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The concentration of polycyclic aromatic hydrocarbons (PAHs) in the atmosphere has been continually monitored since their toxicity became known, whereas nitro-PAHs (NPAHs) and oxy-PAHs (OPAHs), which are derivatives of PAHs by primary emissions or secondary formations in the atmosphere, have gained attention more recently. In this study, a method for the quantification of 18 NPAH and OPAH congeners in the atmosphere based on combined applications of gas chromatography coupled with chemical ionization mass spectrometry is presented. A high sensitivity and selectivity for the quantification of individual NPAH and OPAH congeners without sample preparations from the extract of aerosol samples were achieved using negative chemical ionization (NCI/MS) or positive chemical ionization tandem mass spectrometry (PCI-MS/MS). This analytical method was validated and applied to the aerosol samples collected from three regions in Northeast Asia—namely, Noto, Seoul, and Ulaanbaatar—from 15 December 2020 to 17 January 2021. The ranges of the method detection limits (MDLs) of the NPAHs and OPAHs for the analytical method were from 0.272 to 3.494 pg/m3 and 0.977 to 13.345 pg/m3, respectively. Among the three regions, Ulaanbaatar had the highest total mean concentration of NPAHs and OPAHs at 313.803 ± 176.349 ng/m3. The contribution of individual NPAHs and OPAHs in the total concentration differed according to the regional emission characteristics. As a result of the aerosol samples when the developed method was applied, the concentrations of NPAHs and OPAHs were quantified in the ranges of 0.016~3.659 ng/m3 and 0.002~201.704 ng/m3, respectively. It was concluded that the method could be utilized for the quantification of NPAHs and OPAHs over a wide concentration range. [ABSTRACT FROM AUTHOR]

Oxygenated polycyclic aromatic hydrocarbons (OPAHs) are of increasing interest due to their high toxicity. Thirteen particulate PAHs and ten particulate OPAHs were analyzed by Gas Chromatography/Mass Spectrometry (GC/MS) in atmospheric particulate matter with aerodynamic diameters less than or equal to a nominal 2.5 μm (PM 2.5) for the period between May 2020 and January 2021 in Seoul, Republic of Korea. The mean concentration ten OPAHs (5.49 ± 2.40 ng/m3) was higher than that of thirteen PAHs (3.96 ± 3.36 ng/m3), respectively. The concentration of total OPAHs was high in winter (9.40 ± 2.50 ng/m3) and low in summer (3.58 ± 0.78 ng/m3), showing the same trend with PAHs (9.16 ± 3.30 ng/m3 in winter and 0.62 ± 0.15 ng/m3 in summer). When comparing this study results with the measurement results on 2006 in Seoul, PAHs concentration dropped by 68% while only 22% was reduced for OPAHs. It suggests either improvement of combustion technology, i.e., high temperature combustion process in the region or higher ambient oxidation reaction rates on 2020 than 2006. Major sources and their contributions of PAHs and OPAHs were identified based on correlation analysis and Positive Matrix Factorization (PMF) modeling. Two cases were carried. Case 1 is for source apportionment for PM 2.5 and case 2 is for OPAHs and PAHs. The number of factors or sources in the two cases was determined as 7 and 4, respectively. The results of the PMF modeling using diagnostic ratios (DRs) in case 1 identified 7 factors; secondary nitrate (23%), secondary sulfate (21%), vehicles (20%), biomass burning (16%), coal combustion (12%), waste incineration (5%), and OPAHs (5,12-NAQ) emission-related (3%). The PMF modeling results in case 2 revealed 4 factors; vehicles (36%), coal combustion (30%), biomass burning (25%), and OPAHs (5,12-NAQ) emission related (9%). Significant correlation between OPAHs and indicators of primary emission sources, and high contribution from sources with emission characteristics implied that most sources of OPAHs were heavily influenced by primary emissions rather than secondary formation. • 13 particulate PAHs and 10 OPAHs were analyzed in Seoul, Korea for four seasons. • The mean concentration of 10 OPAHs was higher than that of 13 PAHs. • OPAHs were heavily influenced by primary emissions rather than secondary formation. • OPAHs reduction ratios were lower than PAHs from 2006 to 2020. [ABSTRACT FROM AUTHOR]

