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Nitrated and oxygenated polycyclic aromatic hydrocarbons (NPAHs and OPAHs) are receiving attention because of their high toxicity compared with parent PAHs. However, the experimental data of their physicochemical properties has been limited. This study proposed the gas chromatographic retention time (GC-RT) technique as an effective alternative one to determine octanol-air partition coefficients (K OA ) and sub-cooled liquid vapor pressures (P L ) for 11 NPAHs, 10 OPAHs, and 19 parent PAHs. The slopes and intercepts of the linear regressions between temperature versus K OA and P L were provided and can be used to estimate K OA and P L for the 40 targeted compounds at any temperature. The internal energies of phase transfer (ΔU OA ) and enthalpies of vaporization (ΔH L ) for all targeted compounds were also calculated using the GC-RT technique. High-molecular-weight compounds may release or absorb higher heat energy to transform between different phases. NPAHs and OPAHs had a non-ideal solution behavior with activity in octanol (γ oct ) in the range of 19-53 and 18-1,078, respectively, which is larger than the unity threshold. A comparison among four groups of PAH derivatives showed that a functional group (nitro-, oxygen-, chloro-, and bromo-) in PAH derivatives increased γ oct for corresponding parent PAHs by tens (mono-group) to hundreds of times (di-group). This study suggests that the GC-RT method is applicable for indirectly measuring the physicochemical properties of various groups of organic compounds., (Copyright © 2021 Elsevier Ltd. All rights reserved.)

This study identifies the emission source areas for the atmospheric polycyclic aromatic hydrocarbons (PAHs) detected in Ulsan, South Korea. To achieve this, in addition to a conditional bivariate probability function (CBPF), two hybrid receptor models - the three-dimensional potential source contribution function (3D-PSCF) model and the 3D concentration weighted function (3D-CWT) model - were used, both of which adopt trajectory segments within the mixing layer. Notably, the fraction-weighted trajectory (FWT), a combination of PAH gas/particle partitioning with a hybrid receptor model, was introduced for the first time in this study to support the identification of emission source areas using other approaches ( i.e. , 3D-PSCF, 3D-CWT, and CBPF). Consequently, it was found that gaseous PAHs in Ulsan mostly originated from local emission sources ( i.e. , transportation and industrial emissions) throughout the year, whereas particulate PAHs were likely to originate from emission sources in China ( e.g. , Shandong, Hebei, and Liaoning) during spring and winter via long-range transport. However, in summer and fall, the influence of local emissions on particulate PAHs appeared to be stronger. The FWT was able to distinguish between local and distant sources more effectively, especially in summer and fall, i.e. , the periods when local sources increased their contribution. This study thus increases the understanding of the long-range transport of PAHs in Northeast Asia, and the novel FWT approach exhibits the potential to be employed in the source area identification of various semi-volatile organic chemicals.

Atmospheric halogenated polycyclic aromatic hydrocarbons (Halo-PAHs) and parent PAHs were monitored in Ulsan, South Korea for one year (January‒December 2015) to investigate their seasonal patterns, gas/particle partitioning behavior, and the impact of meteorological conditions. The mean concentrations of 24 chlorinated PAHs, 11 brominated PAHs, and 13 parent PAHs in the gaseous and particulate phases were 8.64 and 9.64 pg/m 3 , 11.6 and 1.62 pg/m 3 , and 2.17 and 2.40 ng/m 3 , respectively. Winter had the highest ClPAH and PAH levels, with significant contributions from poly-chlorine groups and high-molecular-weight compounds. However, BrPAHs showed reverse patterns with the highest concentration in summer and the dominant gaseous fraction throughout the year. This finding could be explained by the strong local sources of BrPAHs, related to automobile and petrochemical industries. In contrast, the effects of the temperature inversion layer and atmospheric transport from the outside of Ulsan were more apparent for ClPAHs and PAHs, particularly in winter and spring. Regarding gas/particle partitioning, Halo-PAHs exhibited different seasonal behaviors from those of parent PAHs. The sorption pathway of Halo-PAHs seemed to shift from absorption as the sole dominant mechanism in winter and spring to both adsorption and absorption in summer and fall, while both partitioning mechanisms contributed equally for parent PAHs during the entire year. This study implies that Halo-PAHs and parent PAHs might not share the same atmospheric behavior, possibly due to different characteristics in atmospheric reactions with other chemicals and particle-size distribution. However, there have been limited studies about the formation of Halo-PAHs and their physicochemical properties; hence, further in-depth investigations are of vital importance., 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 Elsevier Ltd. All rights reserved.)

