-3) as compared with those from an end-of-life vehicle (ELV) dismantling area in Bac Giang (900-1700 ng m-3) and a waste recycling cooperative in Thai Nguyen (870-1300 ng m-3). Domestic chemicals (e.g., n-alkanes, phthalate ester plasticizers, and synthetic phenolic antioxidants) dominated the organic pollutant patterns in all the samples, especially in the urban area. Pesticides (e.g., permethrins, chlorpyrifos, and propiconazole) were found in the atmosphere around the ELV sites at more elevated concentrations than the other areas. Levels of polycyclic aromatic hydrocarbons and their derivatives in the Bac Giang and Thai Nguyen facilities were significantly higher than those measured in Hanoi urban houses, probably due to the waste processing activities. Daily intake doses of organic pollutants via inhalation were estimated for waste processing workers and urban residents. This study shall provide preliminary data on the environmental occurrence, potential emission sources, and effects of multiple classes of organic pollutants in urban and waste processing areas in northern Vietnam.

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Time series (2008-2015) of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) and dioxin-like polychlorinated biphenyls (dl-PCBs) in ambient air from the Spanish Monitoring Program were analyzed. A total of 321 samples were collected seasonally each year in 5 urban and 7 background sites by means of passive air sampling. Air concentrations were higher at urban than background sites (urban vs. background concentration ranges): PCDD/Fs (26.9-1010 vs. 20.0-357 fg/m3), non-ortho PCBs (0.113-3.14 vs. 0.042-2.00 pg/m3) and mono-ortho PCBs (0.644-41.3 vs. 0.500-32.8 pg/m3). Results showed significant decreases from 2009 for non-ortho PCBs and PCDD/Fs as well as for WHO2006-TEQs. These declines were sharper, and sometimes only significant, in urban places resulting in converging levels at urban and background sites for these pollutants at the end of the study period. In contrast, mono-ortho PCBs did not show any significant variation but a steady flat temporal behavior in their concentrations, suggesting the existence of different sources between mono-ortho and non-ortho PCBs. Seasonality was observed for air burdens of all these POPs. PCDD/Fs were mostly measured at higher concentrations in colder than in hot seasons, and the opposite was true for dl-PCBs. Seasonal variations for PCDD/Fs appeared to be related to changes in their sources (e.g. domestic heating, open burning) rather than to temperature per se. In contrast, environmental temperature dependent factors (e.g. increased partitioning into the gas phase) drove seasonal variations in dl-PCBs instead of seasonal changes in their sources. Regarding spatial patterns, significant greater levels of PCDD/Fs and dl-PCBs were generally found in cities compared to background areas, pointing out the role of densely populated areas as sources for these pollutants in Spain. As proven by our results, long-term monitoring activities are essential to assess and understand temporal behaviors for these POPs, as well as to evaluate the achievement of Stockholm Convention objectives.

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The Stockholm Convention (SC) on Persistent Organic Pollutants (POPs) calls for the Parties' effectiveness evaluation of those measures taken to meet the reduction and eventual elimination of POPs from the environment. With that goal, air concentrations of different POP families have been measured uninterruptedly since 2008 under the Spanish Monitoring Program (SMP) by means of passive air sampling. This work focuses on data for polybrominated diphenyl ethers (PBDEs) determined in a total of 321 samples collected seasonally each year in 5 urban and 7 background sites. Neither significant temporal trends nor significant seasonal variations for total PBDE air burdens were detected. In contrast, significant variations were found among PBDE congeners. Those related to the octa-PBDE formulation significantly decreased in the study period. However, PBDEs related to the penta-formulation showed steady concentrations while PBDE-209, the congener found at the greatest levels, showed increasing or steady levels in most sampling sites. Seasonal variations were also markedly different among congeners. Concentrations of the lightest PBDEs (tri- to penta-substituted) were highly influenced by ambient temperature (T), showing maximum values in summer probably due to higher volatilization rates compared to those of heavier PBDEs. Contrarily, no clear seasonal trends were found for hexa- to deca-PBDEs, which were negatively related to precipitation; thereby, indicating an efficient atmospheric wash out by wet deposition episodes. Regarding spatial patterns, overall significant greater PBDE levels were found in cities compared to background areas, pointing out the role of highly populated areas as sources for these pollutants in Spain. Yet and especially in the case of PBDE-209, our results suggested the presence of significant unknown sources of PBDEs in some background sites. Further monitoring efforts are needed to assess potential unknown sources in the sampling network as well as to ensure temporal trends of these pollutants in Spain.

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Organophosphorus pesticides are some of the most widely used insecticides in the US, and spray drift may result in human exposures. We investigate sampling methodologies using the polyurethane foam passive air sampling device to measure cumulative monthly airborne concentrations of OP pesticides chlorpyrifos, azinphos-methyl, and oxygen analogs. Passive sampling rates (m(3)d(-1)) were determined using calculations using chemical properties, loss of depuration compounds, and calibration with side-by-side active air sampling in a dynamic laboratory exposure chamber and in the field. The effects of temperature, relative humidity, and wind velocity on outdoor sampling rates were examined at 23 sites in Yakima Valley, Washington. Indoor sampling rates were significantly lower than outdoors. Outdoor rates significantly increased with average wind velocity, with high rates (>4m(3)d(-1)) observed above 8ms(-1). In exposure chamber studies, very little oxygen analog was observed on the PUF-PAS, yet substantial amounts chlorpyrifos-oxon and azinphos methyl oxon were measured in outdoor samples. PUF-PAS is a practical and useful alternative to AAS because it results in little artificial transformation to the oxygen analog during sampling, it provides cumulative exposure estimates, and the measured sampling rates were comparable to rates for other SVOCs. It is ideal for community based participatory research due to low subject burden and simple deployment in remote areas.

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