The contribution of ozonation to the formation of particulate nitrosodi-methylamine (NDMA) in the aqueous aerosol phase was investigated using measurement data from 2018 in Seoul, Republic of Korea and a box model. The correlation between the NDMA concentration and aerosol liquid water content and box model results showed that aqueous aerosol phase reactions, including nitrosation and ozonation, might contribute to the formation of NDMA. The concentration of NDMA and the ratio of O 3 /dimethylamine exhibited a negative correlation, suggesting that the contribution of ozonation to NDMA formation may not be significant. Furthermore, when the daily concentration of NDMA exceeded 10 ng/m3, the pH was 3.96 ± 0.48, indicating that the impact of ozonation on NDMA concentration might not be significant. To quantitatively investigate the contribution of ozonation, the ozonation mechanism that forms NDMA was included in the box model developed in our previous study. The model results showed that the ozonation contributed to the ambient concentration of NDMA (7.9 ± 3.8% (winter); 1.9 ± 3.0% (spring); 10.0 ± 0.77% (summer); 3.6 ± 7.3% (autumn)). It is estimated that the relatively higher O 3 /NO x ratio in summer (1.63 ± 0.69; 0.64 ± 0.52 (winter); 1.14 ± 0.92 (spring); 0.52 ± 0.54 (autumn)) could enhance ozonation and that relatively lower pH in summer (2.2 ± 0.4; 5.3 ± 1.2 (winter); 3.9 ± 1.2 (spring); 3.9 ± 0.7 (autumn)) could hinder nitrosation compared to that in other seasons. [Display omitted] • Ozonation could be a hidden reaction forming NDMA in the atmosphere. • Ozonation contributed to NDMA formation but the impact was less than nitrosation. • Relatively higher O 3 /NO x and lower pH could contribute ozonation in summer. [ABSTRACT FROM AUTHOR]

Aromatic volatile organic compounds (VOCs) including benzene, toluene, ethylbenzene, xylene, and trimethylbenzene (BTEX) are known to contribute the most to the formation of ozone and secondary organic aerosols (SOA) in an urban atmosphere and their representation in chemical transport models (CTM) is still uncertain. In this study, we evaluated the model representation of BTEX concentrations and their seasonal difference at Beijing and Seoul using the GEOS-Chem CTM and ground observations from the Fine particle Research Initiative in East Asia considering National Differences (FRIEND) project in winter and summer. The model captured different levels of observed BTEX at Beijing and Seoul, where benzene (BENZ) was comparable and toluene + ethylbenzene (TOLU) and xylenes + trimethylbenzenes (XYLE) were higher at Seoul. The observed seasonal variations of BTEX were similar at both sites, with benzene being higher in winter and TOLU and XYLE being higher in summer. However, the magnitude and seasonal variation of TOLU at Seoul and BENZ at Beijing were not reproduced by the model. TOLU was underestimated in both seasons at Seoul especially in summer due to the underestimation of emission rates and evaporative emission being not included in the current emission inventory. At Beijing, BENZ was underestimated especially in winter and showed no seasonal variation which was different from the observations. Underestimated benzene emission rates or missing sources of it cause discrepancies between observed and modeled benzene concentrations at Beijing. • The observed toluene and xylenes were higher in summer while benzene was higher in winter at Beijing and Seoul. • The evaporative emission of toluene at Seoul needs to be considered in the model to reproduce the observed seasonal variation of toluene. • Benzene concentration at Beijing is underestimated likely due to a low bias in emissions from Beijing's own or upwind region. [ABSTRACT FROM AUTHOR]