Particulate matter (PM) in 11 different sizes was collected at a semi-rural site in Ulsan, a multi-industrial city in South Korea, over one year from 2019 to 2020 to investigate the temporal patterns in size distribution and potential sources of polycyclic aromatic hydrocarbons (PAHs). The mean concentration of Σ 21 PAHs was higher in winter (0.29 and 0.45 ng/m3 for coarse and fine PM, respectively) than in summer (0.06 and 0.07 ng/m3). Although there was no statistically significant difference between day and night for the concentration of individual PAHs in both coarse and fine PM, the concentrations were generally higher during the day than at night. During the day, Σ 21 PAHs had two distinct peaks (0.056–0.10 μm and 3.20–5.60 μm) in winter, but they tended to partition to larger particles (1.00–1.80 μm and >18.0 μm) in summer. This result suggests that the volatilization of PAHs in smaller particles was enhanced by high-temperature conditions in summer, followed by their condensation onto larger particles. At night, Σ 21 PAH peaks were mainly around the size of 0.7 μm (droplet mode), suggesting the importance of heterogeneous-aqueous reactions. The results of the conditional bivariate probability function and concentration-weighted trajectory indicate that the high concentrations of PAHs in summer and winter were more affected by local pollution and long-range atmospheric transport, respectively. The results of the health risk assessment demonstrate that PAHs in fine PM contributed significantly to cancer risk compared to those in coarse PM. In conclusion, investigating the size distribution of PAHs in particles is necessary to understand their environmental behaviors and evaluate potential health risks. [Display omitted] • Polycyclic aromatic hydrocarbons (PAHs) were higher during the day than at night. • Day–night variation in the particle-size distribution of PAHs was apparent. • Long-range atmospheric transport became more significant in winter. • The concentration of PAHs in summer was more affected by local pollution. • Fine particles had a higher cancer risk of PAHs than coarse particles. [ABSTRACT FROM AUTHOR]

Polycyclic aromatic hydrocarbons (PAHs) are primarily emitted into the atmosphere through anthropogenic activities and can be transported to receptor sites at varying distances. In this study, the atmospheric PAH deposition was investigated using a dry deposition plate (DDP) with Mylar, a dry deposition disk (DDD) with Velcro, a resin bulk deposition sampler (Resin-BDS), and a water bulk deposition sampler (Water-BDS) in Ulsan, South Korea, during May–October 2013. Additionally, ambient PAH concentrations were monitored using high-volume air samplers. The mean deposition fluxes of Σ 13 PAHs were 8.62 ± 1.44, 36.9 ± 6.81, 56.9 ± 9.74, and 63.8 ± 8.04 μg/m2/d for the DDP, DDD, Resin-BDS, and Water-BDS, respectively. The DDD was more effective than the DDP because it could collect high molecular weight (HMW) PAHs from dry deposition, which are more toxic than low molecular weight PAHs. The Water-BDS had the highest fluxes of Σ 13 PAHs; however, the Resin-BDS may be more suitable for collecting HMW PAHs from both dry and wet deposition due to relatively constant values for the deposition velocity of PAHs. Furthermore, the PAH fluxes in the Resin-BDS samples were significantly positively correlated with the gaseous and total (gaseous + particulate) concentrations of ambient PAHs. Hence, the fluxes obtained by the Resin-BDS were further used to apply principal component analysis, multiple linear regression, and backward air trajectory simultaneously to identify the emission sources of the deposited PAHs. The results indicate that the combustion of fossil fuels and biomass was the major source. In particular, the industrial complexes using petroleum and coal on the city's east coast and vehicular exhausts were the main local sources. Meanwhile, long-range sources may be forest fires, harbors, and industrial activities in nearby countries. Our study suggests that BDS, considering both dry and wet deposition, can be selectively used for research on PAH deposition. [Display omitted] • The performance of four deposition samplers for ambient PAHs was evaluated. • Dry samplers using Mylar and Velcro collected mostly coarse particle-bound PAHs. • The water and resin bulk samplers were suitable to study both dry and wet deposition. • The resin bulk sampler collected more toxic PAHs with a constant deposition velocity. • The burning of fossil fuels and biomass was a major source of the deposited PAHs. [ABSTRACT FROM AUTHOR]

Chlorinated and brominated polycyclic aromatic hydrocarbons (ClPAHs and BrPAHs, respectively) are a new derivative group of PAHs. These halogenated PAHs (Halo-PAHs) have been reported to be carcinogenic and are considered emerging persistent organic pollutants. Gaining a clear understanding of the distribution and behavior of these ubiquitous organic pollutants is essential for the control and mitigation of their emission into the environment. However, research into the characteristics of Halo-PAHs in the atmosphere has been somewhat limited. This review paper thus aims to provide an overview of the seasonal patterns, profiles, potential sources, and particle-size distributions of atmospheric ClPAHs and BrPAHs with 3–5 rings. Most previous studies have focused on particulate Halo-PAHs and reported that their levels are higher during the cold season than during the warm season, with this seasonal variation more apparent for ClPAHs than for BrPAHs. In terms of their phase distribution, ClPAHs and BrPAHs share a similar trend, with their gaseous concentrations highest in summer and lowest in winter and their particulate concentrations exhibiting the opposite trend. Halo-PAH profiles have been shown to differ between sampling locations, possibly reflecting differences in the potential sources present at these sites, e.g., coal burning, traffic emissions, and industrial activity. The majority of Halo-PAHs tend to accumulate as ultrafine particles with an aerodynamic diameter of less than 1.0 µm. Overall, a detailed understanding of the characteristics of Halo-PAHs in the atmosphere has yet to be achieved; hence, further research on atmospheric Halo-PAHs is necessary. [ABSTRACT FROM AUTHOR]

Halogenated polycyclic aromatic hydrocarbons (Halo-PAHs) are a new group of PAH derivatives and are reported to be more toxic than their parent PAHs. However, limited research has been undertaken on their physicochemical properties. In this study, sub-cooled liquid vapor pressures (P L) and octanol–air partition coefficients (K OA) of 24 chlorinated and 11 brominated PAHs (ClPAHs and BrPAHs) were determined using the gas chromatographic retention time (GC-RT) technique. The temperature dependences of P L and K OA for the Halo-PAHs were determined by the slopes and intercepts of the linear regressions. The GC-RT method also provided the enthalpies of vaporization (Δ H L) and internal energies of phase transfer (Δ U OA) for all interested compounds. The activity of Halo-PAHs in octanol (γ oct) ranging from 18 to 87, indicated the non-ideal solution behavior. The number of the chlorine atoms in the PAH rings could influence the interaction of ClPAHs with the organic matter, whereas this interaction for BrPAHs could not be studied due to the limited number of target BrPAHs. The measured values of P L and K OA were applied to investigate the gas/particle partition behaviors of Halo-PAHs in Ulsan, South Korea. This study is so far the first one to report the linear regression coefficients, which can be used to estimate the P L and K OA values of Halo-PAHs at any temperature. Image 1 • P L and K OA for Halo-PAHs were determined using the GC-RT method. • The values of P L and K OA for Halo-PAHs were correlated with molecular weights. • A range of γ oct (18–87) for Halo-PAHs indicated the non-ideal solution behavior. • The number of chlorines influenced the interaction of ClPAHs with organic matter. • The values of P L and K OA were applied to investigate the G/P partitioning behaviors. [ABSTRACT FROM AUTHOR]

• Halo-PAHs and PAHs were monitored in Ulsan, Korea using passive air samplers. • Compound- and site-specific sampling rates were estimated using a prediction model. • High-resolution spatial distribution maps of Halo-PAHs and PAHs were produced. • The profiles of Halo-PAHs in four major industrial complexes were distinguished. • The direct halogenation of PAHs was not the main formation mechanism of Halo-PAHs. 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 Σ 24 ClPAHs, Σ 11 BrPAHs, and Σ 13 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. [ABSTRACT FROM AUTHOR]

Seoul, the capital of South Korea, is one of the largest megacities in northeast Asia. Previous studies have monitored atmospheric polycyclic aromatic hydrocarbons (PAHs) in Seoul, but few have produced highly spatially resolved data. In this study, a total of 144 polyurethane foam-passive air samplers (PUF-PASs) were deployed at 36 sites (4 road, 26 urban, and 6 background sites) in Seoul during the summer of 2016 and the winter of 2017. The concentrations of Σ 13 PAHs fell within a range of 2.6–49.9 ng/m3 in summer and 15.5–77.8 ng/m3 in winter. Low-molecular-weight PAHs with 3–4 rings were dominant (accounting for about 97% of all PAHs) at all sampling sites in both seasons compared to high-molecular-weight PAHs with 5–6 rings. Phenanthrene was the most abundant individual compound, accounting for 35–54% and 42–52% of the total PAHs in summer and winter, respectively. The spatial distribution of PAHs was determined by traffic, domestic heating, topography, transport, and meteorological conditions. The concentration of PAHs at the road sites was higher than at the urban and background sites, indicating that vehicular exhaust was a major source in both seasons. In addition, diagnostic ratios and principal component analysis revealed the influence of various sources, such as gasoline and diesel emissions and coal and biomass combustion. Backward air trajectory analysis highlighted the influence of long-range transport from northern China and North Korea during the winter, whereas the influence of local emissions and satellite cities appeared to dominate during the summer. In conclusion, passive air sampling was successfully employed to identify major sources of PAHs in an Asian megacity, indicating that it could produce data with a high spatial resolution for use in human risk assessment and air monitoring networks. • Passive air sampling was conducted at 36 sites in Seoul, Korea in summer and winter. • The mean concentration of PAHs in winter was higher than that in summer. • Road sites exhibited higher levels of PAHs than urban and background sites. • The influence of long-range transport was evident during the winter. • The influence of local emissions and satellite cities was dominant during the summer. [ABSTRACT FROM AUTHOR]